CA2217541A1 - Biologically degradable polymer mixture - Google Patents
Biologically degradable polymer mixture Download PDFInfo
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- CA2217541A1 CA2217541A1 CA002217541A CA2217541A CA2217541A1 CA 2217541 A1 CA2217541 A1 CA 2217541A1 CA 002217541 A CA002217541 A CA 002217541A CA 2217541 A CA2217541 A CA 2217541A CA 2217541 A1 CA2217541 A1 CA 2217541A1
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- Prior art keywords
- polymer mixture
- acid
- mixture according
- polyester
- starch
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
- C08L3/02—Starch; Degradation products thereof, e.g. dextrin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2003/00—Use of starch or derivatives as moulding material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
- C08L67/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl- and the hydroxy groups directly linked to aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/06—Polyurethanes from polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/12—Polyester-amides
Abstract
A biologically degradable polymer mixture contains at least one biopolymer made from renewable raw materials and a polymer selected from the following materials: an aromatic polyester; a polyester-copolymer with both aliphatic and aromatic blocks; a polyester amide; a polyglycol; a polyester urethane;
and/or mixtures of these components.
and/or mixtures of these components.
Description
CA 02217~41 1997-10-06 siologically degradable polymer mixture The present invention relates to a biologically degradable polymer mixture, to a process for its preparation and to a method of processing the polymer mixture according to the invention.
Proposals for the preparation of biologically degradable polymer mixtures are known from a large number of patent documents and articles. The great problem in the case of polymer mixtures lies, as a rule, in that those mixtures which have an excellent, biological degradability have only limited possibilities for use in the area of engineering plastics, thereby explaining the relatively modest success to date. Polymer mixtures having improved properties are either biologically inadequate or degradable with increased effort, or else are too expensive.
From EP-535 994 a polymer mixture is known essentially consisting of starch and an aliphatic polyester, for example polycaprolactone, where the starch is preferably destructured with water.
Moreover, in an article in the journal "Starke", volume 45, No. 9, September 1, 1993, Weinheim, pages 314 to 322, the use ~ENDED SHEET
IPEA/EP
CA 02217~41 1997-10-06 - la -of starch in the modification of synthetic plastics is described. Here it is proposed first of all to gelatinize the starch by means of water, in connection with which it is mentioned that this gelatinization takes place by means of an endothermic process. This makes it obvious that the gelatinized starch mentioned must be destructured starch, which is mixed with a range of synthetic plastics in order to develop new composite materials.
In contrast, and in knowledge of the inadequacies of starch destructured with water, it is proposed in DE-42 37 535 for a biologically degradable polymer mixture to use thermoplastic starch which is prepared with the exclusion of water and using a suitable plasticizing agent. The proposed polymer mixtures contain thermoplastic starch, a hydrophobic polymer and a phase mediator, thermoplastic starch with polycaprolactone being proposed as preferred mixture.
AMENDED SHEET
IPEA/EP
CA 02217~41 1997-10-06 Aliphatic polyesters are, per se, suitable mixing components for the preparation of biologically degradable polymer mixtures, since they have a good biological degradability.
However, aliphatic polyesters have only moderate material properties, for example with regard to melting point, tensile strength, etc., which is why even corresponding mixtures using a polymer prepared on the basis of renewable raw materials, for example thermoplastic starch, have only moderate properties, thereby again placing in question the possibility for use in the field of engineering plastics.
It is therefore an object of the present invention to propose a biologically degradable polymer mixture which both is flawlessly degradable biologically and in addition has good mechanical and thermal properties, so that use as an engineering plastic or as a polymer material is appropriate.
A further prerequisite for suitability as a polymer material also lies in the price for the polymer mixture proposed in CA 02217~41 1997-10-06 accordance with object having an acceptable magnitude.
In accordance with the invention the object proposed above is achieved by means of a biologically degradable polymer mixture in accordance with the wording of claim 1.
The multitude of biopolymers or biologically degradable ~ _ _ e CA 02217~41 1997-10-06 -3a-extent constructed on the basis of starch or use starch, although native starch is hardly suitable as a technically usable polymer. Starch is proposed because it is readily degradable biologically, has a favorable price and is independent of petroleum products because it is based on a renewable raw material. Because of the poor suitability of native starch as an "engineering plastic" it is proposed according to the invention to use so-called thermoplastic starch, as is proposed, for example, in PCT/WO90/05161. This thermoplastic starch is obtained by processing native starch in the melt, by means of a plasticizing or swelling agent, to a homogeneous mass, where the proportion of swelling or plasticizing agent can as a rule amount to between 10 and about 40~, based on the overall weight of the mixture. As set out in claim 2, suitable swell-ing or plasticizing agents are, inter alia, for example, glycerol or sorbitol.
Because of the in any case limited properties of thermoplas-tic starch for use in polymer materials it is now proposed according to the invention to mix said starch with at least one further polymer, such as with an aromatic polyester, with a polyester copolymer, the polyester copolymer being prepared from customary diols and from aromatic and aliphatic dicarboxylic acids, with a polyesteramide, a polyethylene oxide polymer or a polyglycol, a polyesterurethane and/or mixtures thereof. The polymer classes of the diverse poly-esters and copolyesters or polyglycols have proven in AMENDED SHEET
IPEA/EP
CA 02217~41 1997-10-06 particular to be suitable materials for improving the rather moderate material properties of thermoplastic starch. The aliphatic polyesters proposed in the prior art, which although having good biological degradability are not particularly suitable because of their likewise moderate material properties with regard to melting point and draw-ability, themselves contribute to an improvement in the material properties of the thermoplastic starch. In contrast, aromatic polyesters exhibit excellent material properties but their biological degradability is rather moderate. On the other hand, inter alia, polyester copolymers based on aromatic and aliphatic dicarboxylic acids, polyesteramides and also polyesterurethanes have both outstanding material properties and a rapid biological degradability, which is why Chey 1/
' - CA 0 2 2 1 i ~ 4 1 1 9 9 7 - 1 0 - 0 6 - r _ with thermoplastic starch.
The polyester copolymers proposed for use in accordance with the invention in the polymer mixture with thermoplastic starch are constructed on the basis, besides the customarily used polyols, of aromatic and aliphatic dicarboxylic acids, and have the following general structure:
O O O O
HO (CX2)x-O-~ cH2)y~~~~ (CH2)x-O ~ ~ (CH2)X-OH
1 - n The polyester copolymers proposed according to the invention can be prepared from petrochemical mass products, such as adipic acid, sebacic acid, terephthalic acid and a diol by means of polycondensation, with commercially customary diols, such as 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol and/or 1,6-hexanediol being used. What is important is that both aromatic and aliphatic dicarboxylic acids are u~ed, by means of which the statistical polyester copolymers are prepared, for example by means of a conventional polyconden-sation process.
Statistical copolyesters of aliphatic and aromatic dicar-boxylic acids with a proportion, for example, of about 35 -CA 02217~41 1997-10-06 55 mol% of aromatic acid, for example terephthalic acid, represent an optimum compromise between biological degradab-ility and material properties, as a result of which they are particularly suitable in mixtures with thermoplastic starch.
The biological degradability of statistical copolyesters of this kind lies within 8 - 12 weeks in compost and earth. In this context reference may be made to US Patent 5 446 079, in which the preparation of aliphatic-aromatic copolyesters is described in detail.
Polyalkylene terephthalates and polyethylene terephthalates which are prepared from aliphatic diols and aromatic dicar-boxylic acids have proven, for example, to be suitable co-polyesters for the preparation of a starch/polyester copoly-mer blend according to the invention.
In addition to the starch/polyester copolymer blends described above and proposed according to the invention it has become evident that polyesteramides filled or blended with starch or thermoplastic starch and with ester contents of between 30 and 70% by weight have good mechanical proper-ties, even for the production of films, and have good degradability and compostibility. Proposed are, for example, polyesteramides having a mean molecular weight in a range of 10 - 30a,000, preferably 20 - 150,000. Otherwise reference CA 02217~41 1997-10-06 may be made to the European patent application EP-A-641 817, in which the synthesis of the polyesteramides proposed in accordance with the invention is described in detail. Mention should merely be made that polyesteramides according to the invention can be constructed from monomers of the following groups:
- dialcohols, such as ethylene glycol, 1,4-butanediol, 1,3-propanediol, 1,6-hexanediol diethylene glycol and others;
and/or - dicarboxylic acid, such as oxalic acid, succinic acid, adipic acid and others, including those in the form of their respective esters (methyl, ethyl etc.); and/or - hydroxycarboxylic acids and lactones, such as capro-lactone and others; and/or - amino alcohols, such as ethanolamine, propanolamine etc.; and/or - cyclic lactams, such as ~-caprolactam or laurolactam etc.; and/or - ~-aminocarboxylic acids, such as aminocaproic acid etc.:
and/or - mixtures (1:1 salts) of dicarboxylic acids such as adipic acid, succinic acid etc. and diamines such as hexamethylenediamine, diaminobutane etc.
CA 02217~41 1997-10-06 In the case where the polymer mixture is based extensively on thermoplastic starch and an aromatic polyester, an aliphatic-aromatic copolyester or a polyesteramide it may be advan-tageous to add an aliphatic polyester or copolyester, such as polycaprolactone, for example, as a further component. By this means the relatively poor biological degradability, for example, of the aromatic polyester is compensated by the excellent degradability of the aliphatic polyester. As an example of this there may be mentioned a polymer mixture consisting of thermoplastic starch, at least one polyethylene terephthalate (PET) or a polyalkylene terephthalate, and polycaprolactone. Other examples of aliphatic polyesters or copolyesters are polylactic acid, polyhydroxybutyric acid, polyhyroxybenzoic acid, polyhydroxybutyric acid-hydroxy-valeric acid copolymer and/or mixtures thereof.
Depending on how the preparation of the polymer mixture is carried out it is advantageous if this mixture additionally contains a block copolymer as phase mediator in order to form a continuous, homogeneous phase between the thermoplastic starch and the hydrophobic polymer in the form of the polyester. A phase mediator of this kind can, for example, be a reaction mixture obtained by essentially anhydrous mixing of thermoplastic starch or, if desired, native or destructured starch with an aliphatic or aromatic polyester CA 02217~41 1997-10-06 or copolyester, with an aromatic/aliphatic copolyester, with a polyesteramide and/or a polyesterurethane.
The proportion of thermoplastic starch containing the above-mentioned plasticizing or swelling agent can make up a proportion of between 10 - 95% by weight, based on the overall weight, in the polymer mixture proposed in accordance with the invention; preferably, 30-75% by weight of thermoplastic starch is used. The proportion of thermoplastic starch depends on the one hand on the polyester or copolyester used and on the other hand on the intended use of the polymer mixture, such as injection molding, extrusion or film blowing. The requirements with regard to the material properties also influence the proportion of thermoplastic starch. If, for example, heightened material requirements with respect to mechanical and thermal properties are imposed, a proportion of thermoplastlc starch in the range of 40 - 65% by weight will preferably be targeted; consequently, the price of the mixture re~A; n~ acceptable in any case.
Also a subject of the present invention are mixtures containing 90 - 30, especially 80 - 40% by weight of thermo-plastically processible polyesteramides comprising 30 - 70%
by weight aliphatic esters and 70 - 30% by weight aliphatic amide structures, where, furthermore, preferably 10 - 90% by CA 02217~41 1997-10-06 weight, in particular 20 - 60% by weight of starch or thermoplastic starch are contained.
The addition of further additives, such as plasticizers, stabilizers, antiflaming agents and also further, biologically degradable polymers, such as cellulose esters, cellulose acetate, cellulose, polyhydroxybutyric acid, hydrophobic proteins, polyvinyl alcohol, etc., is possible and again is guided by the requirements with regard to the polymer mixture to be prepared and of course also by the availability of the corresponding components. The polymers indicated below are also suitable as additives, such as gelatins, proteins, zeins, polysaccharides, cellulose derlvatives, polylactides, polyvinyl alcohol, polyvinyl acetate, polyacrylates, sugar alcohols, shellac, casein, fatty acid derivatives, plant fibers, lecithin, chitosan, polyesterpolyurethanes and polyesteramides. Mention should also be made of polyester blends consisting of thermoplastic starch, the aliphatic/aromatic polyester proposed according to the invention and, as further component, copolymers selected from ethylene-acrylic acid copolymer and ethylene-vinyl alcohol copolymer.
Also suitable as fillers are, in particular, organic fillers obtained from renewable raw materials, for example cellulose CA 02217~41 199i-10-06 fibers.
In order to reduce the hydrophilic polymer properties of materials comprising thermoplastic starch it is also possible to add crosslinking agents, for example alkylketene dimers of the following general formula:
~ ~ \
~ / C. = C\ ~C = O
. H / C
where R = linearly saturated alkyl group in the range from C12 - C 24. The concentration of such network agents amounts as a rule to about 0.05 - 2%, based on the weight, proportion of dry thermoplastic starch in the polymer mixture, prefer-ably 0.1 - 1% by weight. The proposed alkylketene dimers react in this case with the hydroxyl group~ of the starch polymer.
The preparation of the polymer mixture proposed according to the invention takes place by mixing starch, such as preferably thermoplastic starch, together with the aromatic polyester and/or the polyester copolymer containing aromatic and aliphatic constituents in the melt, the water content in the mixture being reduced before or during mixing to less than 1% by weight, based on the weight of the mixture.
CA 02217~41 1997-10-06 Especially in the case of the exclusive use of an aromatic polyester together with the thermoplastic starch for the preparation of the polymer mixture it has proven advantageous to add, in addition, an aliphatic polyester during the preparation. Examples of suitable aliphatic polyesters are, for example, polycaprolactone, polylactic acid, etc., as already set out above. Further suitable aliphatic polyesters are, for example, polyethylene succinate (PESU) and poly-butylene succinate (PBSU). The latter aliphatic polyesters are formed by reaction of glycols with aliphatic dicarboxylic acids and other acids and have the following general structural formula:
(O (CH2-)m-0-C-~CH2-)n-C-)N
O O
In every case it is proposed, in accordance with a preferred variant embodiment of the process according to the invention, to reduce the water content during the mixing of the melt to below 0.5~ by weight, preferably even to below 0.1~ by weight, based on the overall weight of the mixture.
In the preparation of the polymer mixture proposed in accordance with the invention, the thermoplastic starch is present to begin with as a so-called disperse phase, while the polyester or the copolyester, the polyesteramide or the CA 02217~41 1997-10-06 .
polyesterurethane, representing a hydrophobic polymer, is present as a substantially coherent, continuous phase. An obvious supposition, then, is that when the two polymers are mixed with the exclusion of water the ester groups incorporated in the molecule chains of the polyester or - copolyester, etc. undergo esterification reactions with the thermoplastic starch, as a result of which the molecule ch~; n~ reacting in this way form a phase mediator with the starch which allows a molecular coupling of the two phases, and consequently a continuous phase is formed. In the case of moisture this reaction is in competition, since in the absence of water the acid ester groups do not react with the starch, to form the phase mediator, but instead are hydrolyzed. This, however, prevents formation of the phase mediator, which renders flawless dispersing or homogenizing impossible. It is of course possible to use a phase mediator from the outset, such as a block copolymer which comprises at least two blocks, one block being at least substantially soluble in the hydrophobic polyester phase and the other block being at least substantially soluble in the starch phase. In this context reference may be made to DE-42 37 535.5.
Depending on the aromatic, aliphatic, aromatic/aliphatic copolyester polyesteramide and/or polyesterurethane used, CA 022l7~4l l997-l0-06 mixing is conducted in the melt in a temperature range between 120 - 260~C, preferably in a range of 140 - 160~C.
The mixing temperature must be chosen so that no damage can occur to the polyester or copolyester used. The mixing of the thermoplastic starch with the polyester component or components, together if desired with further additives and components, takes place preferably in an extruder or kneader, which preferably has a devolatilizing device, for the continuous removal of moisture, in order to attain the required freedom from water. It has been found that, when the thermoplastic starch is mixed with the polyester or polyesters water is formed, which allows one to draw the conclusion of, for example, the above-mentioned reaction of the ester groups with the starch to form the phase mediator.
On leaving the extruder or kneader through the die the melt has an extremely low water content, preferably ~ 0.5 or < 0.1% by weight. After removal from the die the melt is preferably cooled in a water bath and conditioned before being subjected subsequently granulated, for example. It has proven advantageous if the melt, which is dry per se, is cooled in a water bath 80 that it absorbs within the order of magnitude of 2 - about 6% by weight, based on the overall weight, of water, in order to ensure flawless granulation.
CA 02217~41 1997-10-06 The polymer mixture prepared in accordance with the invention, comprising at least thermoplastic starch and, for example, the polyester copolymer comprising aromatic and aliphatic blocks, is outstandingly suitable as a polymer material for a very wide variety of applications in the field of so-called "engineering plastics". Processing in the injection molding process, as well as by extrusion and film blowing, is possible, for instance. However, when processing the polymer mixture according to the invention it has been found advantageous if the polymer mixture, which is present for example as granules, is conditioned before processing, either by means of water or with a plasticizer, such as .,~
CA 02217~41 1997-10-06 - 15a -glycerol or a mixture thereof. The target is, for example, a water content of about 1 - 6~ by weight, based on the overall weight, preferably 3 - 5~ by weight, as is usual, for example, in the processing of polyesters. Also, the injection moldings, extrudates or films produced are preferably stored directly after their preparation in an environment having a relative humidity of at least 40~, preferably at least 45 -50~.
Examples of possible and preferred polymer mixtures, exhib-iting at least starch or thermoplastic starch and a hydro-phobic polymer as claimed in one of the dependent claims 2 -15 or prepared in accordance with a process set out in one of claims 16 - 22 are listed in Tables 1 - 4 depicted below.
These examples are supplemented by an additional experiment 29.
The total of 29 examples indicated in this case include both components which have been used for the preparation of thermoplastic starch in the sense of plasticizing agents or swelling agents and the possible polymeric mixing partners to the thermoplastic starch for the preparation of the polymer mixtures proposed in accordance with the invention. The tables include, moreover, the processing conditions and, in particular, the water content in the extruder which prevails during the preparation of the polymer mixture, and which without exception amounted to < than 0.1~ by weight. In addition, preferred application options for the polymer mixtures prepared by way of example are set out in the AMENDED SHEET
IPEA/EP
CA 02217~41 1997-10-06 tables. The tables of course contain only examples, and all components mentioned at the outset are suitable for mixing with starch or thermoplastic starch for preparing starting polymer mixtures, defined in accordance with the invention, for both technical and nontechnical applications.
CA 022l7~4l l997-l0-06 Table 1 Examples Example 1 2 3 4 5 6 7 Starch ~ 42.2 24.0 29.9 24.0 33.0 38.0 21.5 Sorbitol ~ 14.0 8.0 9.5 8.0 9.9 11.8 6.9 1Glycerol ~ 9.5 6.0 6.5 6.0 7.9 9.3 2.1 2TPS ~ 60.5 34.9 42.0 34.9 46.7 54.5 27.8 H20 96 ~0.1 ~0.1 ~0.1 ~0.1 ~0.1 ~0.1 ~0.1 3PLA ~ - - - - 40.0 10.9 4Polyamide 1 34.3 50.0 - - 9.2 - 69.5 sPolyester 1 - - 54.1 45.0 - 30.0 6PCL % - 12.0 - 17.0 H20 96 <0.1 ~0.1 cO.l ~0.1 ~0.1 ~0.1 <0.1 7Extrusion ZSK 40 ZSK 40 ZSK 40 ZSK 40 ZSK 40 ZSK 40 ZSK 40 T ~C 212 225 210 210 215 210 200 Pressure bar 8.5 2.0 2.5 2.5 6.2 7.5 0.5 MFI g/10' 9 13 11.5 13 8.5 8.0 29 Granules 4 mm 4 mm 4 mm 4 mm 4 mm 4 mm 4 mm Gra H2O ~ 3.0 3.6 3.4 3.6 3.4 3.4 3.0 Application Blown film + + + + + +
Flat film + + + + + +
Sheets + + + + + +
Injection mol- +
ding <0.4~-Fiber~ - + - + - - +
lStarch = native potato starch dried 3.5% H20, sorbitol =
sorbitol LG DHR 71%, glycerol 99.5%;
2TPS = thermoplastic starch = starch+sorbitol+glycerol c 0.1%
H20. - Water content by devolatilization, according to the known process EP O 397 819 anhydrous TPS consists of starch, CA 02217~41 1997-10-06 sorbitol and glycerol;
3PLA (polylactic acid resin) - Mitsui Toatsu Chemicals LACEA
H 100 MFR 13 190~C 2.16 kg:
4Polyamide 1 = Bayer BAK 1095 polyersteramide MFI 2.5 150~C
Proposals for the preparation of biologically degradable polymer mixtures are known from a large number of patent documents and articles. The great problem in the case of polymer mixtures lies, as a rule, in that those mixtures which have an excellent, biological degradability have only limited possibilities for use in the area of engineering plastics, thereby explaining the relatively modest success to date. Polymer mixtures having improved properties are either biologically inadequate or degradable with increased effort, or else are too expensive.
From EP-535 994 a polymer mixture is known essentially consisting of starch and an aliphatic polyester, for example polycaprolactone, where the starch is preferably destructured with water.
Moreover, in an article in the journal "Starke", volume 45, No. 9, September 1, 1993, Weinheim, pages 314 to 322, the use ~ENDED SHEET
IPEA/EP
CA 02217~41 1997-10-06 - la -of starch in the modification of synthetic plastics is described. Here it is proposed first of all to gelatinize the starch by means of water, in connection with which it is mentioned that this gelatinization takes place by means of an endothermic process. This makes it obvious that the gelatinized starch mentioned must be destructured starch, which is mixed with a range of synthetic plastics in order to develop new composite materials.
In contrast, and in knowledge of the inadequacies of starch destructured with water, it is proposed in DE-42 37 535 for a biologically degradable polymer mixture to use thermoplastic starch which is prepared with the exclusion of water and using a suitable plasticizing agent. The proposed polymer mixtures contain thermoplastic starch, a hydrophobic polymer and a phase mediator, thermoplastic starch with polycaprolactone being proposed as preferred mixture.
AMENDED SHEET
IPEA/EP
CA 02217~41 1997-10-06 Aliphatic polyesters are, per se, suitable mixing components for the preparation of biologically degradable polymer mixtures, since they have a good biological degradability.
However, aliphatic polyesters have only moderate material properties, for example with regard to melting point, tensile strength, etc., which is why even corresponding mixtures using a polymer prepared on the basis of renewable raw materials, for example thermoplastic starch, have only moderate properties, thereby again placing in question the possibility for use in the field of engineering plastics.
It is therefore an object of the present invention to propose a biologically degradable polymer mixture which both is flawlessly degradable biologically and in addition has good mechanical and thermal properties, so that use as an engineering plastic or as a polymer material is appropriate.
A further prerequisite for suitability as a polymer material also lies in the price for the polymer mixture proposed in CA 02217~41 1997-10-06 accordance with object having an acceptable magnitude.
In accordance with the invention the object proposed above is achieved by means of a biologically degradable polymer mixture in accordance with the wording of claim 1.
The multitude of biopolymers or biologically degradable ~ _ _ e CA 02217~41 1997-10-06 -3a-extent constructed on the basis of starch or use starch, although native starch is hardly suitable as a technically usable polymer. Starch is proposed because it is readily degradable biologically, has a favorable price and is independent of petroleum products because it is based on a renewable raw material. Because of the poor suitability of native starch as an "engineering plastic" it is proposed according to the invention to use so-called thermoplastic starch, as is proposed, for example, in PCT/WO90/05161. This thermoplastic starch is obtained by processing native starch in the melt, by means of a plasticizing or swelling agent, to a homogeneous mass, where the proportion of swelling or plasticizing agent can as a rule amount to between 10 and about 40~, based on the overall weight of the mixture. As set out in claim 2, suitable swell-ing or plasticizing agents are, inter alia, for example, glycerol or sorbitol.
Because of the in any case limited properties of thermoplas-tic starch for use in polymer materials it is now proposed according to the invention to mix said starch with at least one further polymer, such as with an aromatic polyester, with a polyester copolymer, the polyester copolymer being prepared from customary diols and from aromatic and aliphatic dicarboxylic acids, with a polyesteramide, a polyethylene oxide polymer or a polyglycol, a polyesterurethane and/or mixtures thereof. The polymer classes of the diverse poly-esters and copolyesters or polyglycols have proven in AMENDED SHEET
IPEA/EP
CA 02217~41 1997-10-06 particular to be suitable materials for improving the rather moderate material properties of thermoplastic starch. The aliphatic polyesters proposed in the prior art, which although having good biological degradability are not particularly suitable because of their likewise moderate material properties with regard to melting point and draw-ability, themselves contribute to an improvement in the material properties of the thermoplastic starch. In contrast, aromatic polyesters exhibit excellent material properties but their biological degradability is rather moderate. On the other hand, inter alia, polyester copolymers based on aromatic and aliphatic dicarboxylic acids, polyesteramides and also polyesterurethanes have both outstanding material properties and a rapid biological degradability, which is why Chey 1/
' - CA 0 2 2 1 i ~ 4 1 1 9 9 7 - 1 0 - 0 6 - r _ with thermoplastic starch.
The polyester copolymers proposed for use in accordance with the invention in the polymer mixture with thermoplastic starch are constructed on the basis, besides the customarily used polyols, of aromatic and aliphatic dicarboxylic acids, and have the following general structure:
O O O O
HO (CX2)x-O-~ cH2)y~~~~ (CH2)x-O ~ ~ (CH2)X-OH
1 - n The polyester copolymers proposed according to the invention can be prepared from petrochemical mass products, such as adipic acid, sebacic acid, terephthalic acid and a diol by means of polycondensation, with commercially customary diols, such as 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol and/or 1,6-hexanediol being used. What is important is that both aromatic and aliphatic dicarboxylic acids are u~ed, by means of which the statistical polyester copolymers are prepared, for example by means of a conventional polyconden-sation process.
Statistical copolyesters of aliphatic and aromatic dicar-boxylic acids with a proportion, for example, of about 35 -CA 02217~41 1997-10-06 55 mol% of aromatic acid, for example terephthalic acid, represent an optimum compromise between biological degradab-ility and material properties, as a result of which they are particularly suitable in mixtures with thermoplastic starch.
The biological degradability of statistical copolyesters of this kind lies within 8 - 12 weeks in compost and earth. In this context reference may be made to US Patent 5 446 079, in which the preparation of aliphatic-aromatic copolyesters is described in detail.
Polyalkylene terephthalates and polyethylene terephthalates which are prepared from aliphatic diols and aromatic dicar-boxylic acids have proven, for example, to be suitable co-polyesters for the preparation of a starch/polyester copoly-mer blend according to the invention.
In addition to the starch/polyester copolymer blends described above and proposed according to the invention it has become evident that polyesteramides filled or blended with starch or thermoplastic starch and with ester contents of between 30 and 70% by weight have good mechanical proper-ties, even for the production of films, and have good degradability and compostibility. Proposed are, for example, polyesteramides having a mean molecular weight in a range of 10 - 30a,000, preferably 20 - 150,000. Otherwise reference CA 02217~41 1997-10-06 may be made to the European patent application EP-A-641 817, in which the synthesis of the polyesteramides proposed in accordance with the invention is described in detail. Mention should merely be made that polyesteramides according to the invention can be constructed from monomers of the following groups:
- dialcohols, such as ethylene glycol, 1,4-butanediol, 1,3-propanediol, 1,6-hexanediol diethylene glycol and others;
and/or - dicarboxylic acid, such as oxalic acid, succinic acid, adipic acid and others, including those in the form of their respective esters (methyl, ethyl etc.); and/or - hydroxycarboxylic acids and lactones, such as capro-lactone and others; and/or - amino alcohols, such as ethanolamine, propanolamine etc.; and/or - cyclic lactams, such as ~-caprolactam or laurolactam etc.; and/or - ~-aminocarboxylic acids, such as aminocaproic acid etc.:
and/or - mixtures (1:1 salts) of dicarboxylic acids such as adipic acid, succinic acid etc. and diamines such as hexamethylenediamine, diaminobutane etc.
CA 02217~41 1997-10-06 In the case where the polymer mixture is based extensively on thermoplastic starch and an aromatic polyester, an aliphatic-aromatic copolyester or a polyesteramide it may be advan-tageous to add an aliphatic polyester or copolyester, such as polycaprolactone, for example, as a further component. By this means the relatively poor biological degradability, for example, of the aromatic polyester is compensated by the excellent degradability of the aliphatic polyester. As an example of this there may be mentioned a polymer mixture consisting of thermoplastic starch, at least one polyethylene terephthalate (PET) or a polyalkylene terephthalate, and polycaprolactone. Other examples of aliphatic polyesters or copolyesters are polylactic acid, polyhydroxybutyric acid, polyhyroxybenzoic acid, polyhydroxybutyric acid-hydroxy-valeric acid copolymer and/or mixtures thereof.
Depending on how the preparation of the polymer mixture is carried out it is advantageous if this mixture additionally contains a block copolymer as phase mediator in order to form a continuous, homogeneous phase between the thermoplastic starch and the hydrophobic polymer in the form of the polyester. A phase mediator of this kind can, for example, be a reaction mixture obtained by essentially anhydrous mixing of thermoplastic starch or, if desired, native or destructured starch with an aliphatic or aromatic polyester CA 02217~41 1997-10-06 or copolyester, with an aromatic/aliphatic copolyester, with a polyesteramide and/or a polyesterurethane.
The proportion of thermoplastic starch containing the above-mentioned plasticizing or swelling agent can make up a proportion of between 10 - 95% by weight, based on the overall weight, in the polymer mixture proposed in accordance with the invention; preferably, 30-75% by weight of thermoplastic starch is used. The proportion of thermoplastic starch depends on the one hand on the polyester or copolyester used and on the other hand on the intended use of the polymer mixture, such as injection molding, extrusion or film blowing. The requirements with regard to the material properties also influence the proportion of thermoplastic starch. If, for example, heightened material requirements with respect to mechanical and thermal properties are imposed, a proportion of thermoplastlc starch in the range of 40 - 65% by weight will preferably be targeted; consequently, the price of the mixture re~A; n~ acceptable in any case.
Also a subject of the present invention are mixtures containing 90 - 30, especially 80 - 40% by weight of thermo-plastically processible polyesteramides comprising 30 - 70%
by weight aliphatic esters and 70 - 30% by weight aliphatic amide structures, where, furthermore, preferably 10 - 90% by CA 02217~41 1997-10-06 weight, in particular 20 - 60% by weight of starch or thermoplastic starch are contained.
The addition of further additives, such as plasticizers, stabilizers, antiflaming agents and also further, biologically degradable polymers, such as cellulose esters, cellulose acetate, cellulose, polyhydroxybutyric acid, hydrophobic proteins, polyvinyl alcohol, etc., is possible and again is guided by the requirements with regard to the polymer mixture to be prepared and of course also by the availability of the corresponding components. The polymers indicated below are also suitable as additives, such as gelatins, proteins, zeins, polysaccharides, cellulose derlvatives, polylactides, polyvinyl alcohol, polyvinyl acetate, polyacrylates, sugar alcohols, shellac, casein, fatty acid derivatives, plant fibers, lecithin, chitosan, polyesterpolyurethanes and polyesteramides. Mention should also be made of polyester blends consisting of thermoplastic starch, the aliphatic/aromatic polyester proposed according to the invention and, as further component, copolymers selected from ethylene-acrylic acid copolymer and ethylene-vinyl alcohol copolymer.
Also suitable as fillers are, in particular, organic fillers obtained from renewable raw materials, for example cellulose CA 02217~41 199i-10-06 fibers.
In order to reduce the hydrophilic polymer properties of materials comprising thermoplastic starch it is also possible to add crosslinking agents, for example alkylketene dimers of the following general formula:
~ ~ \
~ / C. = C\ ~C = O
. H / C
where R = linearly saturated alkyl group in the range from C12 - C 24. The concentration of such network agents amounts as a rule to about 0.05 - 2%, based on the weight, proportion of dry thermoplastic starch in the polymer mixture, prefer-ably 0.1 - 1% by weight. The proposed alkylketene dimers react in this case with the hydroxyl group~ of the starch polymer.
The preparation of the polymer mixture proposed according to the invention takes place by mixing starch, such as preferably thermoplastic starch, together with the aromatic polyester and/or the polyester copolymer containing aromatic and aliphatic constituents in the melt, the water content in the mixture being reduced before or during mixing to less than 1% by weight, based on the weight of the mixture.
CA 02217~41 1997-10-06 Especially in the case of the exclusive use of an aromatic polyester together with the thermoplastic starch for the preparation of the polymer mixture it has proven advantageous to add, in addition, an aliphatic polyester during the preparation. Examples of suitable aliphatic polyesters are, for example, polycaprolactone, polylactic acid, etc., as already set out above. Further suitable aliphatic polyesters are, for example, polyethylene succinate (PESU) and poly-butylene succinate (PBSU). The latter aliphatic polyesters are formed by reaction of glycols with aliphatic dicarboxylic acids and other acids and have the following general structural formula:
(O (CH2-)m-0-C-~CH2-)n-C-)N
O O
In every case it is proposed, in accordance with a preferred variant embodiment of the process according to the invention, to reduce the water content during the mixing of the melt to below 0.5~ by weight, preferably even to below 0.1~ by weight, based on the overall weight of the mixture.
In the preparation of the polymer mixture proposed in accordance with the invention, the thermoplastic starch is present to begin with as a so-called disperse phase, while the polyester or the copolyester, the polyesteramide or the CA 02217~41 1997-10-06 .
polyesterurethane, representing a hydrophobic polymer, is present as a substantially coherent, continuous phase. An obvious supposition, then, is that when the two polymers are mixed with the exclusion of water the ester groups incorporated in the molecule chains of the polyester or - copolyester, etc. undergo esterification reactions with the thermoplastic starch, as a result of which the molecule ch~; n~ reacting in this way form a phase mediator with the starch which allows a molecular coupling of the two phases, and consequently a continuous phase is formed. In the case of moisture this reaction is in competition, since in the absence of water the acid ester groups do not react with the starch, to form the phase mediator, but instead are hydrolyzed. This, however, prevents formation of the phase mediator, which renders flawless dispersing or homogenizing impossible. It is of course possible to use a phase mediator from the outset, such as a block copolymer which comprises at least two blocks, one block being at least substantially soluble in the hydrophobic polyester phase and the other block being at least substantially soluble in the starch phase. In this context reference may be made to DE-42 37 535.5.
Depending on the aromatic, aliphatic, aromatic/aliphatic copolyester polyesteramide and/or polyesterurethane used, CA 022l7~4l l997-l0-06 mixing is conducted in the melt in a temperature range between 120 - 260~C, preferably in a range of 140 - 160~C.
The mixing temperature must be chosen so that no damage can occur to the polyester or copolyester used. The mixing of the thermoplastic starch with the polyester component or components, together if desired with further additives and components, takes place preferably in an extruder or kneader, which preferably has a devolatilizing device, for the continuous removal of moisture, in order to attain the required freedom from water. It has been found that, when the thermoplastic starch is mixed with the polyester or polyesters water is formed, which allows one to draw the conclusion of, for example, the above-mentioned reaction of the ester groups with the starch to form the phase mediator.
On leaving the extruder or kneader through the die the melt has an extremely low water content, preferably ~ 0.5 or < 0.1% by weight. After removal from the die the melt is preferably cooled in a water bath and conditioned before being subjected subsequently granulated, for example. It has proven advantageous if the melt, which is dry per se, is cooled in a water bath 80 that it absorbs within the order of magnitude of 2 - about 6% by weight, based on the overall weight, of water, in order to ensure flawless granulation.
CA 02217~41 1997-10-06 The polymer mixture prepared in accordance with the invention, comprising at least thermoplastic starch and, for example, the polyester copolymer comprising aromatic and aliphatic blocks, is outstandingly suitable as a polymer material for a very wide variety of applications in the field of so-called "engineering plastics". Processing in the injection molding process, as well as by extrusion and film blowing, is possible, for instance. However, when processing the polymer mixture according to the invention it has been found advantageous if the polymer mixture, which is present for example as granules, is conditioned before processing, either by means of water or with a plasticizer, such as .,~
CA 02217~41 1997-10-06 - 15a -glycerol or a mixture thereof. The target is, for example, a water content of about 1 - 6~ by weight, based on the overall weight, preferably 3 - 5~ by weight, as is usual, for example, in the processing of polyesters. Also, the injection moldings, extrudates or films produced are preferably stored directly after their preparation in an environment having a relative humidity of at least 40~, preferably at least 45 -50~.
Examples of possible and preferred polymer mixtures, exhib-iting at least starch or thermoplastic starch and a hydro-phobic polymer as claimed in one of the dependent claims 2 -15 or prepared in accordance with a process set out in one of claims 16 - 22 are listed in Tables 1 - 4 depicted below.
These examples are supplemented by an additional experiment 29.
The total of 29 examples indicated in this case include both components which have been used for the preparation of thermoplastic starch in the sense of plasticizing agents or swelling agents and the possible polymeric mixing partners to the thermoplastic starch for the preparation of the polymer mixtures proposed in accordance with the invention. The tables include, moreover, the processing conditions and, in particular, the water content in the extruder which prevails during the preparation of the polymer mixture, and which without exception amounted to < than 0.1~ by weight. In addition, preferred application options for the polymer mixtures prepared by way of example are set out in the AMENDED SHEET
IPEA/EP
CA 02217~41 1997-10-06 tables. The tables of course contain only examples, and all components mentioned at the outset are suitable for mixing with starch or thermoplastic starch for preparing starting polymer mixtures, defined in accordance with the invention, for both technical and nontechnical applications.
CA 022l7~4l l997-l0-06 Table 1 Examples Example 1 2 3 4 5 6 7 Starch ~ 42.2 24.0 29.9 24.0 33.0 38.0 21.5 Sorbitol ~ 14.0 8.0 9.5 8.0 9.9 11.8 6.9 1Glycerol ~ 9.5 6.0 6.5 6.0 7.9 9.3 2.1 2TPS ~ 60.5 34.9 42.0 34.9 46.7 54.5 27.8 H20 96 ~0.1 ~0.1 ~0.1 ~0.1 ~0.1 ~0.1 ~0.1 3PLA ~ - - - - 40.0 10.9 4Polyamide 1 34.3 50.0 - - 9.2 - 69.5 sPolyester 1 - - 54.1 45.0 - 30.0 6PCL % - 12.0 - 17.0 H20 96 <0.1 ~0.1 cO.l ~0.1 ~0.1 ~0.1 <0.1 7Extrusion ZSK 40 ZSK 40 ZSK 40 ZSK 40 ZSK 40 ZSK 40 ZSK 40 T ~C 212 225 210 210 215 210 200 Pressure bar 8.5 2.0 2.5 2.5 6.2 7.5 0.5 MFI g/10' 9 13 11.5 13 8.5 8.0 29 Granules 4 mm 4 mm 4 mm 4 mm 4 mm 4 mm 4 mm Gra H2O ~ 3.0 3.6 3.4 3.6 3.4 3.4 3.0 Application Blown film + + + + + +
Flat film + + + + + +
Sheets + + + + + +
Injection mol- +
ding <0.4~-Fiber~ - + - + - - +
lStarch = native potato starch dried 3.5% H20, sorbitol =
sorbitol LG DHR 71%, glycerol 99.5%;
2TPS = thermoplastic starch = starch+sorbitol+glycerol c 0.1%
H20. - Water content by devolatilization, according to the known process EP O 397 819 anhydrous TPS consists of starch, CA 02217~41 1997-10-06 sorbitol and glycerol;
3PLA (polylactic acid resin) - Mitsui Toatsu Chemicals LACEA
H 100 MFR 13 190~C 2.16 kg:
4Polyamide 1 = Bayer BAK 1095 polyersteramide MFI 2.5 150~C
2.16 kg;
sPolyester 1 = BASF ZK 242/108 copolyester of aliphatic diols and aliphatic/aromatic dicarboxylic acids MVR 3.0 at 190~C/2.16 kg;
6PCL (polycaprolactone) + Union Carbide Tone Polymer P-787 MFI 1.0 125~C 44 psi g/10 min;
7Extrusion Equipment = Werner&Pfleiderer ZSK 40;
~0.1 - 0.4% water content CA 022l7~4l l997-l0-06 Table 2 Examples Example 8 9 10 11 12 13 14 Starch % 38.2 24.6 29.2 24.6 30.7 28.0 21.5 Sorbitol ~ 12.8 8.2 9.4 8.8 9.1 8.8 6.9 1Glycerol % 8.5 6.0 6.2 6.0 7.4 6.2 4.1 7TPS % 54.5 35.5 41.1 36.0 43.5 39.5 29.7 H20 96 ~0.1 <0.1 ~0.1 ~0.1 cO.l ~0.1 ~0.1 3PPDX ~ 34.0 - - 6.5 - - 33.8 ~PT-C300 - - 45.1 sPT-T8-200 - 32.5 - - 47.0 57.0 6BAK 6.5 28.7 10.1 54.1 5.8 - 33.7 H20 96 ~0.1 ~0.1 ~0.1 ~0.1 ~0.1 ~0.1 ~0.1 7Extrusion ZSK 40 ZSK 40 ZSK 40 ZSK 40 ZSK 40 ZSK 40 ZSK 40 T ~C 220 214 240 215 215 210 205 Pressure bar 6.5 3.5 5.5 7.5 4.5 7.5 0.5 MFI g/10' 8 13 2.5 11.5 8.5 8.0 30 Granules 4 mm 4 mm 4 mm 4 mm 4 mm 4 mm 4 mm Gra H2O % 3.9 3.6 3.5 3.3 3.4 3.6 3.2 Application Blown film + + + + + +
Flat film + + + + + +
Sheets + + + + + +
Injection mol- + - +~0.4*
ding c0.15*
Fibers - - - - - - +
lStarch = native potato starch dried 3.5~ H20, sorbitol =
sorbitol LG DHR 71%, glycerol 99.5~;
2TPS = thermoplastic starch = starch+sorbitol+glycerol ~ 0.1%
H20. - Water content by devolatilization, according to the known process EP O 397 819 anhydrous TPS consists of starch, CA 02217~41 1997-10-06 sorbitol and glycerol;
3PPDX. Polyparadioxanone. Shell International Chemicals Ltd.
peak melting deg ~C 110.;
4PT-C300ZT. Enviro Plastic, Plantet Polymers, VICAT Softening Temp. 89~C. Polyethylene oxide polymers;
sPT-T8-200DL. Enviro-Plastic C. Planet Polymers, Polyethylene oxide polymers;
6Polyesteramide BAK 1095, Bayer AG, MFI 2.5 150~C, 2.16 kg;
7Extrusion Equipment = Werner&Pfleiderer ZSK 40;
~0.1 - 0.4% water content CA 022l7~4l l997-l0-06 Table 3 Examples Example 15 16 17 18 19 20 21 Starch % 20.9 24.6 20.4 24.6 9.2 9.2 9.2 Sorbitol ~ 7.0 8.2 6.6 8.8 2.7 2.7 2.7 lGlycerol ~ 4.7 6.0 4.4 6.0 2.2 2.2 2.2 2TPS ~ 29.9 35.5 28.6 36.0 13.0 13.0 13.0 H20 % ~0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 3Filler % 26.9 - 25.0 - 60.0 - 60.0 ~Polyamide 1 40.5 36.2 - - 25.9 27.9 sPolye6ter 1 - - 43.6 35.6 - - 25.9 6Filler % - 25.0 - 25.0 - 58.0 H20 9~ <0.1 <0.1 <0.1 ~0.1 cO.l <0.1 cO.l 7Extrusion ZSK 40 ZSK 40 ZSK 40 ZSK 40 ZSK 40 ZSK 40 ZSK 40 T ~C 203 206 220 215 205 205 220 Pressure bar 156.5 21 15 22 35 40 35 MFI g/10' 13 9 12.5 8.5 3 2.8 2.2 Granules 4 mm 4 mm 4 mm 4 mm 4 mm 4 mm 4 mm Gra H2O ~ 3.5 3.6 3.4 3.6 3.4 3.4 3.0 Application Blown film Flat film (+) (+) (+) (+) Sheets + + + + + + +
Injection mol- + + + + + + +
ding ~0.2%* ~0.2%* ~0.2%* ~0.2%* ~0.2%* ~0.2%* ~0.2%*
Fibers -Starch = nat ve potato st~rch dried 3.~% H20, sorbitol =
sorbitol LG DHR 71%, glycerol 99.5%;
2TPS = thermoplastic starch = starch+sorbitol+glycerol c 0.1%
H20. - Water content by devolatilization, according to the known process EP O 397 819 anhydrous TPS consists of starch, sorbitol and glycerol;
CA 02217~41 1997-10-06 3Filler, micronized cellulose;
4Polyamide 1 = Bayer BAK 1095 polyesteramide MFI 2.5 150~C
2.16 kg;
sPolyester 1 = BASF ZK 242/108 copolyester of aliphatic diols and aliphatic/aromatic dicarboxylic acids MVR 3.0 at 190~C/2.16 kg;
6Filler, micronized cotton 7Extrusion Equipment = Werner&Pfleiderer ZSK 40;
~0.1 - 0.4% water content CA 02217~41 1997-10-06 Table 4 Examples Example 22 23 24 25 26 27** 28**
Starch % 34.5 35.5 40.5 50.5 60.7 70.3 67.8 lSorbitol % - - _, _ _ _ _ 'Glycerol % 16.3 16.5 12.0 7.1 4.0 4.5 2Polyamide 1 25.0 23.5 47.5 42.4 35.3 25.2 32.2 3TPS% 74.8 74.4 98.6 98.5 98.2 87.4 87.8 H20 % ~0.1 <0.1 ~0.1 ~0.1 ~0.1 ~0.1 ~0.1 ~PLA 24.2 - - - - - -sPolyester 1 - 24.5 H20 % ~0.1 ~0.1 ~0.1 ~0.1 ~0.1 ~0.1 ~0.1 7Extrusion ZSK 40 ZSK 40 ZSK 40 ZSK 40 ZSK 40 ZSK 40 ZSK 40 T ~C 200 206 190 170 160 155 155 Pressure bar 15 15 20 26 31 35 37 MFI g/10' 12 14 122.5 10 6 5 5.5 Granules 4 mm 4 mm 4 mm 4 mm 4 mm 4 mm 4 mm Gra H2O % 2.1 2.1 2.2 2.6 0.4 0.4 0.3 Application Blown film + + + + + + +
Flat film + + + + + + +
Sheets + + + + + + +
Injection - - - (+) +~ + +
molding 0.15~* c 0.2%* <0.2%*
Fibers 1Starch = native potato starch dried 3.5% H2O, sorbitol =
sorbitol LG DHR 71%, glycerol 99.5%;
4Polyamide 1 = Bayer BAK 1095 polyesteramide MFI 2.5 150~C
2.16 kg, function of plasticizer;
2TPS = thermoplastic starch = starch+sorbitol+glycerol and/or CA 022l7~4l l997-l0-06 BAK 1095, < 0.1% H2O. - Water content by devolatilization, according to the known process EP 0 397 819. 27** + 28**
starch = native potato starch 18% H2O:
3PLA (Polylactic acid resin) = Mitsui Toatsu Chemicals LACEA
H 100 MFR 13 190~C 2.16 kg;
5Polyester 1 = BASF ZK 242/108 copolyester of aliphatic diols and aliphatic/aromatic dicarboxylic acids MVR 3.0 at 190~C/2.16 kg;
6PCL (Polycaprolactone) = Union Carbide Tone Polymer P-787 MFI 1.0 125~C 44psi g/10 min;
7Extrusion Equipment = Werner&Pfleiderer ZSK 40;
~0.1 - 0.4~ water content CA 02217~41 1997-10-06 Experiment Example 29:
In analogy to experiment 28, the polyesteramide BAK 1095 was in example 29 compounded with 10~ potato starch in the twin-screw extruder ZSK 40 at 155~C and 20 bar with removal of water, extruded with 0.15~ residual moisture, and, after the polyester extrudate had cooled, was granulated. The polymer mixture has an MFI g/10' of 25 at 150~C/5 kg and is suitable for producing blown and flat films.
Injection moldings, extrudates and films produced by means of polymer mixtures proposed in accordance with the invention have not only relatively good material properties but also an outstanding biological degradability, which is why they are able to make a significant contribution to the acute problem of waste. For example, films produced from a polymer mixture proposed in accordance with the invention are outstandingly suitable for a very wide variety of applications in the agricultural sector, for example for the covering of fields, since such films after their use can either be composted or else ploughed into the earth in the field. Polymer mixtures of this kind are also suitable for the production of composting sacks, containers for composting waste, etc. In addition, containers and bottles, for example, can be produced from the polymer mixture proposed in accordance with CA 02217~41 1997-10-06 the invention by means of blow molding.
The polymer mixtures according to the invention are also suitable, however, for the production of textile articles, for example for the production of fibers, monofilaments, sheetlike structures, such as wovens, felts, nonwovens, so-called backsheets, textile composites, flocks, wadding, and linear structures, for example filaments, yarns, cables, cords, etc. In particular it has been found in practice that the polymer mixtures according to the invention are suitable for the production of sanitary articles, such as diapers, sanitary towels, incontinence products and bed liners. The structure of these hygiene articles includes, inter alia, nonwovens produced from the polymer material according to the invention, since this material has a very good skin compatibility, is respiratorily active, is permeable to water vapor at the same time as being watertight, and yet is fully biologically degradable.
A large proportion of the polymer mixtures proposed in accordance with the invention, especially those containing thermoplastic starch and/or a copolyester and/or a polyester-amide and/or a polyesterurethane, are suitable, moreover, as adhesives or else can be used as coatings, for example for the impregnation of textile wovens. In this case it has been CA 02217~41 1997-10-06 found that the polymer mixtures proposed in accordance with the invention which are suitable for these areas of application are introduced and applied preferably in a form in which they are at least partially dissolved in alcoholic solvents. For example, in connection with experiment example 29 it was found, surprisingly, that the polymer mixture thus prepared is soluble in hot alcohol/ethanol mixture. A 20%
strength alcoholic solution directly after preparation has a viscosity of lOOm Pas. In this case too there was a possible use in the context of a biologically degradable adhesive, as a coating or as an impregnation which brings about hydrophobic properties and is permeable to water vapor. The use ascertained with regard to experiment example 29 can also be transferred to a large number of the other experiment examples and to further polymer mixtures proposed in accordance with the invention.
The polymer mixtures according to the invention are, however, of course suitable for umpteen other applications, for example for disposable injection-molded products, etc.
sPolyester 1 = BASF ZK 242/108 copolyester of aliphatic diols and aliphatic/aromatic dicarboxylic acids MVR 3.0 at 190~C/2.16 kg;
6PCL (polycaprolactone) + Union Carbide Tone Polymer P-787 MFI 1.0 125~C 44 psi g/10 min;
7Extrusion Equipment = Werner&Pfleiderer ZSK 40;
~0.1 - 0.4% water content CA 022l7~4l l997-l0-06 Table 2 Examples Example 8 9 10 11 12 13 14 Starch % 38.2 24.6 29.2 24.6 30.7 28.0 21.5 Sorbitol ~ 12.8 8.2 9.4 8.8 9.1 8.8 6.9 1Glycerol % 8.5 6.0 6.2 6.0 7.4 6.2 4.1 7TPS % 54.5 35.5 41.1 36.0 43.5 39.5 29.7 H20 96 ~0.1 <0.1 ~0.1 ~0.1 cO.l ~0.1 ~0.1 3PPDX ~ 34.0 - - 6.5 - - 33.8 ~PT-C300 - - 45.1 sPT-T8-200 - 32.5 - - 47.0 57.0 6BAK 6.5 28.7 10.1 54.1 5.8 - 33.7 H20 96 ~0.1 ~0.1 ~0.1 ~0.1 ~0.1 ~0.1 ~0.1 7Extrusion ZSK 40 ZSK 40 ZSK 40 ZSK 40 ZSK 40 ZSK 40 ZSK 40 T ~C 220 214 240 215 215 210 205 Pressure bar 6.5 3.5 5.5 7.5 4.5 7.5 0.5 MFI g/10' 8 13 2.5 11.5 8.5 8.0 30 Granules 4 mm 4 mm 4 mm 4 mm 4 mm 4 mm 4 mm Gra H2O % 3.9 3.6 3.5 3.3 3.4 3.6 3.2 Application Blown film + + + + + +
Flat film + + + + + +
Sheets + + + + + +
Injection mol- + - +~0.4*
ding c0.15*
Fibers - - - - - - +
lStarch = native potato starch dried 3.5~ H20, sorbitol =
sorbitol LG DHR 71%, glycerol 99.5~;
2TPS = thermoplastic starch = starch+sorbitol+glycerol ~ 0.1%
H20. - Water content by devolatilization, according to the known process EP O 397 819 anhydrous TPS consists of starch, CA 02217~41 1997-10-06 sorbitol and glycerol;
3PPDX. Polyparadioxanone. Shell International Chemicals Ltd.
peak melting deg ~C 110.;
4PT-C300ZT. Enviro Plastic, Plantet Polymers, VICAT Softening Temp. 89~C. Polyethylene oxide polymers;
sPT-T8-200DL. Enviro-Plastic C. Planet Polymers, Polyethylene oxide polymers;
6Polyesteramide BAK 1095, Bayer AG, MFI 2.5 150~C, 2.16 kg;
7Extrusion Equipment = Werner&Pfleiderer ZSK 40;
~0.1 - 0.4% water content CA 022l7~4l l997-l0-06 Table 3 Examples Example 15 16 17 18 19 20 21 Starch % 20.9 24.6 20.4 24.6 9.2 9.2 9.2 Sorbitol ~ 7.0 8.2 6.6 8.8 2.7 2.7 2.7 lGlycerol ~ 4.7 6.0 4.4 6.0 2.2 2.2 2.2 2TPS ~ 29.9 35.5 28.6 36.0 13.0 13.0 13.0 H20 % ~0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 3Filler % 26.9 - 25.0 - 60.0 - 60.0 ~Polyamide 1 40.5 36.2 - - 25.9 27.9 sPolye6ter 1 - - 43.6 35.6 - - 25.9 6Filler % - 25.0 - 25.0 - 58.0 H20 9~ <0.1 <0.1 <0.1 ~0.1 cO.l <0.1 cO.l 7Extrusion ZSK 40 ZSK 40 ZSK 40 ZSK 40 ZSK 40 ZSK 40 ZSK 40 T ~C 203 206 220 215 205 205 220 Pressure bar 156.5 21 15 22 35 40 35 MFI g/10' 13 9 12.5 8.5 3 2.8 2.2 Granules 4 mm 4 mm 4 mm 4 mm 4 mm 4 mm 4 mm Gra H2O ~ 3.5 3.6 3.4 3.6 3.4 3.4 3.0 Application Blown film Flat film (+) (+) (+) (+) Sheets + + + + + + +
Injection mol- + + + + + + +
ding ~0.2%* ~0.2%* ~0.2%* ~0.2%* ~0.2%* ~0.2%* ~0.2%*
Fibers -Starch = nat ve potato st~rch dried 3.~% H20, sorbitol =
sorbitol LG DHR 71%, glycerol 99.5%;
2TPS = thermoplastic starch = starch+sorbitol+glycerol c 0.1%
H20. - Water content by devolatilization, according to the known process EP O 397 819 anhydrous TPS consists of starch, sorbitol and glycerol;
CA 02217~41 1997-10-06 3Filler, micronized cellulose;
4Polyamide 1 = Bayer BAK 1095 polyesteramide MFI 2.5 150~C
2.16 kg;
sPolyester 1 = BASF ZK 242/108 copolyester of aliphatic diols and aliphatic/aromatic dicarboxylic acids MVR 3.0 at 190~C/2.16 kg;
6Filler, micronized cotton 7Extrusion Equipment = Werner&Pfleiderer ZSK 40;
~0.1 - 0.4% water content CA 02217~41 1997-10-06 Table 4 Examples Example 22 23 24 25 26 27** 28**
Starch % 34.5 35.5 40.5 50.5 60.7 70.3 67.8 lSorbitol % - - _, _ _ _ _ 'Glycerol % 16.3 16.5 12.0 7.1 4.0 4.5 2Polyamide 1 25.0 23.5 47.5 42.4 35.3 25.2 32.2 3TPS% 74.8 74.4 98.6 98.5 98.2 87.4 87.8 H20 % ~0.1 <0.1 ~0.1 ~0.1 ~0.1 ~0.1 ~0.1 ~PLA 24.2 - - - - - -sPolyester 1 - 24.5 H20 % ~0.1 ~0.1 ~0.1 ~0.1 ~0.1 ~0.1 ~0.1 7Extrusion ZSK 40 ZSK 40 ZSK 40 ZSK 40 ZSK 40 ZSK 40 ZSK 40 T ~C 200 206 190 170 160 155 155 Pressure bar 15 15 20 26 31 35 37 MFI g/10' 12 14 122.5 10 6 5 5.5 Granules 4 mm 4 mm 4 mm 4 mm 4 mm 4 mm 4 mm Gra H2O % 2.1 2.1 2.2 2.6 0.4 0.4 0.3 Application Blown film + + + + + + +
Flat film + + + + + + +
Sheets + + + + + + +
Injection - - - (+) +~ + +
molding 0.15~* c 0.2%* <0.2%*
Fibers 1Starch = native potato starch dried 3.5% H2O, sorbitol =
sorbitol LG DHR 71%, glycerol 99.5%;
4Polyamide 1 = Bayer BAK 1095 polyesteramide MFI 2.5 150~C
2.16 kg, function of plasticizer;
2TPS = thermoplastic starch = starch+sorbitol+glycerol and/or CA 022l7~4l l997-l0-06 BAK 1095, < 0.1% H2O. - Water content by devolatilization, according to the known process EP 0 397 819. 27** + 28**
starch = native potato starch 18% H2O:
3PLA (Polylactic acid resin) = Mitsui Toatsu Chemicals LACEA
H 100 MFR 13 190~C 2.16 kg;
5Polyester 1 = BASF ZK 242/108 copolyester of aliphatic diols and aliphatic/aromatic dicarboxylic acids MVR 3.0 at 190~C/2.16 kg;
6PCL (Polycaprolactone) = Union Carbide Tone Polymer P-787 MFI 1.0 125~C 44psi g/10 min;
7Extrusion Equipment = Werner&Pfleiderer ZSK 40;
~0.1 - 0.4~ water content CA 02217~41 1997-10-06 Experiment Example 29:
In analogy to experiment 28, the polyesteramide BAK 1095 was in example 29 compounded with 10~ potato starch in the twin-screw extruder ZSK 40 at 155~C and 20 bar with removal of water, extruded with 0.15~ residual moisture, and, after the polyester extrudate had cooled, was granulated. The polymer mixture has an MFI g/10' of 25 at 150~C/5 kg and is suitable for producing blown and flat films.
Injection moldings, extrudates and films produced by means of polymer mixtures proposed in accordance with the invention have not only relatively good material properties but also an outstanding biological degradability, which is why they are able to make a significant contribution to the acute problem of waste. For example, films produced from a polymer mixture proposed in accordance with the invention are outstandingly suitable for a very wide variety of applications in the agricultural sector, for example for the covering of fields, since such films after their use can either be composted or else ploughed into the earth in the field. Polymer mixtures of this kind are also suitable for the production of composting sacks, containers for composting waste, etc. In addition, containers and bottles, for example, can be produced from the polymer mixture proposed in accordance with CA 02217~41 1997-10-06 the invention by means of blow molding.
The polymer mixtures according to the invention are also suitable, however, for the production of textile articles, for example for the production of fibers, monofilaments, sheetlike structures, such as wovens, felts, nonwovens, so-called backsheets, textile composites, flocks, wadding, and linear structures, for example filaments, yarns, cables, cords, etc. In particular it has been found in practice that the polymer mixtures according to the invention are suitable for the production of sanitary articles, such as diapers, sanitary towels, incontinence products and bed liners. The structure of these hygiene articles includes, inter alia, nonwovens produced from the polymer material according to the invention, since this material has a very good skin compatibility, is respiratorily active, is permeable to water vapor at the same time as being watertight, and yet is fully biologically degradable.
A large proportion of the polymer mixtures proposed in accordance with the invention, especially those containing thermoplastic starch and/or a copolyester and/or a polyester-amide and/or a polyesterurethane, are suitable, moreover, as adhesives or else can be used as coatings, for example for the impregnation of textile wovens. In this case it has been CA 02217~41 1997-10-06 found that the polymer mixtures proposed in accordance with the invention which are suitable for these areas of application are introduced and applied preferably in a form in which they are at least partially dissolved in alcoholic solvents. For example, in connection with experiment example 29 it was found, surprisingly, that the polymer mixture thus prepared is soluble in hot alcohol/ethanol mixture. A 20%
strength alcoholic solution directly after preparation has a viscosity of lOOm Pas. In this case too there was a possible use in the context of a biologically degradable adhesive, as a coating or as an impregnation which brings about hydrophobic properties and is permeable to water vapor. The use ascertained with regard to experiment example 29 can also be transferred to a large number of the other experiment examples and to further polymer mixtures proposed in accordance with the invention.
The polymer mixtures according to the invention are, however, of course suitable for umpteen other applications, for example for disposable injection-molded products, etc.
Claims (28)
1. Biologically degradable polymer mixture, comprising at least one biopolymer prepared on the basis of renewable raw materials, characterized in that there is present as the biopolymer as least thermoplastic starch which is obtainable by mixing native starch or a derivative thereof with at least one plasticizing or swelling agent in the order of magnitude of 10 - 40% by weight, based on the mixture with native starch or a derivative thereof, at a water content < 5% by weight, the plasticizing or swelling agent being suitable for at least swelling or dissolving the starch or the derivative, and in that in the polymer mixture there is provided at least one polymer selected from the following list:
- an aromatic polyester, - a polyester copolymer having both aliphatic and aromatic blocks, - a polyesteramide, - a polyethylene oxide polymer or a polyglycol, - a polyesterurethane - and/or mixtures thereof, where the polymer mixture is obtainable by mixing the thermoplastic starch with the polymer of which there is at least one at a water content < 1% by weight, based on the polymer mixture.
- an aromatic polyester, - a polyester copolymer having both aliphatic and aromatic blocks, - a polyesteramide, - a polyethylene oxide polymer or a polyglycol, - a polyesterurethane - and/or mixtures thereof, where the polymer mixture is obtainable by mixing the thermoplastic starch with the polymer of which there is at least one at a water content < 1% by weight, based on the polymer mixture.
2. Biologically degradable polymer mixture according to claim 1, characterized in that the thermoplastic starch contains, as swelling or plasticizing agent, at least one of the following substances: sorbitol, glycerol, a hydroxy acid, such as lactic acid or oligomers thereof and/or their salts, polyvinyl alcohol, an aliphatic polyester, such as low molecular polylactic acid or polycaprolactone, a polyester-amide and/or mixtures thereof.
3. Biologically degradable polymer mixture according to one of claims 1 or 2, characterized in that the polyester copolymer is prepared, besides polyols, from aromatic or aliphatic dicarboxylic acids.
4. Biologically degradable polymer mixture according to one of claims 1 - 3, characterized in that the polyester copolymer has the following general structure:
where 1 and m are variable and are subject to a distribution and their mean values are guided by the composition of the reaction mixture.
where 1 and m are variable and are subject to a distribution and their mean values are guided by the composition of the reaction mixture.
5. Biologically degradable polymer mixture according to one of claims 1 - 4, characterized in that the polyester copolymer is prepared by polycondensation of, on the one hand, at least one diol from the series 1,2-ethanediol, 1,3-propane-diol, 1,4-butanediol and/or 1,6-hexanediol with, on the other hand, at least one aromatic dicarboxylic acid, for example terephthalic acid and, if desired, at least one aliphatic dicarboxylic acid, such as adipic acid and/or sebacic acid.
6. Biologically degradable polymer mixture according to one of claims 1 - 5, characterized in that the polyester copolymer is a polyalkylene terephthalate or a polyethylene terephthalate.
7. Biologically degradable polymer mixture according to one of claims 1 - 6, characterized in that an aliphatic polyester or copolyester, for example polylactic acid, poly-hydroxybutyric acid, polyhydroxybenzoic acid, polyhydroxy-butyric acid-hydroxyvaleric acid copolymer or polycaprolactone, is provided as a further component.
8. Biologically degradable polymer mixture according to claim 7, characterized by thermoplastic starch, at least one polyethylene terephthalate or a polyalkylene terephthalate and by polycaprolactone.
9. Biologically degradable polymer mixture according to one of claims 1 - 8, characterized in that the mixture contains a block copolymer as phase mediator, obtained by anhydrous mixing and reacting in the melt of starch or thermoplastic starch with at least one of the following polymers:
- a polyester copolymer having aliphatic and aromatic blocks, - an aromatic polyester, - an aliphatic polyester, - a polyesteramide and/or - a polyesterurethane.
- a polyester copolymer having aliphatic and aromatic blocks, - an aromatic polyester, - an aliphatic polyester, - a polyesteramide and/or - a polyesterurethane.
10. Biologically degradable polymer mixture according to one of claims 1 - 9, characterized in that at least one further component, such as an additive, adjuvant or filler, is included, such as a plasticizer, a stabilizer, an antiflaming agent, a further biologically degradable biopolymer, such as cellulose ester, cellulose, polyhydroxybutyric acid, a hydrophobic protein, polyvinyl alcohol, gelatin, zein, polysaccharide, polylactide, polyvinyl acetate, polyacrylate, a sugar alcohol, shellac, casein, a fatty acid derivative, plant fibers, lecithin or chitosan.
11. Biologically degradable polymer mixture according to one of claims 1 - 10, characterized in that the polymer mixture at least one organic filler obtained from renewable raw materials, such as especially cellulose fibers.
12. Biologically degradable polymer mixture according to one of claims 1 - 11, characterized in that for the further reduction of the hydrophilic properties of the thermoplastic starch there is provided a crosslinking agent, for example a dicarboxylic acid or a polycarboxylic acid and the anhydride thereof, an isocyanate, formaldehyde and derivatives thereof, urea-formaldehyde, a melamine-formaldehyde or a phenol-formaldehyde resin, phosphate, polyphosphate, and/or an = = O
where R = linearly saturated alkyl group in the range from C12 to C24.
where R = linearly saturated alkyl group in the range from C12 to C24.
13. Biologically degradable polymer mixture according to one of claims 1 - 12, characterized in that the proportion of thermoplastic starch containing a plasticizing or a swelling agent amounts to 10 - 95% by weight, based on the overall weight of the mixture.
14. Biologically degradable polymer mixture according to one of claims 1 - 13, characterized in that the proportion of thermoplastic starch in the mixture amounts to 40 - 65% by weight.
15. Biologically degradable polymer mixture according to one of claims 1 - 5, characterized by thermoplastic starch, a polyester copolymer having both aliphatic and aromatic blocks and a copolymer selected from ethylene-acrylic acid copolymer and ethylene vinyl alcohol copolymer.
16. Process for preparing a polymer mixture according to one of claims 1 - 15, characterized in that thermoplastic starch, obtained by exothermic conversion of native starch or a derivative thereof, is mixed with at least one of the following polymers:
- an aromatic polyester - a polyester copolymer having aromatic and aliphatic blocks, - a polyesteramide, - a polyethylene oxide polymer or polyglycol, - a polyesterurethane - and/or mixtures, where the mixing of the melt takes place and the water content is reduced, before and/or during mixing, to < 1.0% by weight, based on the weight of the mixture.
- an aromatic polyester - a polyester copolymer having aromatic and aliphatic blocks, - a polyesteramide, - a polyethylene oxide polymer or polyglycol, - a polyesterurethane - and/or mixtures, where the mixing of the melt takes place and the water content is reduced, before and/or during mixing, to < 1.0% by weight, based on the weight of the mixture.
17. Process according to claim 16, characterized in that an aliphatic polyester is additionally added to the melt.
18. Process according to one of claims 16 or 17, characterized in that the water content is reduced before or during mixing to < 0.5% by weight, preferably < 0.1% by weight.
19. Process according to one of claims 16 - 18, characterized in that the mixing of the melt takes place in a temperature range of 120 - 260°C.
20. Process according to one of claims 16 - 19, characterized in that mixing takes place in an extruder or kneader and in that after the melt has been removed from the die it is cooled in a water bath and conditioned before being subsequently granulated, for example.
21. Method of processing a polymer mixture according to one of claims 1 - 15, characterized in that the polymer mixture, which is present for example as granules, is conditioned before processing by injection molding, extrusion or blowing with a plasticizer, such as glycerol, sorbitol, etc. and/or water.
22. Method according to claim 21, characterized in that the polymer mixture, which is present as granules is conditioned to a water content of 1 - 6% by weight and is subsequently injection-molded, extruded or blown to films, the injection molding or extrudate or film produced preferably being stored directly after its preparation in a relatively moist environment having a relative humidity > 40%.
23. Use of a polymer mixture according to one of claims 1 to 15 for the production of a single-layer or multilayer film.
24. Use of a polymer mixture according to claims 1 to 15 for the production of a container or a bottle produced by means of blow molding.
25. Use of a polymer mixture according to one of claims 1 to 15 for the production of textile products, such as fibers, monofilaments, yarns, cables, cords, flocks, wadding, wovens, felts, nonwovens.
26. Use of a polymer mixture according to one of claims 1 to 15 for the production of sanitary articles, such as diapers, sanitary towels, incontinence products, bed liners and the like having at least one nonwoven and/or a backsheet, consisting of the polymer mixture.
27. Use of a polymer mixture according to one of claims 1 to 15 or of an alcoholic solution thereof for the production of an adhesive.
28. Use of a polymer mixture according to one of claims 1 to 15 or an alcoholic solution thereof for the production of a coating, such as especially an impregnating composition.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE1995113237 DE19513237A1 (en) | 1995-04-07 | 1995-04-07 | Bio-degradable polymer mixt. for adhesive, hygiene articles etc. |
| DE19513237.8 | 1995-04-24 | ||
| DE19515013 | 1995-04-24 | ||
| DE19515013.9 | 1995-04-24 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2217541A1 true CA2217541A1 (en) | 1996-10-10 |
Family
ID=26014241
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002217541A Abandoned CA2217541A1 (en) | 1995-04-07 | 1996-04-02 | Biologically degradable polymer mixture |
Country Status (12)
| Country | Link |
|---|---|
| US (2) | US6096809A (en) |
| EP (1) | EP0819147B1 (en) |
| JP (1) | JP3107830B2 (en) |
| CN (1) | CN1181098A (en) |
| AT (1) | ATE242295T1 (en) |
| AU (1) | AU705499B2 (en) |
| CA (1) | CA2217541A1 (en) |
| DE (1) | DE59610506D1 (en) |
| DK (1) | DK0819147T3 (en) |
| ES (1) | ES2201173T3 (en) |
| PT (1) | PT819147E (en) |
| WO (1) | WO1996031561A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011117549A1 (en) | 2010-03-25 | 2011-09-29 | Roquette Freres | Plant material compositions and method for preparing same |
Families Citing this family (183)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7176251B1 (en) | 1996-11-05 | 2007-02-13 | Novamont S.P.A. | Biodegradable polymeric compositions comprising starch and a thermoplastic polymer |
| AU7544398A (en) * | 1997-06-20 | 1999-01-04 | Bio-Tec Biologische Naturverpackungen Gmbh & Co. Kg | Disposable articles for the military or pyrotechnic industries, non-folding roads, driving or walking aids made of biodegradable materials |
| DE19822979A1 (en) * | 1998-05-25 | 1999-12-02 | Kalle Nalo Gmbh & Co Kg | Film with starch or starch derivatives and polyester urethanes and process for their production |
| WO1999065977A1 (en) * | 1998-06-17 | 1999-12-23 | Bio-Tec Biologische Naturverpackungen Gmbh & Co. Kg | Foamed thermoplastic film made from biodegradable materials |
| ITTO980524A1 (en) * | 1998-06-17 | 1999-12-17 | Novamont Spa | COMPOSITIONS CONTAINING STARCH WITH HIGH RESISTANCE TO AGING. |
| DE19860836C1 (en) * | 1998-12-30 | 2000-05-18 | Haller Formholz | Continuous extrusion of products based on plant material and thermoplastic binder by compressing the plant material, adding plastic and compressing and relaxing mixture |
| US6440364B1 (en) * | 1999-02-16 | 2002-08-27 | Ethicon, Inc. | Method of degassing absorbable suture products |
| NZ503231A (en) | 1999-03-08 | 2001-09-28 | Humatro Corp | Absorbent, flexible structure comprising pseudo-thermoplastic starch fibers, plasticizer (such as sorbitol, PVA) |
| US6632925B1 (en) * | 1999-05-04 | 2003-10-14 | Iowa State University Research Foundation, Inc. | Biodegradable plant protein composites and related methods |
| US6515054B1 (en) | 1999-11-02 | 2003-02-04 | Nippon Shokubai Co., Ltd. | Biodegradable resin composition and its molded product |
| US6231970B1 (en) * | 2000-01-11 | 2001-05-15 | E. Khashoggi Industries, Llc | Thermoplastic starch compositions incorporating a particulate filler component |
| KR20010081685A (en) * | 2000-02-18 | 2001-08-29 | 윤여생 | Container of Plastic having biodegradation and hygroscopic property |
| US20020028857A1 (en) * | 2000-03-31 | 2002-03-07 | Holy Norman L. | Compostable, degradable plastic compositions and articles thereof |
| DE10027905A1 (en) * | 2000-06-06 | 2001-12-13 | Bayer Ag | Biodegradable molding composition, useful for the production of plant covers, disposable cutlery, casings or packaging, comprises a biodegradable polymer and a mineral and/or a renewable material, |
| AU2001276597A1 (en) * | 2000-08-11 | 2002-02-25 | Bio-Tec Biologische Naturverpackungen Gmbh And Co.Kg | Biodegradable polymeric blend |
| US6573340B1 (en) * | 2000-08-23 | 2003-06-03 | Biotec Biologische Naturverpackungen Gmbh & Co. Kg | Biodegradable polymer films and sheets suitable for use as laminate coatings as well as wraps and other packaging materials |
| JP2002088161A (en) * | 2000-09-14 | 2002-03-27 | Sony Corp | Method for improving modulus of elasticity of biodegradable resin |
| US7402618B2 (en) * | 2000-11-23 | 2008-07-22 | Hao Xu | Biodegradable composition for the preparation of tableware, drink container, mulching film and package and method for preparing the same |
| CN1121452C (en) * | 2000-11-23 | 2003-09-17 | 许浩 | Formular and preparing process of environment protection type biodegradable dinner set |
| US7029620B2 (en) | 2000-11-27 | 2006-04-18 | The Procter & Gamble Company | Electro-spinning process for making starch filaments for flexible structure |
| US20030203196A1 (en) * | 2000-11-27 | 2003-10-30 | Trokhan Paul Dennis | Flexible structure comprising starch filaments |
| US6811740B2 (en) | 2000-11-27 | 2004-11-02 | The Procter & Gamble Company | Process for making non-thermoplastic starch fibers |
| US7297394B2 (en) * | 2002-03-01 | 2007-11-20 | Bio-Tec Biologische Naturverpackungen Gmbh & Co. Kg | Biodegradable films and sheets suitable for use as coatings, wraps and packaging materials |
| US7241832B2 (en) * | 2002-03-01 | 2007-07-10 | bio-tec Biologische Naturverpackungen GmbH & Co., KG | Biodegradable polymer blends for use in making films, sheets and other articles of manufacture |
| WO2002083784A1 (en) * | 2001-04-18 | 2002-10-24 | Food & Packaging Centre Management Limited | Biodegradable polymer |
| US6783854B2 (en) * | 2001-05-10 | 2004-08-31 | The Procter & Gamble Company | Bicomponent fibers comprising a thermoplastic polymer surrounding a starch rich core |
| US6623854B2 (en) | 2001-05-10 | 2003-09-23 | The Procter & Gamble Company | High elongation multicomponent fibers comprising starch and polymers |
| US6946506B2 (en) | 2001-05-10 | 2005-09-20 | The Procter & Gamble Company | Fibers comprising starch and biodegradable polymers |
| US20030148690A1 (en) | 2001-05-10 | 2003-08-07 | Bond Eric Bryan | Multicomponent fibers comprising a dissolvable starch component, processes therefor, and fibers therefrom |
| US20020168912A1 (en) * | 2001-05-10 | 2002-11-14 | Bond Eric Bryan | Multicomponent fibers comprising starch and biodegradable polymers |
| US20030077444A1 (en) | 2001-05-10 | 2003-04-24 | The Procter & Gamble Company | Multicomponent fibers comprising starch and polymers |
| US6743506B2 (en) | 2001-05-10 | 2004-06-01 | The Procter & Gamble Company | High elongation splittable multicomponent fibers comprising starch and polymers |
| US20020168518A1 (en) * | 2001-05-10 | 2002-11-14 | The Procter & Gamble Company | Fibers comprising starch and polymers |
| US7276201B2 (en) * | 2001-09-06 | 2007-10-02 | The Procter & Gamble Company | Process for making non-thermoplastic starch fibers |
| US7071249B2 (en) * | 2001-10-05 | 2006-07-04 | William Ho | Biodegradable starch resin and method for making same |
| US7077994B2 (en) * | 2001-10-19 | 2006-07-18 | The Procter & Gamble Company | Polyhydroxyalkanoate copolymer/starch compositions for laminates and films |
| DE10214327A1 (en) | 2001-10-23 | 2003-05-22 | Innogel Ag Zug | Polysaccharide-based network and process for its manufacture |
| US6723160B2 (en) * | 2002-02-01 | 2004-04-20 | The Procter & Gamble Company | Non-thermoplastic starch fibers and starch composition for making same |
| US7217426B1 (en) | 2002-06-21 | 2007-05-15 | Advanced Cardiovascular Systems, Inc. | Coatings containing polycationic peptides for cardiovascular therapy |
| US7005137B1 (en) * | 2002-06-21 | 2006-02-28 | Advanceed Cardiovascular Systems, Inc. | Coating for implantable medical devices |
| US6821538B2 (en) * | 2002-07-09 | 2004-11-23 | T.F.H. Publications, Inc. | Blends of starch and aliphatic-aromatic based polyester resins |
| US6830810B2 (en) * | 2002-11-14 | 2004-12-14 | The Procter & Gamble Company | Compositions and processes for reducing water solubility of a starch component in a multicomponent fiber |
| DE10258227A1 (en) * | 2002-12-09 | 2004-07-15 | Biop Biopolymer Technologies Ag | Biodegradable multilayer film |
| DE10261786A1 (en) * | 2002-12-23 | 2004-07-01 | Fritz Häcker GmbH + Co.KG | Gelatin based adhesive that is solid at normal temperature, useful for the production of multi-layer tissues and paper towels, contains a water soluble polymer that embues the adhesive with fiber-drawing properties |
| US8791171B2 (en) | 2003-05-01 | 2014-07-29 | Abbott Cardiovascular Systems Inc. | Biodegradable coatings for implantable medical devices |
| US7098292B2 (en) * | 2003-05-08 | 2006-08-29 | The Procter & Gamble Company | Molded or extruded articles comprising polyhydroxyalkanoate copolymer and an environmentally degradable thermoplastic polymer |
| US6706942B1 (en) | 2003-05-08 | 2004-03-16 | The Procter & Gamble Company | Molded or extruded articles comprising polyhydroxyalkanoate copolymer compositions having short annealing cycle times |
| US7172814B2 (en) * | 2003-06-03 | 2007-02-06 | Bio-Tec Biologische Naturverpackungen Gmbh & Co | Fibrous sheets coated or impregnated with biodegradable polymers or polymers blends |
| US7947766B2 (en) | 2003-06-06 | 2011-05-24 | The Procter & Gamble Company | Crosslinking systems for hydroxyl polymers |
| WO2005052056A1 (en) * | 2003-11-25 | 2005-06-09 | Asahi Kasei Life & Living Corporation | Matte film |
| US7368503B2 (en) * | 2003-12-22 | 2008-05-06 | Eastman Chemical Company | Compatibilized blends of biodegradable polymers with improved rheology |
| US7160977B2 (en) * | 2003-12-22 | 2007-01-09 | Eastman Chemical Company | Polymer blends with improved notched impact strength |
| US7368511B2 (en) * | 2003-12-22 | 2008-05-06 | Eastman Chemical Company | Polymer blends with improved rheology and improved unnotched impact strength |
| US7326659B2 (en) * | 2004-02-16 | 2008-02-05 | Conwed Plastics Llc | Biodegradable netting |
| US7153569B2 (en) * | 2004-03-19 | 2006-12-26 | Kimberly-Clark Worldwide, Inc. | Biodegradable aliphatic-aromatic copolyester films |
| US7776020B2 (en) * | 2004-03-19 | 2010-08-17 | Kimberly-Clark Worldwide, Inc. | Absorbent articles having an aliphatic-aromatic copolyester film |
| ITMI20040720A1 (en) * | 2004-04-09 | 2004-07-09 | Novamont Spa | BIODEGRADABLE FILM BAG WITH HIGH RESPIRABILITY |
| US6977116B2 (en) * | 2004-04-29 | 2005-12-20 | The Procter & Gamble Company | Polymeric structures and method for making same |
| US6955850B1 (en) | 2004-04-29 | 2005-10-18 | The Procter & Gamble Company | Polymeric structures and method for making same |
| WO2005113106A1 (en) * | 2004-05-07 | 2005-12-01 | Profile Products L.L.C. | Composite fiber environmental filtration media containing flocculant |
| DK1602600T3 (en) * | 2004-06-03 | 2020-01-27 | Novamont Spa | Ventilated system for organic waste collection |
| ITMI20041125A1 (en) * | 2004-06-03 | 2004-09-03 | Novamont Spa | VENTILATED SYSTEM FOR BIODEGRADABLE BAGS |
| DE102004027673B3 (en) * | 2004-06-07 | 2006-01-19 | Universität Ulm | Biodegradable composite system and its use, as well as methods of making a biodegradable block copolyester urethane |
| US7244443B2 (en) | 2004-08-31 | 2007-07-17 | Advanced Cardiovascular Systems, Inc. | Polymers of fluorinated monomers and hydrophilic monomers |
| US7629405B2 (en) * | 2004-11-19 | 2009-12-08 | Board Of Trustees Of Michigan State University | Starch-polyester biodegradable graft copolyers and a method of preparation thereof |
| US20090160095A1 (en) * | 2004-11-19 | 2009-06-25 | Board Of Trustees Of Michigan State University | Biodegradable thermoplasticized starch-polyester reactive blends for thermoforming applications |
| ITMI20050452A1 (en) * | 2005-03-18 | 2006-09-19 | Novamont Spa | ALYPATIC-AROMATIC BIODEGRADABLE POLYESTER |
| US20070021515A1 (en) * | 2005-07-19 | 2007-01-25 | United States (as represented by the Secretary of Agriculture) | Expandable starch-based beads and method of manufacturing molded articles therefrom |
| US7989524B2 (en) * | 2005-07-19 | 2011-08-02 | The United States Of America, As Represented By The Secretary Of Agriculture | Fiber-reinforced starch-based compositions and methods of manufacture and use |
| US8435354B2 (en) * | 2005-10-11 | 2013-05-07 | The Procter & Gamble Company | Water stable compositions and articles comprising starch and methods of making the same |
| US20070128459A1 (en) * | 2005-12-07 | 2007-06-07 | Kurian Joseph V | Poly(trimethylene terephthalate)/poly(alpha-hydroxy acid) films |
| US20070129503A1 (en) * | 2005-12-07 | 2007-06-07 | Kurian Joseph V | Poly(trimethylene terephthalate)/poly(alpha-hydroxy acid) molded, shaped articles |
| US7666501B2 (en) * | 2005-12-07 | 2010-02-23 | E. I. Du Pont De Nemours And Company | Poly(trimethylene terephthalate)/poly(alpha-hydroxy acid) bi-constituent filaments |
| PL2010380T5 (en) * | 2006-04-14 | 2016-10-31 | Biotec Biologische Naturverpackungen Gmbh & Co Kg | Multilayered film and method for manufacturing same |
| US9028859B2 (en) | 2006-07-07 | 2015-05-12 | Advanced Cardiovascular Systems, Inc. | Phase-separated block copolymer coatings for implantable medical devices |
| JP5030501B2 (en) * | 2006-07-31 | 2012-09-19 | 関西ペイント株式会社 | Starch-based paint composition |
| US7909003B2 (en) | 2006-08-07 | 2011-03-22 | J. W. Pet Company, Inc. | Chew toys comprising biologically degradable material |
| CN101506278B (en) * | 2006-08-31 | 2012-11-14 | 金伯利-克拉克环球有限公司 | Highly breathable biodegradable films |
| WO2008073099A1 (en) * | 2006-12-15 | 2008-06-19 | Kimberly-Clark Worldwide, Inc. | Biodegradable polyesters for use in forming fibers |
| US8592641B2 (en) | 2006-12-15 | 2013-11-26 | Kimberly-Clark Worldwide, Inc. | Water-sensitive biodegradable film |
| WO2008089098A1 (en) * | 2007-01-12 | 2008-07-24 | L & P Property Management Company | Environmentally friendly polymeric textile coating |
| DE102007037166A1 (en) | 2007-08-07 | 2009-02-19 | Endress + Hauser Flowtec Ag | gauge |
| KR101420473B1 (en) * | 2007-08-14 | 2014-07-16 | 도요세이칸 그룹 홀딩스 가부시키가이샤 | Biodegradable resin container having deposited film, and method for formation of deposited film |
| US8329977B2 (en) | 2007-08-22 | 2012-12-11 | Kimberly-Clark Worldwide, Inc. | Biodegradable water-sensitive films |
| CA2688516A1 (en) * | 2007-10-03 | 2009-04-09 | Universidad De Concepcion | Biodegradable composition, preparation method and their application in the manufacture of functional containers for agricultural and/or forestry use |
| DE102007050770A1 (en) * | 2007-10-22 | 2009-04-23 | Biotec Biologische Naturverpackungen Gmbh & Co. Kg | Polymeric material and process for its preparation |
| DE102007050769A1 (en) | 2007-10-22 | 2009-04-23 | Biotec Biologische Naturverpackungen Gmbh & Co. Kg | Polymeric material and process for its preparation |
| DE102007057768A1 (en) * | 2007-11-30 | 2009-06-04 | Universität Ulm | Biodegradable composite system and its use |
| US8227658B2 (en) | 2007-12-14 | 2012-07-24 | Kimberly-Clark Worldwide, Inc | Film formed from a blend of biodegradable aliphatic-aromatic copolyesters |
| JP2009155531A (en) * | 2007-12-27 | 2009-07-16 | Mitsubishi Chemicals Corp | Resin composition, preparation method, and film including the resin composition |
| US7998888B2 (en) * | 2008-03-28 | 2011-08-16 | Kimberly-Clark Worldwide, Inc. | Thermoplastic starch for use in melt-extruded substrates |
| US8420710B2 (en) * | 2008-04-30 | 2013-04-16 | Armstrong World Industries, Inc. | UV/EB curable biobased coating for flooring application |
| AU2009241730B2 (en) * | 2008-04-30 | 2014-06-26 | Armstrong World Industries, Inc. | Biobased resilient floor tile |
| US8822584B2 (en) | 2008-05-06 | 2014-09-02 | Metabolix, Inc. | Biodegradable polyester blends |
| US8338508B2 (en) * | 2008-05-14 | 2012-12-25 | Kimberly-Clark Worldwide, Inc. | Water-sensitive film containing an olefinic elastomer |
| US8147965B2 (en) | 2008-05-14 | 2012-04-03 | Kimberly-Clark Worldwide, Inc. | Water-sensitive film containing thermoplastic polyurethane |
| US8470222B2 (en) | 2008-06-06 | 2013-06-25 | Kimberly-Clark Worldwide, Inc. | Fibers formed from a blend of a modified aliphatic-aromatic copolyester and thermoplastic starch |
| WO2009153275A1 (en) * | 2008-06-18 | 2009-12-23 | Basf Se | Glyoxal and methylglyoxal as additives for polymer blends |
| US8927617B2 (en) * | 2008-06-30 | 2015-01-06 | Kimberly-Clark Worldwide, Inc. | Fragranced water-sensitive film |
| US8188185B2 (en) * | 2008-06-30 | 2012-05-29 | Kimberly-Clark Worldwide, Inc. | Biodegradable packaging film |
| US8759279B2 (en) * | 2008-06-30 | 2014-06-24 | Kimberly-Clark Worldwide, Inc. | Fragranced biodegradable film |
| FR2934272B1 (en) * | 2008-07-24 | 2013-08-16 | Roquette Freres | PROCESS FOR THE PREPARATION OF COMPOSITIONS BASED ON AMYLACEOUS MATERIAL AND SYNTHETIC POLYMER |
| DE102008042893A1 (en) * | 2008-10-16 | 2010-04-29 | Wacker Chemie Ag | Mixtures for the production of biodegradable moldings based on aliphatic polyesters and water-redispersible polymer powders |
| US8283006B2 (en) * | 2008-12-18 | 2012-10-09 | Kimberly-Clark Worldwide, Inc. | Injection molding material containing starch and plant protein |
| US8329601B2 (en) | 2008-12-18 | 2012-12-11 | Kimberly-Clark Worldwide, Inc. | Biodegradable and renewable film |
| WO2010074185A1 (en) * | 2008-12-26 | 2010-07-01 | 三菱化学株式会社 | Resin composition, film, bag product, and process for producing resin composition |
| CN101525487B (en) * | 2009-03-31 | 2012-01-11 | 武汉华丽生物材料有限公司 | Composite material degraded by environment and preparation method thereof |
| AU2009202397A1 (en) * | 2009-06-16 | 2011-01-06 | Because We Care Pty Ltd | Biodegradable Polymeric Compositions |
| FR2947557B1 (en) | 2009-07-03 | 2011-12-09 | Ulice | PROCESS FOR PRODUCING BIODEGRADABLE MATERIAL |
| JP5519996B2 (en) | 2009-10-20 | 2014-06-11 | 日東電工株式会社 | Surface protection adhesive sheet |
| IT1396597B1 (en) | 2009-11-05 | 2012-12-14 | Novamont Spa | BIODEGRADABLE POLYESTER MIXTURES |
| IT1399031B1 (en) | 2009-11-05 | 2013-04-05 | Novamont Spa | BIODEGRADABLE ALIPHATIC-AROMATIC COPOLIESTERE |
| PT104846A (en) | 2009-11-26 | 2011-05-26 | Cabopol Ind De Compostos S A | POLYMERIC MIXTURES BIOFUELS |
| US8586821B2 (en) * | 2009-12-23 | 2013-11-19 | Kimberly-Clark Worldwide, Inc. | Melt-processed films of thermoplastic cellulose and microbial aliphatic polyester |
| CN102115576B (en) * | 2009-12-31 | 2014-09-17 | 金伯利-克拉克环球有限公司 | Natural biological polymer thermoplastic film |
| US9226524B2 (en) | 2010-03-26 | 2016-01-05 | Philip Morris Usa Inc. | Biopolymer foams as filters for smoking articles |
| US20120016328A1 (en) * | 2010-07-19 | 2012-01-19 | Bo Shi | Biodegradable films |
| US8907155B2 (en) | 2010-11-19 | 2014-12-09 | Kimberly-Clark Worldwide, Inc. | Biodegradable and flushable multi-layered film |
| RU2013125088A (en) | 2010-11-23 | 2014-12-27 | Дзе Проктер Энд Гэмбл Компани | THERMOPLASTIC COMPOSITIONS CONTAINING STARCH |
| US20120178858A1 (en) | 2011-01-10 | 2012-07-12 | Andrew Julian Wnuk | Isosorbide-Plasticized Starch And Uses Thereof |
| US20120283364A1 (en) * | 2011-05-06 | 2012-11-08 | Cerestech, Inc. | Polymer blends comprising phase-encapsulated thermoplastic starch and process for making the same |
| RU2013147758A (en) | 2011-05-20 | 2015-06-27 | Дзе Проктер Энд Гэмбл Компани | FILMS IN THE STARCH, POLYMER, WAX AND OIL COMPOSITIONS |
| EP2710072A1 (en) | 2011-05-20 | 2014-03-26 | The Procter and Gamble Company | Molded articles of starch-polymer-wax-oil compositions |
| US20130053478A1 (en) | 2011-05-20 | 2013-02-28 | Eric Bryan Bond | Starch-polymer-oil compositions, methods of making and using the same |
| CN103547715A (en) | 2011-05-20 | 2014-01-29 | 宝洁公司 | Fiber of starch- polymer -oil compositions |
| CN102321249B (en) | 2011-06-30 | 2013-01-16 | 无锡碧杰生物材料科技有限公司 | Thermoplastic starch (TPS), biodegradable polyester/starch composite material and preparation thereof |
| CN102295816B (en) * | 2011-07-05 | 2012-08-08 | 吉林大学 | Method for preparing full-degradable composite material filled with modified polylactic acid |
| US8933162B2 (en) | 2011-07-15 | 2015-01-13 | Saudi Basic Industries Corporation | Color-stabilized biodegradable aliphatic-aromatic copolyesters, methods of manufacture, and articles thereof |
| US9334360B2 (en) | 2011-07-15 | 2016-05-10 | Sabic Global Technologies B.V. | Color-stabilized biodegradable aliphatic-aromatic copolyesters, methods of manufacture, and articles thereof |
| US8877862B2 (en) | 2011-07-15 | 2014-11-04 | Saudi Basic Industries Corporation | Method for color stabilization of poly(butylene-co-adipate terephthalate |
| CN102912475A (en) * | 2011-08-04 | 2013-02-06 | 周新民 | Method for preparing high-strength chitosan fiber from multi-component coagulated bath lotion |
| US8946345B2 (en) | 2011-08-30 | 2015-02-03 | Saudi Basic Industries Corporation | Method for the preparation of (polybutylene-co-adipate terephthalate) through the in situ phosphorus containing titanium based catalyst |
| US9327438B2 (en) * | 2011-12-20 | 2016-05-03 | Kimberly-Clark Worldwide, Inc. | Method for forming a thermoplastic composition that contains a plasticized starch polymer |
| US9718258B2 (en) | 2011-12-20 | 2017-08-01 | Kimberly-Clark Worldwide, Inc. | Multi-layered film containing a biopolymer |
| US8901273B2 (en) | 2012-02-15 | 2014-12-02 | Saudi Basic Industries Corporation | Amorphous, high glass transition temperature copolyester compositions, methods of manufacture, and articles thereof |
| US8889820B2 (en) | 2012-02-15 | 2014-11-18 | Saudi Basic Industries Corporation | Amorphous, high glass transition temperature copolyester compositions, methods of manufacture, and articles thereof |
| US8969506B2 (en) | 2012-02-15 | 2015-03-03 | Saudi Basic Industries Corporation | Amorphous, high glass transition temperature copolyester compositions, methods of manufacture, and articles thereof |
| US9034983B2 (en) | 2012-03-01 | 2015-05-19 | Saudi Basic Industries Corporation | Poly(butylene-co-adipate terephthalate), method of manufacture and uses thereof |
| US8895660B2 (en) | 2012-03-01 | 2014-11-25 | Saudi Basic Industries Corporation | Poly(butylene-co-adipate terephthalate), method of manufacture, and uses thereof |
| EP2831186B1 (en) * | 2012-03-28 | 2019-06-19 | Thüringisches Institut Für Textil- Und Kunststoff- Forschung E.V. | Multifunctional coating films that can be applied in liquid form |
| US8901243B2 (en) | 2012-03-30 | 2014-12-02 | Saudi Basic Industries Corporation | Biodegradable aliphatic-aromatic copolyesters, methods of manufacture, and articles thereof |
| FR2992652B1 (en) * | 2012-06-27 | 2014-06-20 | Arkema France | USE OF A THERMOPLASTIC STARCH ALLOY AND TPE FOR THE MANUFACTURE OF A ULTRA-FINE IMPER-BREATHABLE ADHESIVE FILM. |
| FR2992651B1 (en) * | 2012-06-27 | 2015-07-17 | Arkema France | USE OF THERMOPLASTIC STARCH ALLOY AND POF FOR THE MANUFACTURE OF A ULTRA-FINE IMPER-BREATHABLE ADHESIVE FILM. |
| CN109054254B (en) | 2012-08-17 | 2021-02-02 | Cj第一制糖株式会社 | Bio-based rubber modifiers for polymer blends |
| JP6033008B2 (en) * | 2012-09-03 | 2016-11-30 | 株式会社クレハ | Resin composition and use thereof |
| GB201217207D0 (en) * | 2012-09-26 | 2012-11-07 | Biome Bioplastics Ltd | Bio-resins |
| CN102907362B (en) * | 2012-11-05 | 2014-05-28 | 连云港耐特网具有限公司 | Alga-resistant type sea farming net |
| WO2014081791A1 (en) | 2012-11-20 | 2014-05-30 | The Procter & Gamble Company | Starch-thermoplastic polymer-grease compositions and methods of making and using the same |
| WO2014081778A1 (en) | 2012-11-20 | 2014-05-30 | The Procter & Gamble Company | Starch-thermoplastic polymer-soap compositions and methods of making and using the same |
| WO2014151221A1 (en) | 2013-03-15 | 2014-09-25 | The Procter & Gamble Company | Renewable thermoplastic starch - polyolefin compositions comprising compatibilizer and flexible thin films made therefrom |
| CN105246972B (en) * | 2013-04-10 | 2018-06-08 | 生物天然包装材料研究与开发有限及两合公司 | Polymer composition |
| EP2799232A1 (en) | 2013-04-30 | 2014-11-05 | The Procter & Gamble Company | Flexible package |
| EP2799231A1 (en) | 2013-04-30 | 2014-11-05 | The Procter & Gamble Company | Flexible package |
| EP2999447B1 (en) | 2013-05-20 | 2019-10-23 | The Procter and Gamble Company | Nonwoven webs with visually distinct bond sites and method of making |
| US10669417B2 (en) | 2013-05-30 | 2020-06-02 | Cj Cheiljedang Corporation | Recyclate blends |
| WO2015066588A1 (en) | 2013-11-04 | 2015-05-07 | The Procter & Gamble Company | Thermoplastic polymer compositions having co-continuous plate-like morphology |
| WO2015149029A1 (en) | 2014-03-27 | 2015-10-01 | Metabolix, Inc. | Highly filled polymer systems |
| CA2945660A1 (en) | 2014-05-12 | 2015-11-19 | The Procter & Gamble Company | Microtextured films with improved tactile impression and/or reduced noise perception |
| ES2556680B1 (en) * | 2014-07-18 | 2016-11-03 | Moreda - Riviere Trefilerías, S.A. | Coated wire, procedure for obtaining it and mesh comprising it |
| CN104212166B (en) * | 2014-09-05 | 2016-06-29 | 东莞市瀛通电线有限公司 | A kind of holding wire degradation material and preparation method thereof |
| CN104371173A (en) * | 2014-11-07 | 2015-02-25 | 苏州维泰生物技术有限公司 | Master batch for degradable packaging materials and preparation method thereof |
| WO2016205018A1 (en) | 2015-06-17 | 2016-12-22 | Hollister Incorporated | Water disintegrable flushable catheter |
| CN104877320A (en) * | 2015-06-18 | 2015-09-02 | 王宏城 | Novel PLC composition for packaging materials and preparing method of novel PLC composition |
| MX2018004729A (en) | 2015-11-03 | 2018-07-06 | Kimberly Clark Co | Paper tissue with high bulk and low lint. |
| CN106544787A (en) * | 2016-12-12 | 2017-03-29 | 墨宝股份有限公司 | A kind of production technology of the non-woven new material with degradation function |
| EP3571254B1 (en) * | 2017-01-20 | 2023-09-27 | Meredian, Inc. | Biodegradable hot melt adhesives |
| CN106967279A (en) * | 2017-03-22 | 2017-07-21 | 中联西北工程设计研究院有限公司 | PLA, starch composite material and its preparation technology for 3D printing |
| EP3606353A1 (en) | 2017-04-06 | 2020-02-12 | Cryovac, LLC | Film, package and method for cheese ripening and preservation |
| US10435576B2 (en) | 2017-05-26 | 2019-10-08 | Infinite Material Solutions, Llc | Water soluble polymer compositions |
| EP3466388B1 (en) | 2017-10-06 | 2020-05-20 | The Procter & Gamble Company | Absorbent article comprising a nonwoven material with antimony-free polyethylene terephthalate |
| EP3466385B1 (en) | 2017-10-06 | 2020-05-27 | The Procter & Gamble Company | Absorbent article or wipe comprising a nonwoven material with bicomponent fibers comprising antimony-free polyethylene terephthalate |
| EP3466389B1 (en) | 2017-10-06 | 2020-05-20 | The Procter & Gamble Company | Absorbent article comprising a carded resin-bonded nonwoven web with fibers comprising antimony-free polyethylene terephthalate |
| CN107780041A (en) * | 2017-10-18 | 2018-03-09 | 芜湖缆胜电缆新材料有限公司 | A kind of netted gasket for packing of flame-retardant polypropelene and preparation method thereof |
| US11255051B2 (en) | 2017-11-29 | 2022-02-22 | Kimberly-Clark Worldwide, Inc. | Fibrous sheet with improved properties |
| CN108517621A (en) * | 2018-03-30 | 2018-09-11 | 徐冬 | A kind of preparation method of non-woven fabrics |
| MX2021000980A (en) | 2018-07-25 | 2021-04-12 | Kimberly Clark Co | Process for making three-dimensional foam-laid nonwovens. |
| PL3689955T3 (en) | 2019-02-01 | 2023-03-13 | United Resins - Produção De Resinas S.A. | Improved starch based biodegradable polymers |
| CN111038027A (en) * | 2019-12-21 | 2020-04-21 | 广东顺德贰发毛绒有限公司 | Production process of biodegradable electrostatic flocking paper product |
| US10882977B1 (en) * | 2020-01-30 | 2021-01-05 | Edward Showalter | Earth plant compostable biodegradable substrate and method of producing the same |
| US11149131B2 (en) * | 2020-01-30 | 2021-10-19 | Edward Showalter | Earth plant compostable biodegradable substrate and method of producing the same |
| WO2022253731A1 (en) * | 2021-06-02 | 2022-12-08 | Periplast Werkzeugbau Und Kunststoffverarbeitung Gmbh & Co. Kg | Thermoplastic material and method for producing a molded body from a thermoplastic material, and molded body |
| CN113462021B (en) * | 2021-07-19 | 2022-05-10 | 江南大学 | Natural filler, high-strength and high-toughness polymer composite material thereof, and preparation method and application thereof |
| CN116695273A (en) * | 2023-05-17 | 2023-09-05 | 百事基材料（青岛）股份有限公司 | Nylon large biological fiber containing saussurea involucrata active ingredient and preparation method thereof |
Family Cites Families (84)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3446079A (en) * | 1967-07-17 | 1969-05-27 | Singer General Precision | Linear electrostatic accelerometer |
| US3850863A (en) * | 1972-07-28 | 1974-11-26 | Union Carbide Corp | Blends of a biodegradable thermoplastic oxyalkanoyl polymer and a naturally occurring biodegradable product |
| US3921333A (en) * | 1972-07-28 | 1975-11-25 | Union Carbide Corp | Transplanter containers made from biodegradable-environmentally degradable blends |
| US3867324A (en) * | 1972-07-28 | 1975-02-18 | Union Carbide Corp | Environmentally degradable-biodegradable blend of an oxyalkanoyl polymer and an environmentally degradable ethylene polymer |
| US4076846A (en) * | 1974-11-22 | 1978-02-28 | Sumitomo Bakelite Company Limited | Protein-starch binary molding composition and shaped articles obtained therefor |
| US3949145A (en) * | 1975-02-27 | 1976-04-06 | The United States Of America As Represented By The Secretary Of Agriculture | Degradable starch-based agricultural mulch film |
| US4133784A (en) * | 1977-09-28 | 1979-01-09 | The United States Of America As Represented By The Secretary Of Agriculture | Biodegradable film compositions prepared from starch and copolymers of ethylene and acrylic acid |
| JPS6054322B2 (en) * | 1977-09-30 | 1985-11-29 | 株式会社林原生物化学研究所 | Manufacturing method for molded products |
| US4337181A (en) * | 1980-01-17 | 1982-06-29 | The United States Of America As Represented By The Secretary Of Agriculture | Biodegradable starch-based blown films |
| EP0045621B1 (en) * | 1980-08-06 | 1985-10-09 | Coloroll Limited | Plastics starch composition |
| US4410571A (en) * | 1980-08-25 | 1983-10-18 | Johnson & Johnson | Absorbent products, process and compositions for immobilization of particulate absorbents |
| US4394930A (en) * | 1981-03-27 | 1983-07-26 | Johnson & Johnson | Absorbent foam products |
| US4655840A (en) * | 1982-03-26 | 1987-04-07 | Warner-Lambert Company | Hydrophilic polymer compositions for injection molding |
| US4482386A (en) * | 1982-03-26 | 1984-11-13 | Warner-Lambert Company | Method of conditioning a water swellable hydrocolloid |
| US4454268A (en) * | 1983-06-23 | 1984-06-12 | The United States Of America As Represented By The Secretary Of Agriculture | Starch-based semipermeable films |
| US4673438A (en) * | 1984-02-13 | 1987-06-16 | Warner-Lambert Company | Polymer composition for injection molding |
| US4846932A (en) * | 1986-12-31 | 1989-07-11 | Kuromatsu Corporation Co., Ltd. | Water setting paper |
| GB2205323B (en) * | 1987-03-09 | 1991-01-30 | Warner Lambert Co | Destructurized starch and process for making same |
| GB2208651B (en) * | 1987-08-18 | 1991-05-08 | Warner Lambert Co | Shaped articles made from pre-processed starch |
| GB2214918B (en) * | 1988-02-03 | 1992-10-07 | Warner Lambert Co | Polymeric materials made from starch and at least one synthetic thermoplastic polymeric material |
| US5095054A (en) * | 1988-02-03 | 1992-03-10 | Warner-Lambert Company | Polymer compositions containing destructurized starch |
| IE66735B1 (en) * | 1988-11-03 | 1996-02-07 | Biotec Biolog Naturverpack | Thermoplastically workable starch and a method for the manufacture thereof |
| US5362777A (en) * | 1988-11-03 | 1994-11-08 | Ivan Tomka | Thermoplastically processable starch and a method of making it |
| US4863655A (en) * | 1988-12-30 | 1989-09-05 | National Starch And Chemical Corporation | Biodegradable packaging material and the method of preparation thereof |
| US5043196A (en) * | 1989-05-17 | 1991-08-27 | National Starch And Chemical Investment Holding Corporation | Biodegradable shaped products and the method of preparation thereof |
| US5035930A (en) * | 1988-12-30 | 1991-07-30 | National Starch And Chemical Investment Holding Corporation | Biodegradable shaped products and the method of preparation thereof |
| IL93620A0 (en) * | 1989-03-09 | 1990-12-23 | Butterfly Srl | Biodegradable articles based on starch and process for producing them |
| IT1233599B (en) * | 1989-05-30 | 1992-04-06 | Butterfly Srl | POLYMERIC COMPOSITIONS FOR THE PRODUCTION OF BIODEGRADABLE PLASTIC ITEMS AND PROCEDURES FOR THEIR PREPARATION |
| DE474705T1 (en) * | 1989-06-01 | 1992-10-15 | Goodman Fielder Wattie Australia Ltd., Gladesville, Neu Sued Wales, Au | SHAPED OBJECTS DERIVED FROM STRENGTH. |
| IL94647A0 (en) * | 1989-07-06 | 1991-04-15 | Warner Lambert Co | Polymer base blend compositions containing destructurized starch |
| FI102479B1 (en) * | 1989-07-11 | 1998-12-15 | Warner Lambert Co | Polymer-based blend compositions containing modified starch for its structure |
| YU128990A (en) * | 1989-07-11 | 1993-05-28 | Warner-Lambert Co. | PREPARATIONS OF POLYMER MIXTURES CONTAINING DESTRUCTURED STARCH |
| KR0178391B1 (en) * | 1989-07-18 | 1999-05-15 | 토마스 디. 몰리터노 | Polymer base blend compositions containing destructured starch |
| PT94658B (en) * | 1989-07-18 | 1997-02-28 | Warner Lambert Co | PROCESS FOR THE PREPARATION OF POLYMERIC BASED COMPOSITIONS OF DESERATED FRUIT AND PRODUCTS THAT CONTAIN THEM |
| US5288765A (en) * | 1989-08-03 | 1994-02-22 | Spherilene S.R.L. | Expanded articles of biodegradable plastics materials and a method for their production |
| IT1232910B (en) * | 1989-08-07 | 1992-03-05 | Butterfly Srl | POLYMERIC COMPOSITIONS FOR THE PRODUCTION OF BIODEGRADABLE PLASTIC ITEMS AND PROCEDURES FOR THEIR PREPARATION |
| US5059642A (en) * | 1989-09-14 | 1991-10-22 | Iowa State University Research Foundation, Inc. | Degradable plastics from octenyl succinate starch |
| JPH03199245A (en) * | 1989-12-27 | 1991-08-30 | Agency Of Ind Science & Technol | Microorganism-degradable thermoplastic resin foam and production thereof |
| DE69125965T2 (en) * | 1990-02-28 | 1997-09-25 | Agency Ind Science Techn | Process for the production of a biodegradable, moldable material |
| US5108807A (en) * | 1990-03-14 | 1992-04-28 | First Brands Corporation | Degradable multilayer thermoplastic articles |
| US5219646A (en) * | 1990-05-11 | 1993-06-15 | E. I. Du Pont De Nemours And Company | Polyester blends and their use in compostable products such as disposable diapers |
| US5115000A (en) * | 1990-06-19 | 1992-05-19 | Iowa State University Research Foundation, Inc. | Biodegradable starch plastics incorporating modified polyethylene |
| IT1240503B (en) * | 1990-07-25 | 1993-12-17 | Butterfly Srl | STARCH POLYMERIC MIXTURE PARTICULARLY FOR THE PRODUCTION OF FILMS AND SIMILAR AND PROCEDURE FOR ITS PRODUCTION. |
| GB9017300D0 (en) * | 1990-08-07 | 1990-09-19 | Cerestar Holding Bv | Starch treatment process |
| WO1992009654A2 (en) * | 1990-11-30 | 1992-06-11 | Eastman Kodak Company | Aliphatic-aromatic copolyesters and cellulose ester/polymer blends |
| US5046730A (en) * | 1990-12-10 | 1991-09-10 | Bio Dynamics, Ltd. | Golf tee |
| US5292782A (en) * | 1991-02-20 | 1994-03-08 | Novamont S.P.A. | Biodegradable polymeric compositions based on starch and thermoplastic polymers |
| US5186990A (en) * | 1991-04-05 | 1993-02-16 | Eagle Scientific Co. | Biodegradable and water soluble packaging material |
| JP2527523B2 (en) * | 1991-05-03 | 1996-08-28 | ノバモント・ソシエタ・ペル・アチオニ | Biodegradable polymer composition based on starch and thermoplastic polymer |
| EP0525245A1 (en) * | 1991-08-01 | 1993-02-03 | NOVAMONT S.p.A. | Disposable absorbent articles |
| US5412005A (en) * | 1991-05-03 | 1995-05-02 | Novamont S.P.A. | Biodegradable polymeric compositions based on starch and thermoplastic polymers |
| IT1256693B (en) * | 1992-03-10 | 1995-12-12 | Novamont Spa | FILMABLE AMIDACEA POLYMERIC COMPOSITION, AND SHAPED ITEMS, PARTICULARLY FILMS AND LEAVES OBTAINED FROM SUCH COMPOSITION, HAVING HIGH BARRIER EFFECT AND RELATED PROCEDURE. |
| DE4116404A1 (en) * | 1991-05-18 | 1992-11-19 | Tomka Ivan | POLYMERMISCHUNG FOR THE MANUFACTURE OF FOILS |
| KR100215378B1 (en) * | 1991-06-26 | 1999-09-01 | 데이비드 엠 모이어 | Biodegradable, liquid impervious films |
| DE4122212C2 (en) * | 1991-07-04 | 1994-06-16 | Inventa Ag | Thermoplastically processable mass of starch and acrylate copolymers |
| ATE138601T1 (en) * | 1991-07-26 | 1996-06-15 | Mundigler Norbert Dipl Ing Dr | NEW MODELS |
| US5256711A (en) * | 1991-10-04 | 1993-10-26 | Director-General Of Agency Of Industrial Science | Starch-containing biodegradable plastic and method of producing same |
| DE4133335C2 (en) * | 1991-10-08 | 1995-11-02 | Inventa Ag | Starch mixture, process for its preparation and use thereof |
| DE4134190A1 (en) * | 1991-10-16 | 1993-04-22 | Tomka Ivan | METHOD FOR IMPROVING THE MECHANICAL PROPERTIES OF ONE-OR MULTILAYER FOILS |
| US5252271A (en) * | 1991-10-22 | 1993-10-12 | Bio-Products International | Biodegradable packaging foam and method of preparation |
| SG47625A1 (en) * | 1991-11-14 | 1998-04-17 | Bio Tech Biolog Naturverparkun | Biodegradable mould material |
| US5185382A (en) * | 1992-01-21 | 1993-02-09 | Kansas State University Research Foundation | Starch-based, biodegradable packing filler and method of preparing same |
| US5208267A (en) * | 1992-01-21 | 1993-05-04 | Univ Kansas State | Starch-based, biodegradable packing filler and method of preparing same |
| US5248702A (en) * | 1992-01-21 | 1993-09-28 | Kansas State University Research Foundation | Starch-based, biodegradable packing filler and method of preparing same |
| US5427614A (en) * | 1992-02-14 | 1995-06-27 | Warner-Lambert Company | Starch based formulations |
| US5266368A (en) * | 1992-04-16 | 1993-11-30 | International Grain & Milling Company | Biodegradable packing material and method |
| US5372877A (en) * | 1992-04-16 | 1994-12-13 | Sealed Air | Biodegradable cushioning product |
| DE4228016C1 (en) * | 1992-08-24 | 1994-03-31 | Biotec Biolog Naturverpack | Process for producing biodegradable films from vegetable raw materials |
| US5308879A (en) * | 1992-09-07 | 1994-05-03 | Nippon Gohsei Kagaku Kogyo Kabushiki Kaisha | Process for preparing biodegradable resin foam |
| JP3019631B2 (en) | 1992-11-04 | 2000-03-13 | 松下電器産業株式会社 | Document image printing device |
| US5844023A (en) * | 1992-11-06 | 1998-12-01 | Bio-Tec Biologische Naturverpackungen Gmbh | Biologically degradable polymer mixture |
| DE4237535C2 (en) * | 1992-11-06 | 2000-05-25 | Biotec Biolog Naturverpack | Biodegradable polymer blend, process and film |
| US5272181A (en) * | 1992-11-18 | 1993-12-21 | Evergreen Solutions, Inc. | Biodegradable expanded foam material |
| US5393804A (en) * | 1992-11-24 | 1995-02-28 | Parke, Davis & Company | Biodegradable compositions comprising starch and alkenol polymers |
| KR950006538B1 (en) * | 1992-12-31 | 1995-06-16 | 김두현 | Method of manufacturing container for one use |
| DE4400330C2 (en) * | 1993-03-24 | 1997-10-02 | Naturpack Gmbh Verpackungen Au | Process for producing a foamed product or foam material from unmodified starch and device for carrying out the process |
| US5512090A (en) * | 1993-06-24 | 1996-04-30 | Free-Flow Packaging Corporation | Compositions for resilient biodegradable packaging material products |
| US5288318A (en) * | 1993-07-01 | 1994-02-22 | The United States Of America As Represented By The Secretary Of The Army | Cellulose acetate and starch based biodegradable injection molded plastics compositions and methods of manufacture |
| DE4327024A1 (en) * | 1993-08-12 | 1995-02-16 | Bayer Ag | Thermoplastically processable and biodegradable aliphatic polyesteramides |
| US5397834A (en) * | 1993-09-03 | 1995-03-14 | Iowa State University Research Foundation, Inc. | Biodegradable thermoplastic composition of aldehyde starch and protein |
| DE4335983A1 (en) * | 1993-10-21 | 1995-04-27 | Inventa Ag | Process for increasing the transparency of mouldings or films made from thermoplastic starch or thermoplastic starch-polymer blend |
| US5500465A (en) * | 1994-03-10 | 1996-03-19 | Board Of Trustees Operating Michigan State University | Biodegradable multi-component polymeric materials based on unmodified starch-like polysaccharides |
| DE19500756A1 (en) * | 1995-01-13 | 1996-07-18 | Basf Ag | Biodegradable polymers, processes for their production and their use for the production of biodegradable moldings |
| DE19536505A1 (en) * | 1995-09-29 | 1997-04-10 | Biotec Biolog Naturverpack | Biodegradable filter material and process for its manufacture |
-
1996
- 1996-04-02 AT AT96905977T patent/ATE242295T1/en active
- 1996-04-02 CA CA002217541A patent/CA2217541A1/en not_active Abandoned
- 1996-04-02 JP JP08525223A patent/JP3107830B2/en not_active Expired - Lifetime
- 1996-04-02 ES ES96905977T patent/ES2201173T3/en not_active Expired - Lifetime
- 1996-04-02 EP EP96905977A patent/EP0819147B1/en not_active Expired - Lifetime
- 1996-04-02 AU AU49522/96A patent/AU705499B2/en not_active Ceased
- 1996-04-02 PT PT96905977T patent/PT819147E/en unknown
- 1996-04-02 CN CN96193126A patent/CN1181098A/en active Pending
- 1996-04-02 US US08/930,748 patent/US6096809A/en not_active Expired - Lifetime
- 1996-04-02 WO PCT/IB1996/000275 patent/WO1996031561A1/en active IP Right Grant
- 1996-04-02 DE DE59610506T patent/DE59610506D1/en not_active Expired - Lifetime
- 1996-04-02 DK DK96905977T patent/DK0819147T3/en active
-
1999
- 1999-10-27 US US09/428,512 patent/US6235816B1/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011117549A1 (en) | 2010-03-25 | 2011-09-29 | Roquette Freres | Plant material compositions and method for preparing same |
Also Published As
| Publication number | Publication date |
|---|---|
| PT819147E (en) | 2003-10-31 |
| US6235816B1 (en) | 2001-05-22 |
| JP3107830B2 (en) | 2000-11-13 |
| WO1996031561A1 (en) | 1996-10-10 |
| ES2201173T3 (en) | 2004-03-16 |
| DK0819147T3 (en) | 2003-09-29 |
| CN1181098A (en) | 1998-05-06 |
| AU705499B2 (en) | 1999-05-27 |
| AU4952296A (en) | 1996-10-23 |
| JPH10512010A (en) | 1998-11-17 |
| DE59610506D1 (en) | 2003-07-10 |
| ATE242295T1 (en) | 2003-06-15 |
| US6096809A (en) | 2000-08-01 |
| EP0819147B1 (en) | 2003-06-04 |
| EP0819147A1 (en) | 1998-01-21 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Discontinued |