CN101525417B - Polyester - Google Patents
Polyester Download PDFInfo
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- CN101525417B CN101525417B CN2008100186170A CN200810018617A CN101525417B CN 101525417 B CN101525417 B CN 101525417B CN 2008100186170 A CN2008100186170 A CN 2008100186170A CN 200810018617 A CN200810018617 A CN 200810018617A CN 101525417 B CN101525417 B CN 101525417B
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- polyester
- butyleneglycol
- acid
- carbon
- dicarboxylic acid
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Abstract
The invention discloses a polyester, which is a macromolecular polyester prepared by the reaction of aromatic dicarboxylic acid or derivatives of the aromatic dicarboxylic acid and 1,2-butylene glycol, wherein the 1,2-butylene glycol is biologically derived. The carbon element component in the dibasic alcohol component of the raw materials of the polyester is derived from biological materials, but not from petroleum materials, thereby greatly reducing the emission of CO2 generated by petroleum refining.
Description
Technical field:
The present invention relates to the raw-material polyester of a kind of use biogenetic derivation.
Background technology:
In recent years, along with going from bad to worse of environment for human survival, People more and more is paid close attention to development environment friendly material and is used renewable starting material.Oil is most important industrial chemicals as Nonrenewable resources, but because the discharging of a large amount of CO2 in using engineering and in final the discarding, a large amount of dischargings of CO2 have caused a series of problems such as global warming, and the direct threats human existence.How substituting and reduce and use oil as starting material, is that people face one of research problem.
Polyester is because its favorable mechanical performance, moulding processability have purposes widely in fields such as fiber, resin, films, is one of most important synthetic materials in the world.
Because producing the raw material of polyester all is the processed goods that derives from oil.How using non-petroleum exploitation polyester product is an important research project.
People use reproducible Biological resources; Various novel polyester have been developed; For example E.I.Du Pont Company through biology and chemical process, prepares 1 through corn is fermented; 3-PDO, and developed and contain that the 36wt% that has an appointment derives from biomaterial but not PTT (PTT) polymkeric substance of oil material.Natureworks company is raw material equally with farm crop, through biology and chemical process, has produced pure biogenetic derivation and has been easy to biodegradable POLYACTIC ACID (PLA) polymkeric substance.
Summary of the invention:
The object of the present invention is to provide a kind of polyester that meets the environmental protection needs.
Technical solution of the present invention is:
A kind of polyester; It is characterized in that: be by aromatic dicarboxylic acid or derivatives thereof and 1; The macromolecule polyester that the 2-butyleneglycol obtains through reaction, wherein 1, in the 2-butyleneglycol 1 of biogenetic derivation; The 2-butyleneglycol (promptly through biological fermentation and/or the chemical industry course of processing with the carbon elements composition in the biomaterial convert to 1, the 2-butyleneglycol).
Biomaterial wherein is the stalk of corn, sugarcane, wheat or other farm crop.Wherein corn, wheat are its seed and/or stalk.Through biomaterial production obtain 1, in the 2-butyleneglycol, 1,2-butyleneglycol content is between 95%-99.9%, and the transmitance of light is 50%--99% in the scope of 190nm-350nm.Also contain carbon in the polyester and derive from the diprotic acid of petroleum and the copolymer composition of divalent alcohol.The aromatic dicarboxylic acid or derivatives thereof is terephthalic acid or DMT. Dimethyl p-benzenedicarboxylate.The limiting viscosity of polyester is 0.50-0.95.
Farm crop are a kind of renewable resourcess; Can airborne CO2 be passed through photosynthesis; Being converted into various starch, carbohydrate, Mierocrystalline cellulose, xylogen etc. stores in farm crop fruit and stalk thereof; The present invention utilizes the stalk of corn, wheat, sugarcane or other farm crop, and the process biological fermentation and/or the chemical industry course of processing make the raw material 1 of polybutylene terephthalate, 2-butyleneglycol.Biomaterial of the present invention is the stalk of corn, sugarcane, wheat or other farm crop.Obtain butyleneglycol through biology and/or chemical process.For example corn is through the bioprocess separating starch; Obtain the sugar of 5 carbon and 6 carbon through processing; These sugars can be prepared multicomponent binary alcohol through the technology of hydrogenation catalyst, through the rectifying purifying, again through 150 ℃ of-200 ℃ of temperature heat treated; Handle through active carbon filtration, just can obtain raw material diol component of the present invention.In the product 1, the carbon of 2-butyleneglycol derives from biological raw material.
Use in the present invention 1, the 2-butyleneglycol can contain other glycol component, and terepthaloyl moietie, 1 is for example arranged, 2-Ucar 35,1,4-butyleneglycol, 2,3-butyleneglycol and 1, other diol component of 2-pentanediol.
Use among the present invention 1; The purity of 2-butyleneglycol is 95%-99.9%; The carbon of other compositions also is to derive from biomaterial, and the transmitance of light is 50%--99% in the scope of 190nm-350nm, if the transmitance of 1.2-butyleneglycol light in the 190nm-350nm scope of the use in the invention is lower than this scope; Then the color of the finished product is relatively poor, thereby has limited the application of product.
Among the present invention, new polyester is by aromatic dicarboxylic acid or derivatives thereof and 1, the macromolecule polyester that the 2-butyleneglycol obtains through reaction.Wherein diacid is the verivate of terephthalic acid and esterification thereof, can be terephthalic acid, DMT. Dimethyl p-benzenedicarboxylate, diethyl terephthalate etc.Diacid unit further among the present invention contains m-phthalic acid; M-phthalic acid-5-sulphonate; Phthalic acid; The methyl terephthalic acid; The naphthalene diacid; The aryl dicarboxylic acid's class and the Succinic Acid of aromatic carboxylic acids such as biphenyl dicarboxylic acid and ester derivative thereof; Hexanodioic acid; Pimelic acid; Suberic acid; Nonane diacid; Aliphatic carboxylic acid and ester derivative and cyclohexane dicarboxylic acids such as dodecanedicarboxylic acid; The hexahydro-m-phthalic acid; Alicyclic dicarboxylic acid and ester derivatives thereof such as hexahydro-phthalic acid.Be meant materials such as lower alkyl esters, acid anhydrides, acyl chlorides such as dimethyl ester in the described verivate.These dicarboxylicacid can two or more alone or in combination uses.
Preferred aromatic dicarboxylic acid is preferably terephthalic acid and DMT. Dimethyl p-benzenedicarboxylate among the present invention.
The carbon that polyester among the present invention can also contain other derives from the diprotic acid of oil and the copolymer composition of divalent alcohol.Glycol component can be exemplified as: carbon numbers such as pinakon, Ucar 35, butyleneglycol, pentanediol are the saturated and unsaturated divalent alcohol of 2-30; High-molecular weight divalent alcohol such as polyoxyethylene glycol, W 166, polytetramethylene glycol.
The polyester characteristic be diacid and carbon derive from biomaterial glycol through over-churning or transesterification reaction, obtain the polyester that limiting viscosity is 0.60-0.95 after the polycondensation.Polyester of the present invention can pass through existing apparatus and process; At first through esterification or transesterification reaction; In this process, can use known catalyzer, can enumerate by one or more mixture in tetrabutyl titanate, isopropyl titanate, n-butylstannoic acid, manganese acetate, Cobaltous diacetate, the magnesium acetate.It is 95% or 95% above the time that esterification or transesterification reaction reach reactivity, shifts and carries out polycondensation, and the used catalyzer of polycondensation is a metal titanium class catalyzer, and titanium compound is for having
Structure, R wherein
1, R
2, R
3, R
4Alkyl, the alkyl of unsaturated carbon, hydroxyalkyl, acetylize alkyl, wherein R for saturated carbon
1, R
2, R
3, R
4Can be identical group, also can be different moiety combinations.Specifically can be tetrabutyl titanate, sec.-propyl titanic acid ester, propyl group titanic acid ester, propenyl titanic acid ester.
Can add various stablizer phosphorus compounds commonly used among the present invention; Be trivalent or phosphoric organic or inorganic compound; That can simply enumerate has phosphoric acid, trimethyl phosphite 99, a triphenylphosphate; Can be the trivalent of commercially available phosphorus system and the inhibitor of pentavalent, like commercially available PEP36, AP1500, AX-71.Do not enumerate more specifically at this.
Polycondensation is carried out under 200 ℃ of-260 ℃ of conditions in temperature, reaches polycondensation under 200 pascals and the following vacuum condition gradually, deviates from the small molecules glycol, when the viscosity of polymkeric substance is in the 0.60-0.95 scope, can finish reaction, obtains polyester of the present invention.
Polyester of the present invention can use the polymerization of still formula, the semi-continuous polymerzation of discontinuous, the method for successive polymerization to produce.
The polyester that the present invention obtains can use through various ordinary methods, as with the compound use of inorganic reinforcement, inorganic reinforcement can be various long fine, short fibers or nanoparticles.PBT among the present invention can use the polyester working method of various routines that polyester is processed, like single screw extrusion machine, twin screw extruder, Banbury mixer.Polyester can be used in various fields such as resin, film, fiber among the present invention, processes various subsequent products.
The carbon composition derives from biomaterial but not petroleum in the polyester raw material glycol component of the present invention, thereby significantly reduces owing to the smelting oil, and the CO that outwards discharges
2Amount.
Embodiment:
Biogenetic derivation 1, the 2-butyleneglycol: great achievement group in Changchun produces, the carbon source is corn, purity: 97, buy the back 190 ℃ through after 2 hours heat treated, through subsequent use behind the activated carbon filtration, transmitance is 65% during 250nm, transmitance is 90% during 300nm.
Oil source 1, the 2-butyleneglycol: the carbon source is oil, the holy space chemical industry in Shanghai produces.
Terephthalic acid: sub-petrochemical iy produced, polymerization-grade are raised by China.
DMT. Dimethyl p-benzenedicarboxylate: Iranian Fiber Intermediate Products Co. produces.
Above-mentioned biogenetic derivation 1,2-butyleneglycol be through biological fermentation and/or the chemical industry course of processing with the carbon elements composition in the biomaterial convert to 1, the 2-butyleneglycol.
Embodiment 1:
In the device that has stirring and rectifying tower, drop into biogenetic derivation 1; The mixed slurry of 9.2 kilograms of 2-butyleneglycols, 11.3 kilograms of terephthalic acids; Add the butyl stannonic acid of 6.3 grams and the tetrabutyl titanate of 6.8 grams, be warmed up to gradually in the 200-235 ℃ of scope and carry out esterification, collect water byproduct; But the esterification rate is 95% when above, finishes esterification, add the phosphoric acid of 2.6 grams after, add the tetrabutyl titanate of 6.8 grams, under 230-250 ℃ of scope, carry out polycondensation, when reaching the polymer viscosity moment of torsion of setting, the polymkeric substance that spues, subsequent use after the pelletizing.
Embodiment 2:
With the device of embodiment 1, drop into 13.4 kilograms DMT. Dimethyl p-benzenedicarboxylate and 11.6 kilograms biogenetic derivation 1,2-butyleneglycol raw material adds Cobaltous diacetate 6 grams; In 200-235 ℃ TR, carry out transesterification reaction, deviate from methyl alcohol, the transesterification reaction rate reaches 95% when above; After adding the phosphoric acid of 2.6 grams, add the tetrabutyl titanate of 6.8 grams, be 230-250 ℃ in temperature and carry out polycondensation; After reaching the polymer viscosity of setting, the polymkeric substance that spues, pelletizing is subsequent use.
Comparative Examples:
With device and the additive amount of embodiment 1, process is also identical, and with 1 of biogenetic derivation, the 2-butyleneglycol is replaced by 1 of oil source, 2-butyleneglycol.
Evaluation method:
Limiting viscosity (IV): adopt polyester national standard testing method: GB/T-14190-1993 tests.
| Embodiment 1 | Embodiment 2 | Comparative Examples | |
| Limiting viscosity | 0.70 | 0.88 | 0.85 |
Claims (4)
1. polyester is characterized in that: be by aromatic dicarboxylic acid or derivatives thereof and 1, and the macromolecule polyester that the 2-butyleneglycol obtains through reaction; Wherein 1, the 2-butyleneglycol is a biogenetic derivation 1, the 2-butyleneglycol; Carbon source is corn, purity: 97%, at 190 ℃ through after 2 hours heat treated; Through activated carbon filtration, light transmission rate is 65% during 250nm, and light transmission rate is 90% during 300nm.
2. a kind of polyester according to claim 1 is characterized in that: also contain carbon and derive from the diprotic acid of petroleum and the copolymer composition of divalent alcohol.
3. a kind of polyester according to claim 1 is characterized in that: the aromatic dicarboxylic acid or derivatives thereof is terephthalic acid or DMT. Dimethyl p-benzenedicarboxylate.
4. a kind of polyester according to claim 1 is characterized in that: the limiting viscosity of polyester is 0.50-0.95dl/g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100186170A CN101525417B (en) | 2008-03-04 | 2008-03-04 | Polyester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100186170A CN101525417B (en) | 2008-03-04 | 2008-03-04 | Polyester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101525417A CN101525417A (en) | 2009-09-09 |
| CN101525417B true CN101525417B (en) | 2012-05-23 |
Family
ID=41093500
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008100186170A Expired - Fee Related CN101525417B (en) | 2008-03-04 | 2008-03-04 | Polyester |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101525417B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4554344A (en) * | 1985-04-12 | 1985-11-19 | Eastman Kodak Company | Process for preparation of polyesters with improved molecular weight from glycols containing a vicinal secondary hydroxyl group |
| CN1683293A (en) * | 2005-03-01 | 2005-10-19 | 大成多元醇投资有限公司 | Process for producing diatomic alcohol and polyol from cracking sorbierite |
-
2008
- 2008-03-04 CN CN2008100186170A patent/CN101525417B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4554344A (en) * | 1985-04-12 | 1985-11-19 | Eastman Kodak Company | Process for preparation of polyesters with improved molecular weight from glycols containing a vicinal secondary hydroxyl group |
| CN1683293A (en) * | 2005-03-01 | 2005-10-19 | 大成多元醇投资有限公司 | Process for producing diatomic alcohol and polyol from cracking sorbierite |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101525417A (en) | 2009-09-09 |
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Effective date of registration: 20160612 Address after: Japan Tokyo central Nihonbashi Muromachi 2-1-1 Patentee after: Toray Industries, Inc. Address before: 226009 Nantong Province Economic and Technological Development Zone, the New South Road, No. 58, No. Patentee before: Toray Fiber Research Institute (China) Co., Ltd. |
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| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120523 Termination date: 20170304 |