CN114230778A - Polymerization method of chain-extended modified polyester, chain-extended modified polyester and application thereof - Google Patents
Polymerization method of chain-extended modified polyester, chain-extended modified polyester and application thereof Download PDFInfo
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- CN114230778A CN114230778A CN202111327089.9A CN202111327089A CN114230778A CN 114230778 A CN114230778 A CN 114230778A CN 202111327089 A CN202111327089 A CN 202111327089A CN 114230778 A CN114230778 A CN 114230778A
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- 229920000728 polyester Polymers 0.000 title claims abstract description 350
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 32
- 239000000155 melt Substances 0.000 claims abstract description 110
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 88
- 239000004970 Chain extender Substances 0.000 claims abstract description 86
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 238000001816 cooling Methods 0.000 claims abstract description 20
- 239000000289 melt material Substances 0.000 claims abstract description 20
- 229920000229 biodegradable polyester Polymers 0.000 claims abstract description 11
- 239000004622 biodegradable polyester Substances 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 3
- 230000035484 reaction time Effects 0.000 claims description 35
- 238000002156 mixing Methods 0.000 claims description 19
- 239000002253 acid Substances 0.000 claims description 10
- 238000002347 injection Methods 0.000 claims description 10
- 239000007924 injection Substances 0.000 claims description 10
- 125000005442 diisocyanate group Chemical group 0.000 claims description 9
- 239000000539 dimer Substances 0.000 claims description 9
- 238000001125 extrusion Methods 0.000 claims description 8
- 229920000704 biodegradable plastic Polymers 0.000 claims description 3
- 238000000265 homogenisation Methods 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 6
- 230000036632 reaction speed Effects 0.000 abstract description 5
- 239000004033 plastic Substances 0.000 abstract description 4
- 229920003023 plastic Polymers 0.000 abstract description 4
- 238000004134 energy conservation Methods 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 description 15
- 239000000463 material Substances 0.000 description 14
- 230000000694 effects Effects 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 9
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- 238000002360 preparation method Methods 0.000 description 8
- 230000009286 beneficial effect Effects 0.000 description 7
- 230000009467 reduction Effects 0.000 description 7
- 239000000243 solution Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- -1 aliphatic isocyanates Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
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- 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
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Abstract
The invention relates to the technical field of polyester plastics, in particular to a polymerization method of chain-extended modified polyester and a manufacturing process and application thereof, wherein the method comprises the following steps of S1, dividing a prepolymerized polyester melt into a first polyester melt and a second polyester melt; s2, injecting the first polyester melt into a melt pipeline, and injecting the second polyester melt into a polycondensation kettle; cooling the first polyester melt in the melt pipeline, injecting a chain extender, and sequentially feeding the first polyester melt and the chain extender into a melt mixer and a melt homogenizer; polycondensation and tackifying the second polyester melt in a polycondensation kettle in a vacuum state; s3, injecting the obtained first chain extension modified polyester melt and the obtained second polycondensation tackifying polyester melt into a tackifying kettle for tackifying to obtain a tackifying polyester melt material; s4, cooling and dicing the melt material of the tackified polyester to obtain the biodegradable polyester, wherein the polymerization method has the advantages of energy conservation, high reaction speed, complete reaction and low residue.
Description
Technical Field
The invention relates to the technical field of polyester plastics, in particular to a polymerization method of chain-extended modified polyester, the chain-extended modified polyester and application thereof.
Background
The polyester plastic has good molecular flexibility, is easy to be catalyzed and degraded by biological enzyme under the action of microorganisms, and is widely used for various packaging materials, agricultural films, biological medicines and the like.
The polyester plastic is obtained by the polymerization reaction of multiple pure and multiple acids. In the prior art, a prepolymerization-polycondensation-tackifying method is adopted to prepare biodegradable polyester, but the problems of slow reaction and incomplete reaction are caused by the fact that all polyester solution reacts in a polycondensation kettle and more material stays in the polycondensation kettle. In the prior art, a chain extension method is also adopted to polymerize polyester, and the polyester molecular chain is enlarged by the reaction of an active group of a chain extender and a terminal hydroxyl group or a terminal carboxyl group in the polyester.
For example, patent CN201410008404 discloses a method for continuously polymerizing chain-extended modified polyester, in which all polyester melts are injected into a melt pipe, and then enter a dynamic mixer, a homogenizer and a filter with a chain extender in sequence, and then are cooled, solidified and pelletized. However, the polyester continuous polymerization process of the above patent still has disadvantages: the polyester solution has high viscosity, and can be uniformly mixed by injecting the polyester solution at high pressure and using a large power motor, so that the energy consumption of equipment is increased, and the use requirement and the use risk of the equipment are increased.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a polymerization method of chain-extended modified polyester, which has the advantages of energy conservation, high reaction speed, complete reaction and low residue.
The second purpose of the invention is to provide a chain-extended modified polyester.
The invention also aims to provide application of the chain-extended modified polyester.
In order to achieve one of the above purposes, the invention provides the following technical scheme:
provided is a polymerization method of chain-extended modified polyester, comprising the following steps,
s1, dividing the prepolymerized polyester melt into a first polyester melt and a second polyester melt;
s2, injecting the first polyester melt into a melt pipeline, and injecting the second polyester melt into a polycondensation kettle;
cooling the first polyester melt in the melt pipeline until the temperature of the melt pipeline is 120-250 ℃, wherein the temperature is preferably 150-220 ℃, inputting the cooled first polyester melt into a melt mixer, injecting a chain extender into the melt mixer, mixing the first polyester melt with the chain extender, and inputting the mixed first polyester melt and the chain extender into a melt homogenizer for homogenization to obtain a first chain extension modified polyester melt;
the second polyester melt is subjected to polycondensation tackifying in a polycondensation kettle in a vacuum state to obtain a second polycondensation tackifying polyester melt;
s3, injecting the first chain extension modified polyester melt and the second polycondensation tackifying polyester melt into a tackifying kettle for tackifying to obtain a tackifying polyester melt material;
and S4, cooling and pelletizing the tackifying polyester melt material in sequence to obtain the biodegradable polyester.
The principle of the polymerization method of the chain-extended modified polyester is as follows: the prepolymerized polyester melt can reduce the viscosity of the polyester melt and reduce the energy consumption required in the subsequent polymerization reaction; the polyester melt is divided into a first polyester melt and a second polyester melt, the first polyester melt reacts with a chain extender in a melt channel to obtain a first chain extension modified polyester melt, and the second polyester melt is tackified in a polycondensation kettle to obtain a second polycondensation tackified polyester melt, so that the effect of tackification of the modified polyester melt by polycondensation is realized, the polyester amount in the polycondensation process is reduced, the reaction speed and the uniformity are improved, and the energy consumption of equipment is reduced; and injecting the first chain extension modified polyester melt and the second polycondensation tackifying polyester melt into a tackifying kettle for tackifying and reacting at a certain vacuum degree, so that the chain extender fully reacts with all the polyesters to prepare the chain extension modified polyester.
In some embodiments, the chain extender is dimer acid diisocyanate.
The dimer acid diisocyanate (DDI) is aliphatic diisocyanate, and the DDI is a long-chain compound, so that the polyester has better flexibility, water resistance and low toxicity than other aliphatic isocyanates, and the polyester can be suitable for biological mulching films and can prevent weeds, hard soil piles and the like from puncturing the mulching films to cause broken holes. Furthermore, DDI has the characteristics of ultraviolet ray resistance and no yellowing.
In some embodiments, the weight percentage of the chain extender in the first chain extended modified polyester melt is from 0.1% to 10%.
The above-mentioned 0.1 to 10 weight percent of the chain extender brings the most excellent toughening and flexibilizing effect, and the chain extender below or above the weight percent cannot improve the flexibility of the polyester best.
In some embodiments, the ratio of the amounts of the first polyester melt to the second polyester melt is (1:3) to (3: 1).
In some embodiments, in S1, the polyester melt is separated into the first polyester melt and the second polyester melt by a melt metering gear pump, and in S2, the chain extender is injected into a melt pipe by a chain extender injection device.
The melt metering gear pump and the chain extender injection device can accurately meter materials.
In some embodiments, the melt mixer comprises a homogenizing pump, a dynamic mixer, and a twin screw extrusion device.
In some embodiments, in S2, the mixing temperature of the melt mixer is 120 ℃ to 220 ℃, and the reaction time of the first polyester melt and the chain extender in the melt homogenizer after mixing is 2min to 60 min.
Compared with the prior art, the mixing temperature of the first polyester melt and the chain extender in the melt mixer and the reaction time in the melt homogenizer are both reduced, and the excellent mixing effect and homogenizing reaction effect can be ensured.
In some embodiments, the polycondensation kettle has a reaction temperature of 220 ℃ to 260 ℃, a reaction time of 40min to 180min, and a vacuum degree of < 100 pa.
The reaction temperature and the reaction time of the polycondensation kettle are less than those of the prior art, and the requirement on the vacuum degree can be reduced.
In some embodiments, the viscosity increasing kettle has a reaction temperature of 220-260 ℃, a vacuum degree of < 100pa, and a reaction time of 20-100 min.
In the tackifying process of the upper tackifying kettle, under the condition of sufficient reaction time and vacuum, isocyanate contained in the chain extender is fully reacted with all polyester, and the residue is lower.
The polymerization method of the chain-extended modified polyester has the following beneficial effects:
(1) compared with the prior art, the method has the advantages that the prepolymerized polyester melt is used as a raw material, the viscosity of the polyester melt can be reduced, the energy consumption required in the subsequent polymerization reaction is reduced, high-pressure injection of the polyester melt is not required, the equipment requirement and the equipment safety risk are reduced, the requirement on melt mixer equipment is not high, and the purpose of more uniform mixing can be achieved without a large-power motor.
(2) According to the invention, the polyester melt is divided into a first polyester melt and a second polyester melt, the first polyester melt reacts with the chain extender in the melt channel to obtain a first chain extension modified polyester melt, and the second polyester melt is tackified in the polycondensation kettle to obtain a second polycondensation tackified polyester melt, so that the effect of the polycondensation and the tackification of the modified polyester melt is realized, the polyester amount in the polycondensation process is reduced, the reaction speed and the uniformity are improved, and the energy consumption of equipment is reduced; compared with the process flow of prepolymerization, polycondensation and tackifying in the prior art, the method provided by the invention has the advantages that the polyester melt is divided into two parts, the material staying in the polycondensation kettle is reduced, the reaction speed is accelerated, meanwhile, the staying time of the polyester melt in the melt pipeline is also reduced, the thermal degradation of the polyester melt is less, the end group after polymerization is low, and the material quality is improved.
(3) The invention has less melt in the polycondensation kettle, greatly reduces the stirring current and the vacuum energy consumption, and can greatly reduce the energy consumption by adopting the process.
(4) The invention carries out primary polycondensation tackifying in the polycondensation kettle, and carries out tackifying again in the tackifying kettle, thereby ensuring the viscosity of the polyester melt.
(5) The first chain extension modified polyester melt and the second polycondensation tackifying polyester melt are injected into a tackifying kettle for tackifying and react at a certain vacuum degree, so that the chain extender and all polyesters fully react to prepare the chain extension modified polyester.
In order to achieve the second purpose, the invention provides the following technical scheme:
provides a chain-extended modified polyester, which is prepared by the polymerization method of the chain-extended modified polyester. The prepared chain-extended modified polyester has the advantage of good performance.
In order to achieve the third purpose, the invention provides the following technical scheme:
the application of the chain-extended modified polyester is provided, and the chain-extended modified polyester is applied to the manufacturing of mulching film biodegradable plastics. The prepared mulching film biodegradable plastic has the advantages of good biological reduction performance and high flexibility.
Drawings
FIG. 1 is a schematic flow diagram of a polymerization process for chain-extending a modified polyester according to the present invention.
Detailed Description
The present invention will be described in detail below with reference to specific embodiments and the accompanying drawings.
Example 1
In the polymerization method of chain-extended modified polyester disclosed in this example, referring to fig. 1, the polyester melt is stored in an esterification kettle, comprising the following steps,
s1, dividing the polyester melt after prepolymerization in the prepolymerization kettle into a first polyester melt and a second polyester melt;
s2, injecting the first polyester melt into a melt pipeline, and injecting the second polyester melt into a polycondensation kettle;
cooling the first polyester melt in the melt pipeline until the temperature of the melt pipeline is 120 ℃, inputting the cooled first polyester melt into a melt mixer and injecting a chain extender in a chain extender storage tank into the melt mixer to mix the first polyester melt with the chain extender, and inputting the mixed first polyester melt and the chain extender melt into a melt homogenizer to obtain a first chain extension modified polyester melt;
the second polyester melt is subjected to polycondensation tackifying in a polycondensation kettle in a vacuum state to obtain a second polycondensation tackifying polyester melt;
s3, injecting the first chain extension modified polyester melt and the second polycondensation tackifying polyester melt into a tackifying kettle for tackifying to obtain a tackifying polyester melt material;
and S4, cooling and pelletizing the tackifying polyester melt material in sequence to obtain the biodegradable polyester.
The preparation method has the following functions and effects: compared with the reaction process of prepolymerization, polycondensation and tackifying in the prior art, the polyester melt has less material staying in the polycondensation kettle, fast reaction, less reaction time in the melt runner, reduced reduction of the polyester melt, low polymerized end group and more excellent performance of the prepared polyester. And the viscosity of the prepolymerized polyester melt is lower, which is beneficial to reducing the energy consumption of equipment. Injecting the first chain extension modified polyester melt and the second polycondensation tackifying polyester melt into a tackifying kettle for tackifying by adopting a certain vacuum degree, so that the chain extender fully reacts with all polyesters to prepare the chain extension modified polyester.
In this embodiment, the chain extender is dimer acid diisocyanate.
In this example, the weight percentage of the chain extender in the first chain-extended modified polyester melt was 10%.
In this example, the ratio of the amounts of the first polyester melt and the second polyester melt was 1: 3.
In this embodiment, in S1, the polyester melt is separated into the first polyester melt and the second polyester melt by a melt metering gear pump, and in S2, the chain extender is injected into the melt pipe by a chain extender injection pump.
In this embodiment, the melt mixer includes a homogenizing pump, a dynamic mixer, and a twin screw extrusion device.
In this example, in S2, the mixing temperature of the melt mixer was 220 ℃, and the reaction time of the first polyester melt and the chain extender in the melt homogenizer was 2 min.
In this example, the reaction temperature of the polycondensation kettle was 220 ℃, the reaction time was 180min, and the vacuum degree was < 100 pa.
In this embodiment, the reaction temperature of the viscosity increasing kettle is 220 ℃, the vacuum degree is less than 100pa, and the reaction time is 20 min.
Example 2
The polymerization method of chain-extended modified polyester disclosed in this example, referring to fig. 1, comprises the following steps,
s1, dividing the prepolymerized polyester melt into a first polyester melt and a second polyester melt;
s2, injecting the first polyester melt into a melt pipeline, and injecting the second polyester melt into a polycondensation kettle;
cooling the first polyester melt in the melt pipeline until the temperature of the melt pipeline is 250 ℃, inputting the cooled first polyester melt into a melt mixer, injecting a chain extender into the melt mixer, mixing the first polyester melt with the chain extender, inputting the mixed first polyester melt and the chain extender into a melt homogenizer, and homogenizing to obtain a first chain extension modified polyester melt;
the second polyester melt is subjected to polycondensation tackifying in a polycondensation kettle in a vacuum state to obtain a second polycondensation tackifying polyester melt;
s3, injecting the first chain extension modified polyester melt and the second polycondensation tackifying polyester melt into a tackifying kettle for tackifying to obtain a tackifying polyester melt material;
and S4, cooling and pelletizing the tackifying polyester melt material in sequence to obtain the biodegradable polyester.
The preparation method has the following functions and effects: compared with the reaction process of prepolymerization, polycondensation and tackifying in the prior art, the polyester melt has less material staying in the polycondensation kettle, fast reaction, less reaction time in the melt runner, reduced reduction of the polyester melt, low polymerized end group and more excellent performance of the prepared polyester. And the viscosity of the prepolymerized polyester melt is lower, which is beneficial to reducing the energy consumption of equipment. Injecting the first chain extension modified polyester melt and the second polycondensation tackifying polyester melt into a tackifying kettle for tackifying by adopting a certain vacuum degree, so that the chain extender fully reacts with all polyesters to prepare the chain extension modified polyester.
In this embodiment, the chain extender is dimer acid diisocyanate.
In this example, the weight percentage of the chain extender in the first chain-extended modified polyester melt was 0.1%.
In this example, the ratio of the amounts of the first polyester melt to the second polyester melt was 3: 1.
In this embodiment, in S1, the polyester melt is separated into the first polyester melt and the second polyester melt by a melt metering gear pump, and in S2, the chain extender is injected into a melt pipe by a chain extender injection device.
In this embodiment, the melt mixer includes a homogenizing pump, a dynamic mixer, and a twin screw extrusion device.
In this example, the mixing temperature of the melt mixer in the S2 was 120 ℃, and the reaction time of the first polyester melt and the chain extender in the melt homogenizer was 30 min.
In this embodiment, the reaction temperature of the polycondensation kettle is 260 ℃, the reaction time is 40min, and the vacuum degree is less than 100 pa.
In this embodiment, the reaction temperature of the viscosity increasing kettle is 260 ℃, the vacuum degree is less than 100pa, and the reaction time is 100 min.
Example 3
The polymerization method of chain-extended modified polyester disclosed in this example, referring to fig. 1, comprises the following steps,
s1, dividing the prepolymerized polyester melt into a first polyester melt and a second polyester melt;
s2, injecting the first polyester melt into a melt pipeline, and injecting the second polyester melt into a polycondensation kettle;
cooling the first polyester melt in the melt pipeline until the temperature of the melt pipeline is 200 ℃, inputting the cooled first polyester melt into a melt mixer, injecting a chain extender into the melt mixer, mixing the first polyester melt with the chain extender, inputting the mixed first polyester melt and the chain extender into a melt homogenizer, and homogenizing to obtain a first chain extension modified polyester melt;
the second polyester melt is subjected to polycondensation tackifying in a polycondensation kettle in a vacuum state to obtain a second polycondensation tackifying polyester melt;
s3, injecting the first chain extension modified polyester melt and the second polycondensation tackifying polyester melt into a tackifying kettle for tackifying to obtain a tackifying polyester melt material;
and S4, cooling and pelletizing the tackifying polyester melt material in sequence to obtain the biodegradable polyester.
The preparation method has the following functions and effects: compared with the reaction process of prepolymerization, polycondensation and tackifying in the prior art, the polyester melt has less material staying in the polycondensation kettle, fast reaction, less reaction time in the melt runner, reduced reduction of the polyester melt, low polymerized end group and more excellent performance of the prepared polyester. And the viscosity of the prepolymerized polyester melt is lower, which is beneficial to reducing the energy consumption of equipment. Injecting the first chain extension modified polyester melt and the second polycondensation tackifying polyester melt into a tackifying kettle for tackifying by adopting a certain vacuum degree, so that the chain extender fully reacts with all polyesters to prepare the chain extension modified polyester.
In this embodiment, the chain extender is dimer acid diisocyanate.
In this example, the weight percentage of the chain extender in the first chain-extended modified polyester melt was 5%.
In this example, the ratio of the amounts of the first polyester melt and the second polyester melt was 1:2.
In this embodiment, in S1, the polyester melt is separated into the first polyester melt and the second polyester melt by a melt metering gear pump, and in S2, the chain extender is injected into a melt pipe by a chain extender injection device.
In this embodiment, the melt mixer includes a homogenizing pump, a dynamic mixer, and a twin screw extrusion device.
In this example, the mixing temperature of the melt mixer in the S2 was 200 ℃, and the reaction time of the first polyester melt and the chain extender in the melt homogenizer was 60 min.
In this embodiment, the reaction temperature of the polycondensation kettle is 250 ℃, the reaction time is 100min, and the vacuum degree is less than 100 pa.
In this embodiment, the reaction temperature of the viscosity increasing kettle is 250 ℃, the vacuum degree is less than 100pa, and the reaction time is 50 min.
Example 4
The polymerization method of chain-extended modified polyester disclosed in this example, referring to fig. 1, comprises the following steps,
s1, dividing the prepolymerized polyester melt into a first polyester melt and a second polyester melt;
s2, injecting the first polyester melt into a melt pipeline, and injecting the second polyester melt into a polycondensation kettle;
cooling the first polyester melt in the melt pipeline until the temperature of the melt pipeline is 150 ℃, inputting the cooled first polyester melt into a melt mixer, injecting a chain extender into the melt mixer, mixing the first polyester melt with the chain extender, inputting the mixed first polyester melt and the chain extender into a melt homogenizer, and homogenizing to obtain a first chain extension modified polyester melt;
the second polyester melt is subjected to polycondensation tackifying in a polycondensation kettle in a vacuum state to obtain a second polycondensation tackifying polyester melt;
s3, injecting the first chain extension modified polyester melt and the second polycondensation tackifying polyester melt into a tackifying kettle for tackifying to obtain a tackifying polyester melt material;
and S4, cooling and pelletizing the tackifying polyester melt material in sequence to obtain the biodegradable polyester.
The preparation method has the following functions and effects: compared with the reaction process of prepolymerization, polycondensation and tackifying in the prior art, the polyester melt has less material staying in the polycondensation kettle, fast reaction, less reaction time in the melt runner, reduced reduction of the polyester melt, low polymerized end group and more excellent performance of the prepared polyester. And the viscosity of the prepolymerized polyester melt is lower, which is beneficial to reducing the energy consumption of equipment. Injecting the first chain extension modified polyester melt and the second polycondensation tackifying polyester melt into a tackifying kettle for tackifying by adopting a certain vacuum degree, so that the chain extender fully reacts with all polyesters to prepare the chain extension modified polyester.
In this embodiment, the chain extender is dimer acid diisocyanate.
In this example, the weight percentage of the chain extender in the first chain-extended modified polyester melt was 0.1%.
In this example, the ratio of the amounts of the first polyester melt to the second polyester melt was 2: 1.
In this embodiment, in S1, the polyester melt is separated into the first polyester melt and the second polyester melt by a melt metering gear pump, and in S2, the chain extender is injected into a melt pipe by a chain extender injection device.
In this embodiment, the melt mixer includes a homogenizing pump, a dynamic mixer, and a twin screw extrusion device.
In this example, the mixing temperature of the melt mixer in S2 was 150 ℃, and the reaction time of the first polyester melt and the chain extender in the melt homogenizer was 10 min.
In this example, the reaction temperature of the polycondensation kettle was 230 ℃, the reaction time was 60min, and the vacuum degree was < 100 pa.
In this embodiment, the reaction temperature of the viscosity increasing kettle is 230 ℃, the vacuum degree is less than 100pa, and the reaction time is 30 min-.
Example 5
The polymerization method of chain-extended modified polyester disclosed in this example, referring to fig. 1, comprises the following steps,
s1, dividing the prepolymerized polyester melt into a first polyester melt and a second polyester melt;
s2, injecting the first polyester melt into a melt pipeline, and injecting the second polyester melt into a polycondensation kettle;
cooling the first polyester melt in the melt pipeline until the temperature of the melt pipeline is 220 ℃, inputting the cooled first polyester melt into a melt mixer, injecting a chain extender into the melt mixer, mixing the first polyester melt with the chain extender, inputting the mixed first polyester melt and the chain extender into a melt homogenizer, and homogenizing to obtain a first chain extension modified polyester melt;
the second polyester melt is subjected to polycondensation tackifying in a polycondensation kettle in a vacuum state to obtain a second polycondensation tackifying polyester melt;
s3, injecting the first chain extension modified polyester melt and the second polycondensation tackifying polyester melt into a tackifying kettle for tackifying to obtain a tackifying polyester melt material;
and S4, cooling and pelletizing the tackifying polyester melt material in sequence to obtain the biodegradable polyester.
The preparation method has the following functions and effects: compared with the reaction process of prepolymerization, polycondensation and tackifying in the prior art, the polyester melt has less material staying in the polycondensation kettle, fast reaction, less reaction time in the melt runner, reduced reduction of the polyester melt, low polymerized end group and more excellent performance of the prepared polyester. And the viscosity of the prepolymerized polyester melt is lower, which is beneficial to reducing the energy consumption of equipment. Injecting the first chain extension modified polyester melt and the second polycondensation tackifying polyester melt into a tackifying kettle for tackifying by adopting a certain vacuum degree, so that the chain extender fully reacts with all polyesters to prepare the chain extension modified polyester.
In this embodiment, the chain extender is dimer acid diisocyanate.
In this example, the weight percentage of the chain extender in the first chain-extended modified polyester melt was 5%.
In this example, the ratio of the amounts of the first polyester melt to the second polyester melt was 1: 2.5.
In this embodiment, in S1, the polyester melt is separated into the first polyester melt and the second polyester melt by a melt metering gear pump, and in S2, the chain extender is injected into a melt pipe by a chain extender injection device.
In this embodiment, the melt mixer includes a homogenizing pump, a dynamic mixer, and a twin screw extrusion device.
In this example, the mixing temperature of the melt mixer in the S2 was 200 ℃, and the reaction time of the first polyester melt and the chain extender in the melt homogenizer was 30 min.
In this embodiment, the reaction temperature of the polycondensation kettle is 260 ℃, the reaction time is 90min, and the vacuum degree is less than 100 pa.
In this embodiment, the reaction temperature of the viscosity increasing kettle is 250 ℃, the vacuum degree is less than 100pa, and the reaction time is 60 min.
Example 6
The polymerization method of chain-extended modified polyester disclosed in this example, referring to fig. 1, comprises the following steps,
s1, dividing the prepolymerized polyester melt into a first polyester melt and a second polyester melt;
s2, injecting the first polyester melt into a melt pipeline, and injecting the second polyester melt into a polycondensation kettle;
cooling the first polyester melt in the melt pipeline until the temperature of the melt pipeline is 200 ℃, inputting the cooled first polyester melt into a melt mixer, injecting a chain extender into the melt mixer, mixing the first polyester melt with the chain extender, inputting the mixed first polyester melt and the chain extender into a melt homogenizer, and homogenizing to obtain a first chain extension modified polyester melt;
the second polyester melt is subjected to polycondensation tackifying in a polycondensation kettle in a vacuum state to obtain a second polycondensation tackifying polyester melt;
s3, injecting the first chain extension modified polyester melt and the second polycondensation tackifying polyester melt into a tackifying kettle for tackifying to obtain a tackifying polyester melt material;
and S4, cooling and pelletizing the tackifying polyester melt material in sequence to obtain the biodegradable polyester.
The preparation method has the following functions and effects: compared with the reaction process of prepolymerization, polycondensation and tackifying in the prior art, the polyester melt has less material staying in the polycondensation kettle, fast reaction, less reaction time in the melt runner, reduced reduction of the polyester melt, low polymerized end group and more excellent performance of the prepared polyester. And the viscosity of the prepolymerized polyester melt is lower, which is beneficial to reducing the energy consumption of equipment. Injecting the first chain extension modified polyester melt and the second polycondensation tackifying polyester melt into a tackifying kettle for tackifying by adopting a certain vacuum degree, so that the chain extender fully reacts with all polyesters to prepare the chain extension modified polyester.
In this embodiment, the chain extender is dimer acid diisocyanate.
In this example, the weight percentage of the chain extender in the first chain-extended modified polyester melt was 2%.
In this example, the ratio of the amount of the first polyester melt to the second polyester melt was 2.5: 1.5.
In this embodiment, in S1, the polyester melt is separated into the first polyester melt and the second polyester melt by a melt metering gear pump, and in S2, the chain extender is injected into a melt pipe by a chain extender injection device.
In this embodiment, the melt mixer includes a homogenizing pump, a dynamic mixer, and a twin screw extrusion device.
In this example, the mixing temperature of the melt mixer in the S2 was 180 ℃, and the reaction time of the first polyester melt and the chain extender in the melt homogenizer was 20 min.
In this example, the reaction temperature of the polycondensation kettle was 250 ℃, the reaction time was 70min, and the vacuum degree was < 100 pa.
In this embodiment, the reaction temperature of the viscosity increasing kettle is 240 ℃, the vacuum degree is less than 100pa, and the reaction time is 50 min.
Comparative example 1
Comparative example 1 is different from example 1 in that the polyester melt is used instead of the prepolymerized polyester melt in example 1, and other components and preparation methods are the same as those in example 1 and are not described again.
Comparative example 2
Comparative example 2 differs from example 1 in that the polymerization process of the chain-extended modified polyester of comparative example 2 comprises the steps of:
s1, injecting a polyester melt into a melt pipeline, cooling the polyester melt until the temperature of the melt pipeline is 120-250 ℃, injecting a chain extender into the cooled polyester melt, sequentially feeding the polyester melt and the chain extender into a melt mixer and a melt homogenizer, and injecting the homogenized material into a tackifying kettle for tackifying to obtain a tackified polyester melt material;
and S2, cooling and pelletizing the tackifying polyester melt material in sequence to obtain the biodegradable polyester.
Other components and preparation method of comparative example 2 are the same as those of example 1, and are not described herein again.
Comparison of effects
The energy consumption, the reaction time and the performance of the polyester materials obtained by the polymerization methods of examples 1 to 3 and the polymerization methods of comparative examples 1 to 2 were respectively considered, and 1 ton of polyester was prepared as a target product, and the following items were adopted for evaluation, wherein the flexibility was measured according to the GB/T1451-2005 standard, and the evaluation results are shown in Table 1.
TABLE 1
As can be seen from the above comparative Table 1: the invention adopts the prepolymerized polyester melt to reduce energy consumption; the invention separates the polyester melt into two paths for reaction, which can reduce the total reaction time; the flexibility of the polyester material prepared by the invention is better than that of the polyester materials prepared by the comparative examples 1 and 2. Therefore, the polymerization method of the chain-extended modified polyester is suitable for large-scale production and application.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. A polymerization method of chain-extended modified polyester is characterized by comprising the following steps: comprises the following steps of (a) carrying out,
s1, dividing the prepolymerized polyester melt into a first polyester melt and a second polyester melt;
s2, injecting the first polyester melt into a melt pipeline, and injecting the second polyester melt into a polycondensation kettle;
cooling the first polyester melt in the melt pipeline until the temperature of the melt pipeline is 120-250 ℃, inputting the cooled first polyester melt into a melt mixer, injecting a chain extender into the melt mixer, mixing the first polyester melt with the chain extender, and inputting the mixed first polyester melt and the chain extender into a melt homogenizer for homogenization to obtain a first chain extension modified polyester melt;
the second polyester melt is subjected to polycondensation tackifying in a polycondensation kettle in a vacuum state to obtain a second polycondensation tackifying polyester melt;
s3, injecting the first chain extension modified polyester melt and the second polycondensation tackifying polyester melt into a tackifying kettle for tackifying to obtain a tackifying polyester melt material;
and S4, sequentially cooling and dicing the tackifying polyester melt material to obtain the biodegradable polyester.
2. The polymerization process for chain-extended modified polyester according to claim 1, characterized in that: the chain extender is dimer acid diisocyanate.
3. The polymerization process for chain-extended modified polyester according to claim 2, characterized in that: the weight percentage of the chain extender in the first chain extension modified polyester melt is 0.1-10%.
4. The polymerization process for chain-extended modified polyester according to claim 1, characterized in that: in S1, the polyester melt is separated into the first polyester melt and the second polyester melt by a melt metering gear pump; in S2, the chain extender is injected into the melt pipe by a chain extender injection device.
5. The polymerization process for chain-extended modified polyester according to claim 1, characterized in that: the melt mixer includes a homogenizing pump, a dynamic mixer, and a twin screw extrusion device.
6. The polymerization process for chain-extended modified polyester according to claim 1, characterized in that: in the S2, the mixing temperature of the melt mixer is 120-220 ℃; the reaction time of the mixed first polyester melt and the chain extender in the melt homogenizer is 2min to 60 min.
7. The polymerization process for chain-extended modified polyester according to claim 1, characterized in that: the reaction temperature of the polycondensation kettle is 220-260 ℃, the reaction time is 40-180 min, and the vacuum degree is less than 100 pa.
8. The polymerization process for chain-extended modified polyester according to claim 1, characterized in that: the reaction temperature of the tackifying kettle is 220-260 ℃, the vacuum degree is less than 100pa, and the reaction time is 20-100 min.
9. A chain-extended modified polyester is characterized in that: the chain-extended modified polyester is prepared by the polymerization method of the chain-extended modified polyester as described in any one of claims 1 to 8.
10. The application of the chain-extended modified polyester is characterized in that: the chain-extended modified polyester of claim 9 is applied to the manufacture of mulching film biodegradable plastics.
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