WO1991004286A1 - Improvements in or relating to the production of plastics material incorporating starch - Google Patents
Improvements in or relating to the production of plastics material incorporating starch Download PDFInfo
- Publication number
- WO1991004286A1 WO1991004286A1 PCT/GB1990/001402 GB9001402W WO9104286A1 WO 1991004286 A1 WO1991004286 A1 WO 1991004286A1 GB 9001402 W GB9001402 W GB 9001402W WO 9104286 A1 WO9104286 A1 WO 9104286A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- starch
- polymer
- resin
- filler
- plastics material
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/005—Processes for mixing polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
Definitions
- THIS INVENTION relates to the production of plastics material incorporating starch.
- thermoplastic formulations are known to afford various benefits such as enhanced degradability, which reduces the environmental problems presented by plastics products, such as packaging when no longer required, or such as the reduction of product costs, (natural starch is cheaper than synthetic polymers) and the conservation of non-renewable resources (i.e. the synthetic polymers for which the starch is substituted).
- the inventor has observed experimentally that it is possible to establish chemical reactions directly between matrix polymers and the starch particle surfaces in the presence of strong alkali such as sodium hydroxide provided that the polymer itself has reactive structures such as carboxylic acid groups in its molecules and it is reasonable to presume that this is because the mildly acidic nature of the hydrogen atoms in the hydroxy groups pendant from the starch molecules is encouraged by the strong alkali to react and form ester linkages with the carboxylic acid groups in the matrix polymers.
- strong alkali such as sodium hydroxide
- the inventor has now discovered that a useful improvement in the bonding between the surface of natural starch particles and a thermoplastics polymer matrix can be achieved by forming a chemical bridge between the starch hydroxy groups and an intermediate polymer phase by using polyvalent metal hydroxides, in particular the hydroxides of the alkaline earth metals which combine multiple valency with a degree of water solubility.
- polyvalent metal hydroxides in particular the hydroxides of the alkaline earth metals which combine multiple valency with a degree of water solubility.
- natural starch particles can take up significant quantities of basic metal hydroxides from aqueous solution and . that the resultant particles, which are apparently unchanged physically, can interact with carboxylic acid groups in polymers with the metal atoms remaining in position.
- a method of forming a plastics material comprising a thermoplastic resin and a filler in the form of natural starch, wherein the starch, before admixture with the resin, is treated in an aqueous solution of an alkali-earth metal hydroxide, and is subsequently washed and dried before mixing with the molten thermoplastics resin, and wherein the resin comprises a polymer or co-polymer which affords carboxylic acid groups.
- the necessary carboxylic acid groupings can be an integral part of the matrix polymer as introduced by copolymerisation, for example as in a copolymer of styrene and maleic anhydride, or more conveniently can be provided by making use of a minor addition of a carboxylic acid rich polymer such as polyethylene acrylic acid copolymer to an inert polymer typified by polyethylene.
- the poor adhesion that normally prevails between the highly polar untreated natural starch surface and the low polarity waxy surface of polyolefins is sharply improved by the creation of a layer of an acidic polymer such as polyethylene acrylic acid chemically bonded to the starch particle surface because the two polymers (polyolefins and acidic polymer) are mutually compatible.
- the metal hydroxide the obvious chemical candidate, calcium hydroxide, and obtained good results using calcium hydroxide
- the chemistry has been confirmed by showing experimentally that exactly the same benefits can be achieved by using the dibasic hydroxides of the other alkaline earth metals from group two of the periodic classification, strontium hydroxide and barium hydroxide. It is likely that the same benefits can also be obtained by using any inorganic coordination complex with at least two hydroxy groups possessing alkaline character attached to the central metallic atom and which has a sufficient level of water solubility to enable the initial reaction with the starch hydroxy groups to reach equilibrium in a time period compatible with commercial manufacturing requirements.
- the surplus metal hydroxide liquors were removed by centrifugation, the treated starches washed on the centrifuge with deionised water until no significant amounts of metal ions could be detected in the washings, and the treated starches were recovered by spray drying the starches recovered from the centrifuge as a slurry in further deionised water.
- One portion of starch was treated in exactly the same way but with the metallic hydroxide solution replaced by deionised water so as to provide a control sample. All of these starch samples were vacuum dried at 80°C until the moisture content was between 0.5 and 1$ by weight.
- the dry starches were then compounded as masterbatches at 50% weight con ⁇ centration in low density polyethylene of melt flow index 2 to which had been added 10% of a polyethylene acrylic acid copolymer sold by Exxon Chemicals Ltd. as "Escor 5100" having a melt flow index of 8 and an acid number of 70 mgs. of K0H per gramme.
- These masterbatches made on a laboratory 2-roll mill, were granulated and blended with more low density polyethylene of melt flow index 2 at such proportion as to produce a final product containing 6% ww of starch and 1.2% of ethylene acrylic acid copolymer.
- the final product was a film of 50 micrometre thickness made by extrusion film blowing and using identical conditions of speed and temperature in each case.
- Figure 1 is a bar chart showing the elongation at break 'for the products incorporating respectively the starch treated by deionised water (identified as "Blank” in the bar chart) and the starch treated with calcium, strontium and barium hydroxide solutions. All tests were based on at least five samples.
- the starch content of the final product is 6% by weight
- this value has been selected for convenience and the proportion of starch may be varied over a wide range depending upon the desired characteristics of the final product, or economic con ⁇ siderations.
- the starch content may be any value within the range providing 1 to 60% by volume. (At starch contents below 1% the advantages of using the starch filler become neglibible, whilst at starch contents above 60% by volume the strength of the product becomes reduced to an extent which is likely to be unacceptable for most purposes) .
- the acidic polymer or copolymer might, instead of being incorporated in the masterbatch, be introduced in blending the final product.
Abstract
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA002066437A CA2066437A1 (en) | 1989-09-12 | 1990-09-11 | Production of plastics material incorporating starch |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB8920626.2 | 1989-09-12 | ||
GB898920626A GB8920626D0 (en) | 1989-09-12 | 1989-09-12 | Improvements in or relating to the production of plastics material incorporating starch |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1991004286A1 true WO1991004286A1 (en) | 1991-04-04 |
Family
ID=10662952
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/GB1990/001402 WO1991004286A1 (en) | 1989-09-12 | 1990-09-11 | Improvements in or relating to the production of plastics material incorporating starch |
Country Status (7)
Country | Link |
---|---|
EP (1) | EP0491799A1 (en) |
JP (1) | JPH05503541A (en) |
AU (1) | AU6404890A (en) |
CA (1) | CA2066437A1 (en) |
GB (1) | GB8920626D0 (en) |
IL (1) | IL95670A0 (en) |
WO (1) | WO1991004286A1 (en) |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4021388A (en) * | 1972-05-18 | 1977-05-03 | Coloroll Limited | Synthetic resin sheet material |
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 |
EP0032802A1 (en) * | 1980-01-17 | 1981-07-29 | THE GOVERNMENT OF THE UNITED STATES OF AMERICA as represented by the Secretary Department of Commerce | Flexible, self-supporting and biodegradable films and their production |
US4420576A (en) * | 1980-08-06 | 1983-12-13 | Coloroll Limited | Plastics based composition containing a polyester resin and alkaline modified starch granules |
US4454268A (en) * | 1983-06-23 | 1984-06-12 | The United States Of America As Represented By The Secretary Of Agriculture | Starch-based semipermeable films |
-
1989
- 1989-09-12 GB GB898920626A patent/GB8920626D0/en active Pending
-
1990
- 1990-09-11 AU AU64048/90A patent/AU6404890A/en not_active Abandoned
- 1990-09-11 EP EP90913853A patent/EP0491799A1/en not_active Withdrawn
- 1990-09-11 CA CA002066437A patent/CA2066437A1/en not_active Abandoned
- 1990-09-11 WO PCT/GB1990/001402 patent/WO1991004286A1/en not_active Application Discontinuation
- 1990-09-11 JP JP2512906A patent/JPH05503541A/en active Pending
- 1990-09-12 IL IL95670A patent/IL95670A0/en unknown
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4021388A (en) * | 1972-05-18 | 1977-05-03 | Coloroll Limited | Synthetic resin sheet material |
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 |
EP0032802A1 (en) * | 1980-01-17 | 1981-07-29 | THE GOVERNMENT OF THE UNITED STATES OF AMERICA as represented by the Secretary Department of Commerce | Flexible, self-supporting and biodegradable films and their production |
US4420576A (en) * | 1980-08-06 | 1983-12-13 | Coloroll Limited | Plastics based composition containing a polyester resin and alkaline modified starch granules |
US4454268A (en) * | 1983-06-23 | 1984-06-12 | The United States Of America As Represented By The Secretary Of Agriculture | Starch-based semipermeable films |
Also Published As
Publication number | Publication date |
---|---|
AU6404890A (en) | 1991-04-18 |
EP0491799A1 (en) | 1992-07-01 |
GB8920626D0 (en) | 1989-10-25 |
CA2066437A1 (en) | 1991-03-13 |
IL95670A0 (en) | 1991-06-30 |
JPH05503541A (en) | 1993-06-10 |
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