CN102229702A - Production method of complete biodegradable aliphatic polyester - Google Patents
Production method of complete biodegradable aliphatic polyester Download PDFInfo
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- CN102229702A CN102229702A CN2011101199502A CN201110119950A CN102229702A CN 102229702 A CN102229702 A CN 102229702A CN 2011101199502 A CN2011101199502 A CN 2011101199502A CN 201110119950 A CN201110119950 A CN 201110119950A CN 102229702 A CN102229702 A CN 102229702A
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Abstract
The invention discloses a production method of complete biodegradable aliphatic polyester. The production method comprises the following three steps: (1) an esterification phase that: aliphatic dibasic acid monomer and aliphatic dibasic alcohol monomer are added to a reactor according to certain proportions, an esterification catalyst is added, and a normal-pressure esterification reaction is carried out under the protection of an inert gas; (2) a pre-concentration phase that: when the esterification reaction is completely finished, a main catalyst is added, and the mixture is subject to a reaction for 1 to 2 hours; (3) a concentration phase: an auxiliary catalyst is added, and the mixture is subject to a reaction for 4 to 9 hours, such that aliphatic with a weight average molecular weight greater than 150 thousands is obtained. The polyester product provided by the present invention has good heat stability, stretching ductility, environment friendly performance and a good color, and can be biodegraded.
Description
Technical field
The present invention relates to a kind of production method of aliphatic polyester of fully biodegradable, particularly adopt the effective catalyst single stage method to prepare the method for weight-average molecular weight at 15 ~ 200,000 high-molecular aliphatic polyester.
Background technology
Plastic material is to use one of maximum material in our daily life at present, and conventional plastics have excellent comprehensive performances, are widely used in all respects such as building, agricultural, packing.But these materials are highly stable at occurring in nature, and waste is difficult to be decomposed at occurring in nature.People begin degradation material has been carried out a large amount of research for this reason, and aliphatic polyester obtains paying close attention to very widely as a kind of material of fully biodegradable.It is known already thing that aliphatic polyester has Biodegradable, so is unfavorable for because of its mechanical characteristics and processibility are all not good using.But along with the progress of polymerization technique, a lot of aliphatic polyesters have entered in the middle of our life, wherein use more have poly(lactic acid) and poly-diprotic acid binary alcohol esters, and they can substitute polyethylene and polypropylene material aspect a lot.
At present, aliphatic dibasic acid dibasic alcohol polyester generally uses melt-polycondensation and solution polycondensation preparation.Because solution polycondensation subsequent disposal complexity, so aliphatic dibasic acid dibasic alcohol polyester all is the method preparation of adopting melt phase polycondensation in the polyester now, but this preparation method is because esterification is reversible reaction, production of by-products, cause esterification incomplete, while polycondensation phase temperature of reaction height, the depolymerization of ring, thermolysis, oxidation etc. make the molecular weight of polymkeric substance promote difficulty.
The aliphatic polyester weight-average molecular weight just has comprehensive preferably Practical Performance about reaching 100,000.In the existing disclosed patent application document, the method that improves the aliphatic polyester molecular weight has:
Publication number discloses with diprotic acid for the CN02100758.6 Chinese patent, and dibasic alcohol and carboxylic acid carry out prepared in reaction terminal hydroxy group performed polymer, is that chainextender prepares the aliphatic polyester of weight-average molecular weight at 6-13 ten thousand with the organic silazane hydride compounds again.
Publication number discloses a kind of method of thermoplasticity Biodegradable resin for the CN93121098.4 Chinese patent, and this method is to carry out the polyester that melt phase polycondensation obtains weight-average molecular weight 5 ~ 90,000 with diprotic acid, excessive dibasic alcohol, and range of application is too little.
Publication number discloses the method that a kind of solution polycondensation prepares aliphatic polyester for the CN03153246.2 Chinese patent.This method be with aliphatic dibasic acid and aliphatic dihydroxy alcohol in the perhydronaphthalene solvent, add catalyzer, be warmed up to 100 ~ 200 ℃, react and obtained aliphatic polyester in 1 ~ 14 hour.The shortcoming of this method has been to use solvent, need to purify and operation such as separates.
Publication number discloses the method that a kind of two-step approach prepares high-molecular aliphatic polyester for the CN200510093775.9 Chinese patent.This method is with diprotic acid and dibasic alcohol melt phase polycondensation, obtains low molecule and comes that end carboxyl performed polymer, carries out chain extension, the preparation aliphatic polyester with two lactan of aliphatics diacyl and the two lactan of aromatic series diacyl again.Shortcoming is to have increased chain extending reaction, the range of molecular weight distributions broad.
Based on above-mentioned method certain defective is arranged all, produce the aliphatic polyester of weight-average molecular weight at the blown film more than 150,000 but the present invention has studied a kind of new preparation method.
Summary of the invention
Purpose of the present invention provides a kind of production method of aliphatic polyester of fully biodegradable; it can not use chainextender such as isocyanate compound, the two lactan of diacyl and organosilazanes etc.; do not add and cause the unsettled branching agent of physicals; as the acid phosphorus compound; do not use under the method for solvent preparation high-molecular weight aliphatic dibasic acid binary alcohol esters.
The present invention will solve is that the aliphatic polyester weight-average molecular weight that obtains of existing production method is low, and thermostability, stretching ductility and environmental friendliness performance are poor, complex manufacturing, need to add chainextender and branching agent problem.
The present invention is a monomer with aliphatic dibasic acid and aliphatic dihydroxy alcohol mainly, by using efficiently catalyzer and The optimum reaction conditions esterification and polycondensation is carried out to favourable direction.
Production method of the present invention comprises following three phases:
(1) Esterification Stage: binary aliphatic acid mono and binary aliphatic alcohol monomer are added reactor with certain proportion, at the 20000 ~ 50000pa that reduces pressure under the protection of rare gas element or under the protection of inert gas, be warmed up to 140 ~ 180 ℃, add esterifying catalyst and carry out the normal pressure esterification reaction, the endpoint of esterification is for recording acid number less than 10mg;
(2) precondensation stage: after treating that esterification fully, add Primary Catalysts, be warmed up to 180 ~ 220 ℃, the 1000 ~ 20000pa that reduces pressure reaction 1 ~ 2 hour;
(3) polycondensation phase: add cocatalyst, be warmed up to 220 ~ 260 ℃, the 5 ~ 1000pa that reduces pressure reacted 4 ~ 9 hours, just can obtain weight-average molecular weight at the aliphatic dibasic acid binary alcohol esters more than 150,000.
The binary aliphatic acid mono that relates among the present invention is the dicarboxylic acid molecule that also has two carboxyls in the molecule, is specially a kind of of Succinic Acid and hexanodioic acid or two kinds of mixing.
The aliphatic dihydroxy alcohol that the present invention relates to is the glycol molecules that contains hydroxyl in the two ends of molecule, is specially the mixing of ethylene glycol and 1.4 butyleneglycols or two kinds.
The aliphatic dibasic acid that this is clearly demarcated and the mol ratio of aliphatic dihydroxy alcohol are 1:1.05 ~ 2, preferred 1:1.2 ~ 1.5.
Ratio in the aliphatic dibasic acid between Succinic Acid and the hexanodioic acid is selected as required, and extreme case is a kind of with in Succinic Acid and the hexanodioic acid only, and promptly the Succinic Acid consumption is zero or the hexanodioic acid consumption is zero; Ratio in the aliphatic dihydroxy alcohol between ethylene glycol, 1,4 butyleneglycol is selected as required, and extreme case is a kind of in an ethylene glycol, 1,4 butyleneglycol, and promptly the ethylene glycol consumption is zero or 1,4 butyleneglycol consumption is zero.
Because the aliphatic dihydroxy alcohol that participates in reaction is easy to generate other by product, excess fats family dibasic alcohol can be taken away by vacuumizing, and does not influence reaction result.
Esterification of the present invention is a normal pressure or in protection of inert gas under protection of inert gas
Under reduce pressure and carry out under 20000 ~ 50000pa, can prevent the oxidation in the reaction process, simultaneously lazy
The property gas can take away the by products such as water molecules that produce in the esterification, preferred atmospheric pressure state.
Rare gas element is a kind of in nitrogen, helium, neon, the argon gas.
The esterifying catalyst that uses in the esterification of the present invention is lewis acid, the compound of organic sulfonic acid class, strongly-acid ion exchange resin etc., heteropolyacid, boron fluoride, aluminum chloride, tin chloride, titanium chloride, titanium bromide, methylsulphonic acid, tosic acid etc. are specifically arranged, the molar weight that adds catalyzer is 0.0001 ~ 0.05 times of molar weight of reaction acid, preferred 0.001 ~ 0.01 times.
Esterification emphasis of the present invention is judged the method for using the survey acid number, and acid number can react the level of response of aliphatic carboxylic acid accurately.Acid number can assert that below 10mg esterification finishes.
Prepolymerization reaction process of the present invention is for excess fats family dibasic alcohol is slowly detached, to avoid the loss of pipeline obstruction and material, can make simultaneously polymer polymerizing is molecular weight ratio oligopolymer uniformly, and molecular weight is easy to promote in polycondensation.
Primary Catalysts of the present invention is to add in the time of prepolymerization reaction, and this Primary Catalysts is nano titanium oxide and nano silicon interpolymer, and this catalyzer has very high catalytic activity to polyester, and is nontoxic, and facile hydrolysis can well not disperse in the ethylene glycol.The adding molar weight of Primary Catalysts is 0.0001 ~ 0.05 times of molar weight of reaction acid, preferred 0.001 ~ 0.01 times.Described reaction acid is an aliphatic dibasic acid.
Primary Catalysts of the present invention is to add in the time of prepolymerization reaction, and this Primary Catalysts is nano titanium oxide and nano silicon interpolymer, and this catalyzer has very high catalytic activity to polyester, and is nontoxic, and facile hydrolysis can well not disperse in the ethylene glycol.The adding molar weight of Primary Catalysts is 0.0001 ~ 0.05 times of molar weight of reaction acid, preferred 0.001 ~ 0.01 times.The reaction acid here is an aliphatic dibasic acid.
Prepolymerization reaction temperature of the present invention is 180 ~ 220 ℃.Vacuum requires at 1000 ~ 20000pa, and the time of preferred 2000 ~ 5000pa. prepolymerization reaction was controlled at 1 ~ 2 hour.Preferred 1.5 ~ 2 hours.
The cocatalyst that polycondensation of the present invention adds is a kind of or mixing arbitrarily of the compound of germanium, antimony, tin class, the compound of germanium class has four butoxy germanium, tetraisopropoxide germanium, ethylene glycol germanium etc., the antimony class compound antimonous oxide, antimony glycol, antimony acetate etc. are arranged, the compound of tin class has tin protochloride, stannous octoate etc.The adding molar weight of catalyzer is 0.0001 ~ 0.05 times of molar weight of reaction acid, preferred 0.001 ~ 0.01 times.The reaction acid here is an aliphatic dibasic acid.
The temperature range of polycondensation of the present invention is 220 ~ 260 ℃, because the too high meeting of temperature causes aliphatic oxidation, cyclisation and thermolysis, so temperature of reaction is unsuitable too high.
The vacuum pressure of polycondensation of the present invention is at 5 ~ 1000pa, preferred 10 ~ 70pa.
The time of polycondensation of the present invention is 4 ~ 9 hours, preferred 4 ~ 6 hours.
After reaction finishes, use rare gas element, extrude resulting aliphatic dibasic acid binary alcohol esters as nitrogen.This polyester has excellent heat resisting, the favorable mechanical performance,
Advantage of the present invention is: under the condition that need not add chainextender and branching agent, and preparation high-molecular weight aliphatic dibasic acid dibasic alcohol polyester, weight-average molecular weight is more than 150,000.This polyester has good thermostability, and stretching ductility and environmental friendliness performance can biological decomposition, and color and luster is better, and it can be used for blown film, aspects such as injection moulding.
Embodiment
Now in conjunction with specific embodiments the present invention is explained in detail.
Embodiment one
Reaction flask at 1L (has whipping appts; the inflated with nitrogen device; condenser device; vacuum extractor) 1.4 butyleneglycols that add 1.3mol in, the Succinic Acid of 0.8mol, the hexanodioic acid of 0.2mol; begin to start whipping appts; be heated to 160 ℃ under nitrogen protection, add the 0.005mol methylsulphonic acid, the by product that reaction generates is discharged by prolong.The test acid number adds the interpolymer of the titanium dioxide and silicon dioxide of 0.005mol after below the 10mg after reaction for some time, is heated to 200 ℃, and the 5000pa that reduces pressure reacted 1.5 hours.Add the tin protochloride of 0.002mol, be warmed up to 250 ℃, the 70pa that reduces pressure reacted 6 hours, obtained the copolyesters of poly-succinic-butyleneglycol-hexanodioic acid.
The weight-average molecular weight of this polyester is about 180,000, and range of molecular weight distributions is about 1.8.The polymkeric substance of gained is the solid of white, and melting index is below 10 gram/min, and tensile property and thermostability are fine.
Embodiment two
Reaction flask at 1L (has whipping appts; the inflated with nitrogen device; condenser device; vacuum extractor) add 1.4 butyleneglycols of 1.5mol in, the Succinic Acid of 1mol begins to start whipping appts; under nitrogen protection, be heated to 150 ℃; the 30000pa that reduces pressure simultaneously adds the 0.001mol heteropolyacid, and the by product that reaction generates is discharged by prolong.The test acid number adds the interpolymer of the titanium dioxide and silicon dioxide of 0.002mol after below the 10mg after reaction for some time, is heated to 200 ℃, and the 5000pa that reduces pressure reacted 1 hour.Add the antimony acetate of 0.005mol, be warmed up to 240 ℃, the 50pa that reduces pressure reacted 5 hours, obtained poly butylene succinate.
The weight-average molecular weight of this polyester is about 200,000, and range of molecular weight distributions is about 1.7.The polymkeric substance of gained is the solid of white, and melting index is below 10 gram/min, and tensile property is good, and softening temperature is about 115 ℃.
Embodiment three
Reaction flask at 1L (has whipping appts; the inflated with nitrogen device; condenser device; vacuum extractor) butyleneglycol that adds 1.2mol in; the hexanodioic acid of 1mol begins to start whipping appts, is heated to 170 ℃ under nitrogen protection; add the 0.001mol tosic acid, the by product that reaction generates is discharged by prolong.The test acid number adds the interpolymer of the titanium dioxide and silicon dioxide of 0.004mol after below the 10mg after reaction for some time, is heated to 200 ℃, and the 7000pa that reduces pressure reacted 2 hours.Add the tin protochloride of 0.003mol, be warmed up to 230 ℃, the 100pa that reduces pressure reacted 7 hours, obtained poly adipate succinic acid ester.
The molecular weight of this polyester is at weight average about 160,000, and range of molecular weight distributions is about 1.5.Resulting polymers is the solid of white, and melting index has good stretching extension performance and thermostability below 10 gram/min.
Embodiment four
Reaction flask at 1L (has whipping appts; the inflated with nitrogen device; condenser device; vacuum extractor) ethylene glycol that adds 1.4mol in; the hexanodioic acid of 1mol begins to start whipping appts, is heated to 150 ℃ under nitrogen protection; add the 0.002mol tin chloride, the by product that reaction generates is discharged by prolong.The test acid number adds the interpolymer of the titanium dioxide and silicon dioxide of 0.005mol after below the 10mg after reaction for some time, is heated to 190 ℃, and the 2000pa that reduces pressure reacted 2 hours.Add the antimonous oxide of 0.001mol, be warmed up to 230 ℃, the 90pa that reduces pressure reacted 6 hours, obtained polyethylene glycol adipate.
The molecular weight of this polyester is at weight average about 150,000, and range of molecular weight distributions is about 1.6.Color is the solid of white, and melting index is below 10 gram/min, and tensile property and thermostability are fine.
Embodiment five
Reaction flask at 1L (has whipping appts; the inflated with nitrogen device; condenser device; vacuum extractor) butyleneglycol that adds 1.2mol in; the hexanodioic acid of 1mol begins to start whipping appts, is heated to 170 ℃ under nitrogen protection; add 0.001mol aluminum chloride, the by product that reaction generates is discharged by prolong.The test acid number adds the interpolymer of the titanium dioxide and silicon dioxide of 0.004mol after below the 10mg after reaction for some time, is heated to 200 ℃, and the 7000pa that reduces pressure reacted 2 hours.Add the antimony glycol of 0.003mol, be warmed up to 230 ℃, the 100pa that reduces pressure reacted 7 hours, obtained poly adipate succinic acid ester.
The molecular weight of this polyester is at weight average about 160,000, and range of molecular weight distributions is about 1.5.Resulting polymers is the solid of white, and melting index is below 10 gram/min, and thermostability is fine.
Embodiment six
Reaction flask at 1L (has whipping appts; the inflated with nitrogen device; condenser device; vacuum extractor) 1.4 butyleneglycols that add 1mol in, the ethylene glycol of 0.5mol, the Succinic Acid of 1mol; begin to start whipping appts; be heated to 140 ℃ under nitrogen protection, add the 0.004mol heteropolyacid, the by product that reaction generates is discharged by prolong.The test acid number adds the interpolymer of the titanium dioxide and silicon dioxide of 0.01mol after below the 10mg after reaction for some time, is heated to 190 ℃, and the 6000pa that reduces pressure reacted 2 hours.Add the stannous octoate of 0.003mol, be warmed up to 230 ℃, the 70pa that reduces pressure reacted 8 hours, obtained polyoxyethylene glycol-Succinic Acid-butanediol ester.
The molecular weight of this polyester is at weight average about 180,000, and range of molecular weight distributions is about 1.5.Resulting polymers is the solid of white, and melting index is below 10 gram/min, and tensile property and thermostability are fine.
Claims (10)
1. the production method of the aliphatic polyester of a fully biodegradable is characterized in that this production method comprises following three phases:
(1) Esterification Stage: earlier aliphatic dibasic acid and aliphatic dihydroxy alcohol are added in the reactor with certain proportion, under the esterification condition, add esterifying catalyst and carry out esterification;
(2) prepolymerisation stage: after treating that esterification fully, add Primary Catalysts, adjust to the condition of prepolymerization reaction, reacted 1 ~ 2 hour;
(3) polycondensation phase: add cocatalyst, adjust to the reaction conditions of polycondensation phase, polycondensation 4 ~ 9 hours.
2. according to the production method of the aliphatic polyester of the fully biodegradable described in the claim 1, it is characterized in that aliphatic dibasic acid is at least a in Succinic Acid, the hexanodioic acid, aliphatic dihydroxy alcohol is at least a in ethylene glycol, 1,4 butyleneglycol.
3. according to the production method of the aliphatic polyester of the fully biodegradable described in the claim 2, it is characterized in that the mol ratio between aliphatic dibasic acid and the aliphatic dihydroxy alcohol is 1:1.05 ~ 2; Ratio in the aliphatic dibasic acid between Succinic Acid and the hexanodioic acid is selected as required, and extreme case is a kind of with in Succinic Acid and the hexanodioic acid only, and promptly the Succinic Acid consumption is zero or the hexanodioic acid consumption is zero; Ratio in the aliphatic dihydroxy alcohol between ethylene glycol, 1,4 butyleneglycol is selected as required, and extreme case is a kind of in a spent glycol, 1,4 butyleneglycol, and promptly the ethylene glycol consumption is zero or 1,4 butyleneglycol consumption is zero.
4. according to the production method of the aliphatic polyester of the fully biodegradable described in the claim 1, it is characterized in that esterifying catalyst is compound, the strongly-acid ion exchange resin of lewis acid, organic sulfonic acid class, comprise heteropolyacid, boron fluoride, aluminum chloride, tin chloride, titanium chloride, titanium bromide, methylsulphonic acid, tosic acid, the molar weight of the esterifying catalyst that adds is 0.0001 ~ 0.05 times of molar weight of reaction acid, preferred 0.001 ~ 0.01 times.
5. according to the production method of the aliphatic polyester of the fully biodegradable described in the claim 1, it is characterized in that described Primary Catalysts is nano titanium oxide and nano silicon interpolymer, the molar weight of the Primary Catalysts that adds is 0.0001 ~ 0.05 times of molar weight of reaction acid, preferred 0.001 ~ 0.01 times.
6. according to the production method of the aliphatic polyester of the fully biodegradable described in the claim 1, it is characterized in that described cocatalyst is the mixing of a kind of in the compound of germanium, antimony, tin class or at least two kinds; The compound of germanium class comprises four butoxy germanium, tetraisopropoxide germanium, ethylene glycol germanium, the antimony class compound comprise antimonous oxide, antimony glycol, antimony acetate, the compound of tin class comprises tin protochloride, stannous octoate; The molar weight of the cocatalyst that adds is 0.0001 ~ 0.05 times of molar weight of reaction acid, preferred 0.001 ~ 0.01 times.
7. according to the production method of the aliphatic polyester of the fully biodegradable described in the claim 1, it is characterized in that described esterification condition is the 20000 ~ 50000Pa that reduces pressure under protection of inert gas or the protection of inert gas, temperature is 140 ~ 180 ℃; The reaction and judgement standard in described esterification stage is an acid number, and its acid number can assert that below 10mg esterification finishes; Described acid number is the acid number of polyester, is meant that polyester connects in the section-content of COOH, need neutralize fully with every gram polyester and represent that unit is mgKOH/g for what milligram KOH solution.
8. according to the production method of the aliphatic polyester of the fully biodegradable described in the claim 1, it is characterized in that described prepolymerization reaction condition is the 1000 ~ 20000Pa that reduces pressure, temperature is 180 ~ 220 ℃.
9. according to the production method of the aliphatic polyester of the fully biodegradable described in the claim 1, it is characterized in that described polycondensation condition is the 5 ~ 1000Pa that reduces pressure, temperature is 220 ~ 260 ℃; The time of described polycondensation is 4 ~ 9 hours.
10. according to the production method of the aliphatic polyester of the fully biodegradable described in the claim 1, the weight-average molecular weight that it is characterized in that the aliphatic polyester that obtains is more than 150,000.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102775590A (en) * | 2012-08-15 | 2012-11-14 | 金发科技股份有限公司 | Poly(butylene succinate) and preparation method thereof |
| CN103225176A (en) * | 2013-04-24 | 2013-07-31 | 徐双喜 | Preparation method for completely biodegradable aliphatic polyester spunbond non-woven fabric |
| CN103408736A (en) * | 2013-08-08 | 2013-11-27 | 山东汇盈新材料科技有限公司 | Preparation method of high-molecular-weight biodegradable polyester |
| CN103468195A (en) * | 2013-09-26 | 2013-12-25 | 上海天洋热熔胶有限公司 | Preparation method of biodegradable polyester hot melt adhesive |
| CN104119518A (en) * | 2014-07-22 | 2014-10-29 | 南京大学 | Method for synthesizing poly(butanediol succinate-co-butanediol adipate) (PBSA) by biological organic guanidine salt catalysis process |
| CN110437433A (en) * | 2018-05-03 | 2019-11-12 | 上海回天新材料有限公司 | A kind of purposes of the method for preparing aliphatic polyester polyols and products thereof |
| CN113754874A (en) * | 2021-08-13 | 2021-12-07 | 浙江恒澜科技有限公司 | Preparation method of high molecular weight biodegradable poly (terephthalic acid-adipic acid-ethylene glycol ester) |
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2011
- 2011-05-11 CN CN2011101199502A patent/CN102229702A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102775590A (en) * | 2012-08-15 | 2012-11-14 | 金发科技股份有限公司 | Poly(butylene succinate) and preparation method thereof |
| CN102775590B (en) * | 2012-08-15 | 2014-11-12 | 金发科技股份有限公司 | Poly(butylene succinate) and preparation method thereof |
| CN103225176A (en) * | 2013-04-24 | 2013-07-31 | 徐双喜 | Preparation method for completely biodegradable aliphatic polyester spunbond non-woven fabric |
| CN103408736A (en) * | 2013-08-08 | 2013-11-27 | 山东汇盈新材料科技有限公司 | Preparation method of high-molecular-weight biodegradable polyester |
| CN103408736B (en) * | 2013-08-08 | 2015-12-09 | 山东汇盈新材料科技有限公司 | The preparation method of high-molecular-weighbiodegradable biodegradable polyester |
| CN103468195A (en) * | 2013-09-26 | 2013-12-25 | 上海天洋热熔胶有限公司 | Preparation method of biodegradable polyester hot melt adhesive |
| CN104119518A (en) * | 2014-07-22 | 2014-10-29 | 南京大学 | Method for synthesizing poly(butanediol succinate-co-butanediol adipate) (PBSA) by biological organic guanidine salt catalysis process |
| CN104119518B (en) * | 2014-07-22 | 2016-01-20 | 南京大学 | The method of biological organic guanidinesalt catalysis method synthesis poly-(succinic acid-butanediol ester-altogether-tetramethylene adipate) |
| WO2016011939A1 (en) * | 2014-07-22 | 2016-01-28 | 南京大学 | Process method for synthesizing poly(butylene succinate-co-butylene adipate) catalyzed by biomass creatinine |
| CN110437433A (en) * | 2018-05-03 | 2019-11-12 | 上海回天新材料有限公司 | A kind of purposes of the method for preparing aliphatic polyester polyols and products thereof |
| CN110437433B (en) * | 2018-05-03 | 2021-05-28 | 上海回天新材料有限公司 | Method for preparing aliphatic polyester polyol and application of product thereof |
| CN113754874A (en) * | 2021-08-13 | 2021-12-07 | 浙江恒澜科技有限公司 | Preparation method of high molecular weight biodegradable poly (terephthalic acid-adipic acid-ethylene glycol ester) |
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Application publication date: 20111102 |