CN114621450A - Method for modifying biodegradable polyester through chain extension and application thereof - Google Patents

Method for modifying biodegradable polyester through chain extension and application thereof Download PDF

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Publication number
CN114621450A
CN114621450A CN202110370521.6A CN202110370521A CN114621450A CN 114621450 A CN114621450 A CN 114621450A CN 202110370521 A CN202110370521 A CN 202110370521A CN 114621450 A CN114621450 A CN 114621450A
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melt
biodegradable polyester
chain
reaction
chain extension
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CN114621450B (en
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叶秀丝
胡立楠
刘晨
郭东生
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Guangzhou Deheng Zhiyuan Technology Co.,Ltd.
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Jiangsu Ruian Applied Biotechnology Co ltd
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    • 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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91—Polymers modified by chemical after-treatment
    • C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/916—Dicarboxylic acids and dihydroxy compounds

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention relates to the field of polyester, in particular to a method for modifying biodegradable polyester by chain extension and application thereof. The method comprises the following steps: 1. pumping out the first biodegradable polyester melt from the prepolymerization kettle by a melt metering gear pump, cooling the melt pipeline, and injecting a chain extender; 2. the first biodegradable polyester melt and the chain extender enter a melt mixing device together to be uniformly mixed, and then enter a melt homogenizer to carry out chain extension homogenization reaction, so that a pre-polymerization chain extension modified biodegradable polyester melt is obtained after the reaction; 3. pumping out a second biodegradable polyester melt from the prepolymerization kettle by a melt metering gear pump, allowing the second biodegradable polyester melt to enter a polycondensation kettle for polymerization reaction to obtain a prepolymerization tackifying polyester melt; 4. mixing the pre-polymerization chain extension modified biodegradable polyester melt and the pre-polymerization tackifying polyester melt, then feeding the mixture into a tackifying kettle for tackifying reaction to obtain a chain extension modified biodegradable polyester melt after reaction, and cutting the melt into particles after cooling to obtain chain extension modified biodegradable polyester chips.

Description

Method for modifying biodegradable polyester through chain extension and application thereof
Technical Field
The invention relates to the field of polyester, in particular to a method for modifying biodegradable polyester by chain extension and application thereof.
Background
Polyester is a generic name of polymers prepared by polycondensation of polyhydric alcohols and polybasic acids, and consumption of polyester is also increasing year by year with rapid growth of national economy. The biodegradable polyester is a polyester which can be completely decomposed by microorganisms existing in nature, such as bacteria, mould, algae and the like, has small burden on the environment and is a polyester generally used in the market at the present stage. It is currently a well-accepted method to produce high molecular weight biodegradable polyesters by adding certain chain extenders to the melt.
CN103755941A discloses a method for continuously polymerizing chain-extended modified polyester, which has high requirements on melt viscosity during prepolymerization, and a chain extender needs to be injected into a melt pipeline by a high-pressure injector, so that the requirements on equipment are high, and hidden troubles are increased for the safety production of enterprises.
CN200810112443.4 discloses a method for preparing biodegradable polyesteramide by chain extension, in which bisoxazoline and diacylbislactam are used as chain extenders, and the prepared finished product has high residue of the chain extenders and is not good for health and environment.
Disclosure of Invention
The first aspect of the invention provides a method for chain-extending a modified biodegradable polyester, comprising the steps of:
1. after the raw materials for preparing the biodegradable polyester are completely esterified, pumping the esterified raw materials into a prepolymerization kettle by a melt metering gear pump for reaction;
2. pumping out the first biodegradable polyester melt from the prepolymerization kettle by a melt metering gear pump, cooling the melt pipeline, and injecting a chain extender;
3. the first biodegradable polyester melt and the chain extender enter a melt mixing device together;
4. uniformly mixing the first biodegradable polyester melt and a chain extender in a melt mixing device, and then entering a melt homogenizer for chain extension homogenization reaction to obtain a pre-polymerization chain extension modified biodegradable polyester melt after the reaction;
5. pumping out a second biodegradable polyester melt from the prepolymerization kettle by a melt metering gear pump, and allowing the second biodegradable polyester melt to enter a polycondensation kettle for polymerization reaction to obtain a prepolymerization tackifying polyester melt;
6. and (3) mixing the pre-polymerization chain extension modified biodegradable polyester melt obtained in the step (4) and the pre-polymerization tackifying polyester melt obtained in the step (5), feeding the mixture into a tackifying kettle for tackifying reaction to obtain a chain extension modified biodegradable polyester melt, and granulating the cooled chain extension modified biodegradable polyester melt to obtain the chain extension modified biodegradable polyester slice.
As a preferred embodiment, the temperature of the melt channel is 120-220 ℃.
As a preferred embodiment, the mass ratio of the first biodegradable polyester melt to the second biodegradable polyester melt is 1: (1-6).
As a preferred embodiment, the temperature of the melt mixing device is 120-220 ℃.
As a preferred embodiment, the reaction temperature of the chain extension homogenization reaction is 220-260 ℃, and the reaction time is 2-30 min.
As a preferred embodiment, the reaction temperature in the polycondensation kettle is 220-280 ℃, the reaction time is 40-180min, and the vacuum degree is not more than 120 Pa.
As a preferred embodiment, the reaction temperature in the viscosity increasing kettle is 220-280 ℃, the reaction time is 20-100min, and the vacuum degree is not more than 120 Pa.
As a preferred embodiment, the raw material for preparing the first biodegradable polyester melt and the second biodegradable polyester melt comprises at least one of PBAT, PBST, PBS, PBA, PBT, PHB, PVA, PHA, PLA, PCL, PPC.
In a preferred embodiment, the intrinsic viscosity of the first biodegradable polyester melt and the intrinsic viscosity of the second biodegradable polyester melt are in the range of 0.05 to 0.25 dL/g.
The second aspect of the invention provides an application of a method for chain extension modification of biodegradable polyester, which is applied to the production of biodegradable polyester.
Compared with the prior art, the invention has the following beneficial effects:
1. compared with the prior art, the method for modifying the biodegradable polyester through chain extension only has the advantages that only one part of the biodegradable polyester melt enters the polycondensation kettle for reaction, so that the production time of the whole system is shortened, in addition, the melt in the polycondensation kettle is less, the stirring current required by equipment is greatly reduced, the vacuum energy consumption is reduced, and the economic benefit is improved.
2. According to the method for chain extension modification of the biodegradable polyester, the biodegradable polyester melt is divided into the first biodegradable polyester melt and the second biodegradable polyester melt according to a specific proportion, chain extension homogenization reaction and tackifying reaction are respectively carried out, the processes that the melt is sequentially subjected to the chain extension homogenization reaction and the tackifying reaction in the prior art are replaced, the residence time of the melt in a reaction kettle is shortened, the end group content of the reacted polymer is lower, the thermal degradation rate of the melt is lower, and the mechanical property of the prepared chain extension modified biodegradable polyester slice is more excellent.
3. The method for chain extension modification of biodegradable polyester has low requirement on the melt viscosity of the biodegradable polyester during prepolymerization, has low requirement on melt mixer equipment, can be uniformly mixed without a large power motor, and further improves the economic benefit.
4. According to the method for chain extension modification of biodegradable polyester, the specific reaction temperature, reaction time and vacuum degree of the tackifying kettle are set, so that the chain extender in the melt is fully reacted, the residual amount of the chain extender in the finished chain extension modified biodegradable polyester chip is extremely low, and the method has no adverse effect on the environment and the health of human bodies.
Detailed Description
In order to solve the above technical problems, a first aspect of the present invention provides a method for chain-extending a modified biodegradable polyester, comprising the steps of:
1. after the raw materials for preparing the biodegradable polyester are completely esterified, pumping the esterified raw materials into a prepolymerization kettle by a melt metering gear pump for reaction;
2. pumping out the first biodegradable polyester melt from the prepolymerization kettle by a melt metering gear pump, cooling the melt pipeline, and injecting a chain extender;
3. the first biodegradable polyester melt and the chain extender enter a melt mixing device together;
4. uniformly mixing the first biodegradable polyester melt and a chain extender in a melt mixing device, and then entering a melt homogenizer for chain extension homogenization reaction to obtain a pre-polymerization chain extension modified biodegradable polyester melt after the reaction;
5. pumping out a second biodegradable polyester melt from the prepolymerization kettle by a melt metering gear pump, and allowing the second biodegradable polyester melt to enter a polycondensation kettle for polymerization reaction to obtain a prepolymerization tackifying polyester melt;
6. and (3) mixing the pre-polymerization chain extension modified biodegradable polyester melt obtained in the step (4) and the pre-polymerization tackifying polyester melt obtained in the step (5), feeding the mixture into a tackifying kettle for tackifying reaction to obtain a chain extension modified biodegradable polyester melt, and granulating the cooled chain extension modified biodegradable polyester melt to obtain the chain extension modified biodegradable polyester slice.
As a preferred embodiment, the melting temperature is 270-300 ℃.
As a preferred embodiment, the temperature of the melt pipe after cooling in step 2 is 120-220 ℃.
Preferably, the temperature of the melt pipeline after cooling in the step 2 is 150-200 ℃.
The temperature of the cooled melt pipeline in the method is far lower than the temperature range generally selected in the prior art, and the applicant finds in repeated experiments that if the cooling is carried out according to the temperature range in the prior art, after the chain extender is added in the step 2, the chain extender can react with the first biodegradable polyester melt before entering the homogenizer, but the reaction is not thorough enough and often occurs along with harmful byproducts, so that the applicant finds through a large number of experiments that when the temperature of the cooled melt pipeline is 150-.
As a preferred embodiment, the mass ratio of the first biodegradable polyester melt to the second biodegradable polyester melt is 1: (1-6).
Preferably, the mass ratio of the first biodegradable polyester melt to the second biodegradable polyester melt is 1: (1-4).
Among the prior art, polyester prepolymerization fuse-element passes through the polycondensation cauldron in proper order, mixes with the chain extender after cooling, and because whole polyester fuse-element is after the polycondensation cauldron, self viscosity is too big, again with the chain extender fully react, motor power, the equipment design requirement to fuse-element mixing vessel are very high, power consumption is huge in the mixing process, and appear easily because of the too big unfavorable phenomenon such as equipment card that arouses of viscosity, applicant's creative discovery, be 1 with the polyester fuse-element according to the mass ratio: (1-6), preferably 1: the proportion of (1-4) is divided into a first biodegradable polyester melt and a second biodegradable polyester melt, and the first biodegradable polyester melt is reacted with a chain extender and then mixed with the second biodegradable polyester melt, so that the preparation process not only ensures that the prepared chain-extended modified biodegradable polyester chip has good mechanical property and intrinsic viscosity, but also reduces energy consumption and equipment loss in the preparation process, and greatly improves the economic benefit of enterprises.
As a preferred embodiment, the chain extender is injected into the melt pipe by a chain extender injection device.
As a preferred embodiment, the melt mixing device comprises a jacketed homogenizing pump, a dynamic mixer, a twin screw extrusion apparatus.
In a preferred embodiment, the temperature of the melt mixing device is 120-220 ℃.
Preferably, the temperature of the melt mixing device is 150-200 ℃.
The applicant set the cooled melt line temperature and the melt mixing device temperature to the same preferred range, which is set for the purpose of continuing to suppress the prior reaction of the chain extender and the first biodegradable polyester melt inside the melt mixing device, thereby precluding the occurrence of harmful by-products.
As a preferred embodiment, the reaction temperature of the chain extension homogenization reaction is 220-260 ℃, and the reaction time is 2-30 min.
Preferably, the reaction time of the chain extension homogenization reaction is 5-15 min.
The chain extension homogenization reaction aims to ensure that a chain extender and a polyester melt are fully reacted to increase the viscosity of the polyester melt, in the actual production, too short homogenization time can cause incomplete reaction and residue of the chain extender, the quality of the polyester is influenced, the chain extender is harmful to the environment and human bodies, too long homogenization time can cause thermal degradation of the polyester during the homogenization reaction, the end group content of a polyester finished product is high, and the unqualified rate of the product is high.
As a preferred embodiment, the reaction temperature in the polycondensation kettle is 220-280 ℃, the reaction time is 40-180min, and the vacuum degree is not more than 120 Pa.
Preferably, the reaction temperature in the polycondensation kettle is 230-260 ℃, the reaction time is 60-90min, and the vacuum degree is not more than 100 Pa.
Chain extender after chain extension homogenization and first biodegradable polyester melt carry out polymerization reaction in the polycondensation kettle, compare in prior art, the polyester melt in the polycondensation kettle is still less, consequently reaction time and vacuum all have the reduction by a wide margin than prior art, need not powerful high-pressure vacuum and can reach good finished product quality, have also reduced the production energy consumption simultaneously.
As a preferred embodiment, the reaction temperature in the viscosity increasing kettle is 220-280 ℃, the reaction time is 20-100min, and the vacuum degree is not more than 120 Pa.
Preferably, the reaction temperature in the viscosity increasing kettle is 230-260 ℃, the reaction time is 30-60min, and the vacuum degree is not more than 100 Pa.
In a preferred embodiment, the chain extender is at least one selected from the group consisting of epoxy chain extenders and isocyanate chain extenders.
Preferably, the chain extender is at least one selected from the group consisting of epoxy resin, ethylene oxide, toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, and lysine diisocyanate.
Preferably, the chain extender is hexamethylene diisocyanate.
As a preferred embodiment, the content of the chain extender in the raw materials for the preparation of the first biodegradable polyester melt is from 0.001 to 5% by weight.
Preferably, the content of the chain extender in the raw material for preparing the first biodegradable polyester melt is 0.003 to 3 wt%.
Compared with the prior art, the process of reacting the first biodegradable polyester melt with the chain extender is adopted in the invention, and is cooperated with the subsequent tackifying process of the tackifying kettle, so that the chain extender has longer reaction time and lower residue under the vacuum condition, and the applicant finds that when the content of the chain extender is 0.001-5 wt%, preferably 0.003-3 wt%, the chain extender can fully react with the first biodegradable polyester melt without causing residue, and the whole production flow is optimized.
As a preferred embodiment, the preparation raw material of the first biodegradable polyester melt comprises at least one of PBAT, PBST, PBS, PBA, PBT, PHB, PVA, PHA, PLA, PCL, PPC.
As a preferred embodiment, the intrinsic viscosity of the first biodegradable polyester melt is from 0.05 to 0.25 dL/g.
Preferably, the preparation starting material of the first biodegradable polyester melt comprises PBAT.
As a preferred embodiment, the raw material for preparing the first biodegradable polyester melt further comprises a first catalyst and a first heat stabilizer.
As a preferred embodiment, the first catalyst is contained in the amount of 0.001 to 0.3 wt% in the raw materials for the preparation of the first biodegradable polyester melt.
Preferably, the first catalyst is present in an amount of 0.002 to 0.2 wt.% in the raw material for the first biodegradable polyester melt.
As a preferred embodiment, the first thermostabilizer is present in an amount of 0.001-0.3 wt% in the raw materials for the preparation of the first biodegradable polyester melt.
Preferably, the first heat stabilizer is contained in an amount of 0.002 to 0.2 wt% in the raw material for preparing the first biodegradable polyester melt.
As a preferred embodiment, the raw material for preparing the second biodegradable polyester melt comprises at least one of PBAT, PBST, PBS, PBA, PBT, PHB, PVA, PHA, PLA, PCL, PPC.
As a preferred embodiment, the intrinsic viscosity of the second biodegradable polyester melt is from 0.05 to 0.25 dL/g.
Preferably, the preparation starting material of the second biodegradable polyester melt comprises PBAT.
As a preferred embodiment, the raw material for preparing the second biodegradable polyester melt further comprises a second catalyst and a second heat stabilizer.
As a preferred embodiment, the content of the second catalyst in the raw material for producing the second biodegradable polyester melt is 0.001 to 0.3% by weight.
Preferably, the content of the second catalyst in the raw material for preparing the second biodegradable polyester melt is 0.002-0.2 wt%.
As a preferred embodiment, the second heat stabilizer is contained in an amount of 0.001 to 0.3 wt% in the raw material for the preparation of the second biodegradable polyester melt.
Preferably, the content of the second heat stabilizer in the raw material for preparing the second biodegradable polyester melt is 0.002-0.2 wt%.
The first and second catalysts comprise at least one of titanium catalyst, antimony catalyst and metal acetate.
Preferably, the first and second catalysts comprise at least one of butyl titanate, tetrabutyl titanate, tetraisopropyl titanate, ethylene glycol antimony, antimony acetate, antimony trioxide, sodium acetate, aluminum acetate, calcium acetate and potassium acetate.
Preferably, the first and second catalysts are both butyl titanate.
Preferably, the first and second heat stabilizers include at least one of phosphoric acid and phosphoric acid ester compounds.
Preferably, the first and second heat stabilizers include at least one of orthophosphoric acid, phosphorous acid, pyrophosphoric acid, phosphoric acid esters, phosphorous acid esters, and trimethyl phosphate.
Preferably, the first and second heat stabilizers are trimethyl phosphate.
The second aspect of the invention provides an application of a method for chain extension modification of biodegradable polyester, which is applied to the production of biodegradable polyester.
The present invention will be specifically described below by way of examples. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention.
Hexamethylene diisocyanate CAS number 822-06-0.
PBAT is a copolymer of butylene adipate and butylene terephthalate, purchased from ningbo city blue minister plastication ltd.
Butyl titanate CAS number 5593-70-4.
Trimethyl phosphate CAS number 512-56-1.
In addition, the starting materials used are all commercially available, unless otherwise specified.
Examples
Example 1
Embodiment 1 provides a method for chain-extending a modified biodegradable polyester, comprising the steps of:
1. after the raw materials for preparing the biodegradable polyester are completely esterified, pumping the esterified raw materials into a prepolymerization kettle by a melt metering gear pump for reaction;
2. pumping out the first biodegradable polyester melt from the prepolymerization kettle by a melt metering gear pump, cooling the melt pipeline, and injecting a chain extender;
3. the first biodegradable polyester melt and the chain extender enter a melt mixing device together;
4. uniformly mixing the first biodegradable polyester melt and a chain extender in a melt mixing device, and then entering a melt homogenizer for chain extension homogenization reaction to obtain a pre-polymerization chain extension modified biodegradable polyester melt after the reaction;
5. pumping out a second biodegradable polyester melt from the prepolymerization kettle by a melt metering gear pump, and allowing the second biodegradable polyester melt to enter a polycondensation kettle for polymerization reaction to obtain a prepolymerization tackifying polyester melt;
6. and (3) mixing the pre-polymerization chain extension modified biodegradable polyester melt obtained in the step (4) and the pre-polymerization tackifying polyester melt obtained in the step (5), feeding the mixture into a tackifying kettle for tackifying reaction to obtain a chain extension modified biodegradable polyester melt, and granulating the cooled chain extension modified biodegradable polyester melt to obtain the chain extension modified biodegradable polyester slice.
The melting temperature was 270 ℃.
The melt line temperature after cooling in step 1 is 150 ℃.
The temperature of the melt mixing device was 150 ℃.
The reaction temperature of the homogenization reaction is 220 ℃, and the reaction time is 5 min.
The mass ratio of the first biodegradable polyester melt to the second biodegradable polyester melt is 1: 1.
the reaction temperature in the polycondensation kettle is 230 ℃, the reaction time is 60min, and the vacuum degree is 100 Pa.
The reaction temperature in the tackifying kettle is 230 ℃, the reaction time is 30min, and the vacuum degree is 100 Pa.
The preparation raw materials of the first biodegradable polyester melt comprise PBAT, a chain extender, a first catalyst and a first heat stabilizer; the PBAT has the intrinsic viscosity of 0.05dL/g and the content of 99.996 wt%, the chain extender is hexamethylene diisocyanate, the injection amount is 0.003 wt%, and the first catalyst is butyl titanate with the content of 0.002 wt%; the first heat stabilizer is trimethyl phosphate, and the content of the first heat stabilizer is 0.002 wt%.
The preparation raw materials of the second biodegradable polyester melt comprise PBAT, a second catalyst and a second heat stabilizer; the PBAT has the intrinsic viscosity of 0.05dL/g and the content of 99.996wt percent, and the second catalyst is butyl titanate with the content of 0.002wt percent; the second heat stabilizer is trimethyl phosphate, and the content of the second heat stabilizer is 0.002 wt%.
Example 2
Embodiment 2 provides a method for chain-extending a modified biodegradable polyester, comprising the steps of:
1. after the raw materials for preparing the biodegradable polyester are completely esterified, pumping the esterified raw materials into a prepolymerization kettle by a melt metering gear pump for reaction;
2. pumping out the first biodegradable polyester melt from the prepolymerization kettle by a melt metering gear pump, cooling the melt pipeline, and injecting a chain extender;
3. the first biodegradable polyester melt and the chain extender enter a melt mixing device together;
4. uniformly mixing the first biodegradable polyester melt and a chain extender in a melt mixing device, and then entering a melt homogenizer for chain extension homogenization reaction to obtain a pre-polymerization chain extension modified biodegradable polyester melt after the reaction;
5. pumping out a second biodegradable polyester melt from the prepolymerization kettle by a melt metering gear pump, and allowing the second biodegradable polyester melt to enter a polycondensation kettle for polymerization reaction to obtain a prepolymerization tackifying polyester melt;
6. and (3) mixing the pre-polymerization chain extension modified biodegradable polyester melt obtained in the step (4) and the pre-polymerization tackifying polyester melt obtained in the step (5), feeding the mixture into a tackifying kettle for tackifying reaction to obtain a chain extension modified biodegradable polyester melt, and granulating the cooled chain extension modified biodegradable polyester melt to obtain the chain extension modified biodegradable polyester slice.
The melting temperature was 300 ℃.
The melt pipe temperature after cooling in step 1 is 200 ℃.
The temperature of the melt mixing device was 200 ℃.
The reaction temperature of the homogenization reaction is 260 ℃, and the reaction time is 15 min.
The mass ratio of the first biodegradable polyester melt to the second biodegradable polyester melt is 1: 4.
the reaction temperature in the polycondensation kettle is 260 ℃, the reaction time is 90min, and the vacuum degree is 50 Pa.
The reaction temperature in the viscosity increasing kettle is 230 ℃, the reaction time is 30min, and the vacuum degree is 100 Pa.
The preparation raw materials of the first biodegradable polyester melt comprise PBAT, a chain extender, a first catalyst and a first heat stabilizer; the PBAT has the intrinsic viscosity of 0.25dL/g and the content of 96.6 wt%, the chain extender is hexamethylene diisocyanate, the injection amount is 3 wt%, and the first catalyst is butyl titanate with the content of 0.2 wt%; the first heat stabilizer is trimethyl phosphate, and the content of the first heat stabilizer is 0.2 wt%.
The preparation raw materials of the second biodegradable polyester melt comprise PBAT, a second catalyst and a second heat stabilizer; the PBAT has the intrinsic viscosity of 0.25dL/g and the content of 99.6wt percent, and the second catalyst is tetrabutyl titanate and the content of 0.2wt percent; the second heat stabilizer is trimethyl phosphate, and the content of the second heat stabilizer is 0.2 wt%.
Example 3
Embodiment 3 provides a method for chain-extending a modified biodegradable polyester, comprising the steps of:
1. after the raw materials for preparing the biodegradable polyester are completely esterified, pumping the esterified raw materials into a prepolymerization kettle by a melt metering gear pump for reaction;
2. pumping out the first biodegradable polyester melt from the prepolymerization kettle by a melt metering gear pump, cooling a melt pipeline, and injecting a chain extender;
3. the first biodegradable polyester melt and the chain extender enter a melt mixing device together;
4. uniformly mixing the first biodegradable polyester melt and a chain extender in a melt mixing device, and then entering a melt homogenizer for chain extension homogenization reaction to obtain a pre-polymerization chain extension modified biodegradable polyester melt after the reaction;
5. pumping out a second biodegradable polyester melt from the prepolymerization kettle by a melt metering gear pump, and allowing the second biodegradable polyester melt to enter a polycondensation kettle for polymerization reaction to obtain a prepolymerization tackifying polyester melt;
6. and (3) mixing the pre-polymerization chain extension modified biodegradable polyester melt obtained in the step (4) and the pre-polymerization tackifying polyester melt obtained in the step (5), feeding the mixture into a tackifying kettle for tackifying reaction to obtain a chain extension modified biodegradable polyester melt, and granulating the cooled chain extension modified biodegradable polyester melt to obtain the chain extension modified biodegradable polyester slice.
The melting temperature was 290 ℃.
The temperature of the melt pipe cooled in the step 1 is 180 ℃.
The temperature of the melt mixing device was 170 ℃.
The reaction temperature of the homogenization reaction is 230 ℃, and the reaction time is 10 min.
The mass ratio of the first biodegradable polyester melt to the second biodegradable polyester melt is 1: 3.
the reaction temperature in the polycondensation kettle is 240 ℃, the reaction time is 80min, and the vacuum degree is 70 Pa.
The reaction temperature in the tackifying kettle is 250 ℃, the reaction time is 50min, and the vacuum degree is 60 Pa.
The preparation raw materials of the first biodegradable polyester melt comprise PBAT, a chain extender, a first catalyst and a first heat stabilizer; the PBAT has the intrinsic viscosity of 0.1dL/g and the content of 99.6 wt%, the chain extender is hexamethylene diisocyanate, the injection amount is 0.1 wt%, and the first catalyst is butyl titanate with the content of 0.15 wt%; the first heat stabilizer is trimethyl phosphate, and the content of the first heat stabilizer is 0.15 wt%.
The preparation raw materials of the second biodegradable polyester melt comprise PBAT, a second catalyst and a second heat stabilizer; the PBAT has the intrinsic viscosity of 0.1dL/g and the content of 99.7wt percent, and the second catalyst is tetrabutyl titanate and the content of 0.15wt percent; the second heat stabilizer is trimethyl phosphate, and the content of the second heat stabilizer is 0.15 wt%.
Comparative example 1
Comparative example 1 provides a method for chain extension modification of biodegradable polyester, the specific implementation is the same as example 3, except that the reaction temperature in the tackifying kettle is 180 ℃.
Comparative example 2
Comparative example 2 provides a method for chain extension modification of biodegradable polyester, which is the same as example 3 except that the reaction time in the tackifying kettle is 15 min.
Comparative example 3
Comparative example 3 provides a method for chain extension of a modified biodegradable polyester, which is the same as example 3 except that the degree of vacuum in the tackifying kettle is 150 Pa.
Comparative example 4
Comparative example 4 provides a method of chain extending a modified biodegradable polyester, the specific embodiment being the same as example 3 except that the intrinsic viscosity of PBAT is 0.5 dL/g.
Comparative example 5
Comparative example 5 provides a method for chain extension modification of biodegradable polyester, which is the same as example 3 except that the mass ratio of the first biodegradable polyester melt to the second biodegradable polyester melt is 1: 10.
performance testing
The above examples and comparative examples were subjected to performance tests, and the results are shown in the following table.
Tensile strength test standard: GB1040-92
Elongation at break test standard: GB/T1040-2006
Isocyanate group detection standard: ISO 14896-
Tensile Strength (MPa) Elongation at Break (%) Residual isocyanate groups (ppm)
Example 1 30.5 615 29
Example 2 30.8 619 26
Example 3 31.1 623 15
Comparative example 1 25.3 566 48
Comparative example 2 24.9 552 53
Comparative example 3 24.6 543 51
Comparative example 4 22.8 539 49
Comparative example 5 20.1 489 50
While the invention has been described with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention.

Claims (10)

1. A method for modifying biodegradable polyester by chain extension is characterized by comprising the following steps:
1. after the raw materials for preparing the biodegradable polyester are completely esterified, pumping the esterified raw materials into a prepolymerization kettle by a melt metering gear pump for reaction;
2. pumping out the first biodegradable polyester melt from the prepolymerization kettle by a melt metering gear pump, cooling the melt pipeline, and injecting a chain extender;
3. the first biodegradable polyester melt and the chain extender enter a melt mixing device together;
4. uniformly mixing the first biodegradable polyester melt and a chain extender in a melt mixing device, then feeding the mixture into a melt homogenizer for chain extension homogenization reaction, and obtaining a pre-polymerized chain extension modified biodegradable polyester melt after the reaction;
5. pumping out a second biodegradable polyester melt from the prepolymerization kettle by a melt metering gear pump, and allowing the second biodegradable polyester melt to enter a polycondensation kettle for polymerization reaction to obtain a prepolymerized and tackified polyester melt;
6. and (3) mixing the pre-polymerization chain extension modified biodegradable polyester melt obtained in the step (4) and the pre-polymerization tackifying polyester melt obtained in the step (5), feeding the mixture into a tackifying kettle for tackifying reaction to obtain a chain extension modified biodegradable polyester melt, and granulating the cooled chain extension modified biodegradable polyester melt to obtain the chain extension modified biodegradable polyester slice.
2. The method for chain-extending modified biodegradable polyester as claimed in claim 1, wherein the temperature of the melt pipe is 120-220 ℃.
3. The method for chain-extending modified biodegradable polyester according to claim 1, wherein the mass ratio of the first biodegradable polyester melt to the second biodegradable polyester melt is 1: (1-6).
4. The method for chain-extending modified biodegradable polyester as claimed in claim 1, wherein the temperature of the melt mixing device is 120-220 ℃.
5. The method for chain-extending modified biodegradable polyester as claimed in claim 1, wherein the reaction temperature of the chain-extending homogenization reaction is 220-260 ℃ and the reaction time is 2-30 min.
6. The method for chain-extending modified biodegradable polyester as claimed in claim 1, wherein the reaction temperature in the polycondensation kettle is 220-280 ℃, the reaction time is 40-180min, and the vacuum degree is not greater than 120 Pa.
7. The method for chain-extending modified biodegradable polyester as claimed in claim 1, wherein the reaction temperature in the viscosity increasing kettle is 220-280 ℃, the reaction time is 20-100min, and the vacuum degree is not more than 120 Pa.
8. The method for chain-extending modified biodegradable polyester according to claim 1, wherein the raw material for preparing the first and second biodegradable polyester melts comprises at least one of PBAT, PBST, PBS, PBA, PBT, PHB, PVA, PHA, PLA, PCL, and PPC.
9. The method for chain-extending a modified biodegradable polyester as claimed in claim 1, wherein the intrinsic viscosity of the first biodegradable polyester melt and the intrinsic viscosity of the second biodegradable polyester melt are 0.05-0.25 dL/g.
10. Use of a method of chain extending a modified biodegradable polyester according to any one of claims 1-9 in the production of a biodegradable polyester.
CN202110370521.6A 2021-04-07 2021-04-07 Method for chain extension modified biodegradable polyester and application thereof Active CN114621450B (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102007159A (en) * 2008-04-15 2011-04-06 巴斯夫欧洲公司 Method for the continuous production of biodegradable polyesters
US20130209568A1 (en) * 2010-07-09 2013-08-15 Innocore Technologies B.V. Biodegradable phase separated segmented multi block co-polymers and release of biologically active polypeptides
CN106220836A (en) * 2016-08-30 2016-12-14 无锡市兴盛新材料科技有限公司 A kind of preparation method of high viscosity resistance to thermal degradation PBT polyester
CN109750385A (en) * 2018-12-29 2019-05-14 中国纺织科学研究院有限公司 A kind of continuous process system and preparation method of functional polyester

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102007159A (en) * 2008-04-15 2011-04-06 巴斯夫欧洲公司 Method for the continuous production of biodegradable polyesters
US20130209568A1 (en) * 2010-07-09 2013-08-15 Innocore Technologies B.V. Biodegradable phase separated segmented multi block co-polymers and release of biologically active polypeptides
CN106220836A (en) * 2016-08-30 2016-12-14 无锡市兴盛新材料科技有限公司 A kind of preparation method of high viscosity resistance to thermal degradation PBT polyester
CN109750385A (en) * 2018-12-29 2019-05-14 中国纺织科学研究院有限公司 A kind of continuous process system and preparation method of functional polyester

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