CN114621450B - Method for chain extension modified biodegradable polyester and application thereof - Google Patents
Method for chain extension modified biodegradable polyester and application thereof Download PDFInfo
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- CN114621450B CN114621450B CN202110370521.6A CN202110370521A CN114621450B CN 114621450 B CN114621450 B CN 114621450B CN 202110370521 A CN202110370521 A CN 202110370521A CN 114621450 B CN114621450 B CN 114621450B
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- 229920000229 biodegradable polyester Polymers 0.000 title claims abstract description 175
- 239000004622 biodegradable polyester Substances 0.000 title claims abstract description 175
- 238000000034 method Methods 0.000 title claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 70
- 239000000155 melt Substances 0.000 claims abstract description 69
- 239000004970 Chain extender Substances 0.000 claims abstract description 55
- 238000002156 mixing Methods 0.000 claims abstract description 39
- 229920000728 polyester Polymers 0.000 claims abstract description 33
- 238000000265 homogenisation Methods 0.000 claims abstract description 21
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 21
- 238000001816 cooling Methods 0.000 claims abstract description 17
- 238000005086 pumping Methods 0.000 claims abstract description 15
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 8
- 230000035484 reaction time Effects 0.000 claims description 25
- 238000002360 preparation method Methods 0.000 claims description 24
- 239000002994 raw material Substances 0.000 claims description 23
- 229920001896 polybutyrate Polymers 0.000 claims description 20
- 238000004519 manufacturing process Methods 0.000 claims description 10
- UQLDLKMNUJERMK-UHFFFAOYSA-L di(octadecanoyloxy)lead Chemical compound [Pb+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O UQLDLKMNUJERMK-UHFFFAOYSA-L 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 2
- 239000012760 heat stabilizer Substances 0.000 description 27
- 239000003054 catalyst Substances 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 16
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 10
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 9
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 239000007858 starting material Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000012948 isocyanate Substances 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 230000002411 adverse Effects 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 235000011007 phosphoric acid Nutrition 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- AXKZIDYFAMKWSA-UHFFFAOYSA-N 1,6-dioxacyclododecane-7,12-dione Chemical compound O=C1CCCCC(=O)OCCCCO1 AXKZIDYFAMKWSA-UHFFFAOYSA-N 0.000 description 1
- WSQZNZLOZXSBHA-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione Chemical compound O=C1OCCCCOC(=O)C2=CC=C1C=C2 WSQZNZLOZXSBHA-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229940009827 aluminum acetate Drugs 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- WSXIMVDZMNWNRF-UHFFFAOYSA-N antimony;ethane-1,2-diol Chemical compound [Sb].OCCO WSXIMVDZMNWNRF-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- IAXFXKYCXIOREZ-UHFFFAOYSA-L calcium potassium diacetate Chemical compound C(C)(=O)[O-].[Ca+2].C(C)(=O)[O-].[K+] IAXFXKYCXIOREZ-UHFFFAOYSA-L 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229960004249 sodium acetate Drugs 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
Landscapes
- 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)
- Polyurethanes Or Polyureas (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention relates to the field of polyester, in particular to a method for chain extension modified biodegradable polyester and application thereof. The specific method comprises the following steps: 1. pumping out a first biodegradable polyester melt from a prepolymerization kettle by a melt metering gear pump, cooling a melt pipeline, and injecting a chain extender; 2. the first biodegradable polyester melt and the chain extender are fed into a melt mixing device to be mixed uniformly and then fed into a melt homogenizer for chain extension homogenization reaction, and the prepolymer chain extension modified biodegradable polyester melt is obtained after the reaction; 3. pumping out the second biodegradable polyester melt from the prepolymerization kettle by a melt metering gear pump to enter a polycondensation kettle for polymerization reaction to obtain a prepolymerized tackifying polyester melt; 4. and mixing the pre-polymerized chain-extended modified biodegradable polyester melt and the pre-polymerized tackifying polyester melt, then entering a tackifying kettle for tackifying reaction, obtaining the chain-extended modified biodegradable polyester melt after the reaction, cooling and granulating to obtain the chain-extended modified biodegradable polyester chip.
Description
Technical Field
The invention relates to the field of polyester, in particular to a method for chain extension modified biodegradable polyester and application thereof.
Background
Polyester is a generic term for polymers produced by polycondensation of a polyhydric alcohol and a polybasic acid, and the consumption of polyester is rising year by year with the rapid increase of national economy. The biodegradable polyester is a polyester which can be completely decomposed by microorganisms such as bacteria, mold, algae and the like existing in the nature, has little burden on the environment, and is a polyester commonly used in the market at present. The production of high molecular weight biodegradable polyesters by adding certain chain extenders to the melt is currently a widely accepted process.
CN103755941a discloses a method for continuously polymerizing chain-extended modified polyester, which has higher requirement on melt viscosity during prepolymerization, and the chain extender needs a high-pressure injector to be injected into a melt pipeline, has higher requirement on equipment, and increases hidden trouble for the safety production of enterprises.
CN200810112443.4 discloses a method for preparing biodegradable polyester amide by chain extension, which adopts bisoxazoline and diacyl bislactam as chain extender, and the prepared finished product has high residual quantity of the chain extender, which is unfavorable for health and environment.
Disclosure of Invention
In a first aspect the present invention provides a process for chain extending modified biodegradable polyesters comprising the steps of:
1. after the preparation raw materials of the biodegradable polyester are completely esterified, the biodegradable polyester is pumped into a prepolymerization kettle by a melt metering gear pump for reaction;
2. pumping out a first biodegradable polyester melt from a 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 prepolymerization chain extension modified biodegradable polyester melt;
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 tackifying polyester melt;
6. mixing the pre-polymerized chain-extended modified biodegradable polyester melt obtained in the step 4 with the pre-polymerized tackifying polyester melt obtained in the step 5, then entering a tackifying kettle for tackifying reaction, obtaining the chain-extended modified biodegradable polyester melt after the reaction, cooling the chain-extended modified biodegradable polyester melt, and granulating to obtain the chain-extended modified biodegradable polyester chip.
As a preferred embodiment, the temperature of the melt conduit 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 2-30min.
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 120Pa.
As a preferred embodiment, the reaction temperature in the tackifying kettle is 220-280 ℃, the reaction time is 20-100min, and the vacuum degree is not more than 120Pa.
As a preferred embodiment, the preparation raw materials of the first biodegradable polyester melt and the second biodegradable polyester melt include 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 and the second biodegradable polyester melt is 0.05-0.25dL/g.
In a second aspect, the invention provides the use of a method for chain extending modified biodegradable polyesters for the production of biodegradable polyesters.
Compared with the prior art, the invention has the following beneficial effects:
1. compared with the prior art, the method for chain extension modified biodegradable polyester provided by the invention has the advantages that only a part of 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 preparing the chain-extended modified biodegradable polyester, the biodegradable polyester melt is divided into the first biodegradable polyester melt and the second biodegradable polyester melt according to the specific proportion, and the chain-extended homogenization reaction and the tackifying reaction are respectively carried out, so that the processes of sequentially carrying out the chain-extended homogenization reaction and the tackifying reaction on the melt in the prior art are replaced, the residence time of the melt in a reaction kettle is shortened, the end group content of the polymer after the reaction is lower, the thermal degradation rate of the melt is lower, and the prepared chain-extended modified biodegradable polyester chip is more excellent in mechanical property.
3. The method for chain extension modified biodegradable polyester has lower requirement on melt viscosity of biodegradable polyester in prepolymerization, has lower requirement on melt mixer equipment, can uniformly mix without a large power motor, and further improves economic benefit.
4. According to the method for preparing the chain-extended modified biodegradable polyester, disclosed by the invention, the chain extender in the melt is fully reacted by setting the specific reaction temperature, the specific reaction time and the specific vacuum degree of the tackifying kettle, so that the residual amount of the chain extender in the finished product of the chain-extended modified biodegradable polyester chip is extremely low, and the environment and the human health are not adversely affected.
Detailed Description
In order to solve the technical problems, a first aspect of the present invention provides a method for chain-extending modified biodegradable polyester, comprising the steps of:
1. after the preparation raw materials of the biodegradable polyester are completely esterified, the biodegradable polyester is pumped into a prepolymerization kettle by a melt metering gear pump for reaction;
2. pumping out a first biodegradable polyester melt from a 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 prepolymerization chain extension modified biodegradable polyester melt;
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 tackifying polyester melt;
6. mixing the pre-polymerized chain-extended modified biodegradable polyester melt obtained in the step 4 with the pre-polymerized tackifying polyester melt obtained in the step 5, then entering a tackifying kettle for tackifying reaction, obtaining the chain-extended modified biodegradable polyester melt after the reaction, cooling the chain-extended modified biodegradable polyester melt, and granulating to obtain the chain-extended modified biodegradable polyester chip.
As a preferred embodiment, the melting temperature is 270-300 ℃.
As a preferred embodiment, the temperature of the cooled melt conduit in step 2 is 120-220 ℃.
Preferably, the temperature of the cooled melt pipeline in the step 2 is 150-200 ℃.
The temperature of the cooled melt pipeline in the method is far lower than the temperature range commonly selected in the prior art, and the applicant finds that if the temperature range in the prior art is used for cooling, 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, and harmful byproducts are often generated, so that the applicant finds that after a large amount of experiments, when the temperature of the cooled melt pipeline is 150-200 ℃, good cooling effect can be achieved, and the reaction between the chain extender and the first biodegradable polyester melt can be inhibited in the cooling stage, thereby solving the technical problems in the prior art.
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).
In the prior art, polyester prepolymer melt is mixed with a chain extender after passing through a polycondensation kettle and being cooled in sequence, and as all polyester melt passes through the polycondensation kettle and has overlarge self viscosity, the polyester prepolymer melt fully reacts with the chain extender, the motor power and equipment design requirements of a melt mixing container are very high, the electric energy consumption in the mixing process is huge, and the adverse phenomena such as equipment blocking and the like caused by overlarge viscosity are easy to occur, and the applicant creatively discovers that the polyester melt is prepared by mixing the polyester melt according to the mass ratio of 1: (1-6), preferably 1: the proportion of (1-4) is divided into a first biodegradable polyester melt and a second biodegradable polyester melt, the first biodegradable polyester melt is mixed with the second biodegradable polyester melt after being reacted with a chain extender, and the manufacturing 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 channel by a chain extender injection device.
As a preferred embodiment, the melt mixing device comprises a jacketed homogenizing pump, dynamic mixer, twin screw extrusion equipment.
As 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 sets the temperature of the cooled melt pipeline and the temperature of the melt mixing device to be in the same preferable range, and the aim of the setting is to continuously inhibit the advanced reaction of the chain extender and the first biodegradable polyester melt in the melt mixing device, so as to prevent the occurrence of harmful byproducts.
As a preferred embodiment, the reaction temperature of the chain extension homogenization reaction is 220-260 ℃ and the reaction time is 2-30min.
Preferably, the reaction time of the chain extension homogenization reaction is 5-15min.
The purpose of chain extension homogenization reaction is to make the chain extender fully react with the polyester melt to increase the viscosity of the polyester melt, while in actual production, too short homogenization time can cause incomplete chain extender reaction and residual, which not only affects the quality of the polyester, but also is harmful to the environment and human body, too long homogenization time can cause thermal degradation of the polyester during homogenization reaction, the end group content of the polyester product is high, and the reject ratio 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 120Pa.
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 100Pa.
The chain extender after chain extension homogenization and the first biodegradable polyester melt are subjected to polymerization reaction in the polycondensation kettle, compared with the prior art, the polyester melt in the polycondensation kettle is less, so that the reaction time and the vacuum degree are greatly shortened compared with the prior art, good finished product quality can be achieved without high-power high-pressure vacuum, and meanwhile, the production energy consumption is reduced.
As a preferred embodiment, the reaction temperature in the tackifying kettle is 220-280 ℃, the reaction time is 20-100min, and the vacuum degree is not more than 120Pa.
Preferably, the reaction temperature in the tackifying kettle is 230-260 ℃, the reaction time is 30-60min, and the vacuum degree is not more than 100Pa.
As a preferred embodiment, the chain extender is at least one selected from the group consisting of epoxy-based chain extenders and isocyanate-based chain extenders.
Preferably, the chain extender is at least one selected from 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 chain extender is present in the first biodegradable polyester melt in an amount of 0.001 to 5wt% of the starting material.
Preferably, the chain extender is present in the first biodegradable polyester melt in an amount of 0.003 to 3wt% of the starting material.
Compared with the prior art, the process of reacting the first biodegradable polyester melt with the chain extender adopted in the invention is cooperated with the subsequent tackifying kettle tackifying process, so that the reaction time of the chain extender is longer and the residue is lower under the vacuum condition, and the applicant finds that the polyester chain extender can fully react with the first biodegradable polyester melt and can not cause residue when the content of the chain extender is 0.001-5wt%, preferably 0.003-3wt%, 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 first biodegradable polyester melt has an intrinsic viscosity of 0.05 to 0.25dL/g.
Preferably, the first biodegradable polyester melt is prepared from a material comprising PBAT.
As a preferred embodiment, the preparation raw material of the first biodegradable polyester melt further comprises a first catalyst and a first heat stabilizer.
As a preferred embodiment, the first catalyst is present in the preparation of the first biodegradable polyester melt in an amount of 0.001 to 0.3wt%.
Preferably, the first catalyst is present in an amount of 0.002 to 0.2wt% of the starting material for the preparation of the first biodegradable polyester melt.
As a preferred embodiment, the first heat stabilizer is present in the first biodegradable polyester melt in an amount of 0.001 to 0.3wt% of the starting material.
Preferably, the first heat stabilizer is present in an amount of 0.002 to 0.2wt% in the starting material for the preparation of the first biodegradable polyester melt.
As a preferred embodiment, the preparation raw material of 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 0.25dL/g.
Preferably, the preparation raw material of the second biodegradable polyester melt comprises PBAT.
As a preferred embodiment, the preparation raw material of 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 preparation raw material of the second biodegradable polyester melt is 0.001 to 0.3wt%.
Preferably, the content of the second catalyst in the preparation raw material of the second biodegradable polyester melt is 0.002-0.2wt%.
As a preferred embodiment, the second heat stabilizer is contained in an amount of 0.001 to 0.3wt% in the raw material for preparing the second biodegradable polyester melt.
Preferably, the second heat stabilizer is contained in an amount of 0.002 to 0.2wt% in the raw material for preparing the second biodegradable polyester melt.
The first and second catalysts comprise at least one of titanium catalysts, antimony catalysts and metal acetates.
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 and calcium acetate potassium acetate.
Preferably, the first catalyst and the second catalyst are both butyl titanate.
Preferably, the first and second heat stabilizers include at least one of phosphoric acid and phosphate compounds.
Preferably, the first and second heat stabilizers include at least one of orthophosphoric acid, phosphorous acid, pyrophosphoric acid, phosphoric acid esters, phosphites, and trimethyl phosphate.
Preferably, the first and second heat stabilizers are trimethyl phosphate.
In a second aspect, the invention provides the use of a method for chain extending modified biodegradable polyesters for the production of biodegradable polyesters.
The present invention will be specifically described below by way of examples. It is noted herein that the following examples are given solely for the purpose of further illustration and are not to be construed as limitations on the scope of the invention, as will be apparent to those skilled in the art in light of the foregoing disclosure.
Hexamethylene diisocyanate CAS number 822-06-0.
PBAT is a copolymer of butylene adipate and butylene terephthalate, purchased from Ningbo city, blue minister plasticization limited.
Butyl titanate CAS number 5593-70-4.
Trimethyl phosphate CAS number 512-56-1.
In addition, the raw materials used are commercially available unless otherwise indicated.
Examples
Example 1
Example 1 provides a method of chain extending modified biodegradable polyesters comprising the steps of:
1. after the preparation raw materials of the biodegradable polyester are completely esterified, the biodegradable polyester is pumped into a prepolymerization kettle by a melt metering gear pump for reaction;
2. pumping out a first biodegradable polyester melt from a 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 prepolymerization chain extension modified biodegradable polyester melt;
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 tackifying polyester melt;
6. mixing the pre-polymerized chain-extended modified biodegradable polyester melt obtained in the step 4 with the pre-polymerized tackifying polyester melt obtained in the step 5, then entering a tackifying kettle for tackifying reaction, obtaining the chain-extended modified biodegradable polyester melt after the reaction, cooling the chain-extended modified biodegradable polyester melt, and granulating to obtain the chain-extended modified biodegradable polyester chip.
The melting temperature was 270 ℃.
The temperature of the cooled melt pipeline in the 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 5min.
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 100Pa.
The reaction temperature in the tackifying kettle is 230 ℃, the reaction time is 30min, and the vacuum degree is 100Pa.
The preparation raw materials of the first biodegradable polyester melt comprise PBAT, a chain extender, a first catalyst and a first heat stabilizer; the intrinsic viscosity of PBAT is 0.05dL/g, the content is 99.996wt%, the chain extender is hexamethylene diisocyanate, the injection amount is 0.003wt%, the first catalyst is butyl titanate, and the content is 0.002wt%; the first heat stabilizer is trimethyl phosphate, and the content of the first heat stabilizer is 0.002wt%.
The preparation raw materials of the second biodegradable polyester melt comprise PBAT, a second catalyst and a second heat stabilizer; the intrinsic viscosity of PBAT is 0.05dL/g, the content is 99.996wt%, the second catalyst is butyl titanate, and the content is 0.002wt%; the second heat stabilizer is trimethyl phosphate, and the content of the second heat stabilizer is 0.002wt%.
Example 2
Example 2 provides a method of chain extending modified biodegradable polyesters comprising the steps of:
1. after the preparation raw materials of the biodegradable polyester are completely esterified, the biodegradable polyester is pumped into a prepolymerization kettle by a melt metering gear pump for reaction;
2. pumping out a first biodegradable polyester melt from a 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 prepolymerization chain extension modified biodegradable polyester melt;
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 tackifying polyester melt;
6. mixing the pre-polymerized chain-extended modified biodegradable polyester melt obtained in the step 4 with the pre-polymerized tackifying polyester melt obtained in the step 5, then entering a tackifying kettle for tackifying reaction, obtaining the chain-extended modified biodegradable polyester melt after the reaction, cooling the chain-extended modified biodegradable polyester melt, and granulating to obtain the chain-extended modified biodegradable polyester chip.
The melting temperature was 300 ℃.
The temperature of the cooled melt pipeline in the 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 15min.
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 50Pa.
The reaction temperature in the tackifying kettle is 230 ℃, the reaction time is 30min, and the vacuum degree is 100Pa.
The preparation raw materials of the first biodegradable polyester melt comprise PBAT, a chain extender, a first catalyst and a first heat stabilizer; the intrinsic viscosity of PBAT is 0.25dL/g, the content is 96.6wt%, the chain extender is hexamethylene diisocyanate, the injection amount is 3wt%, the first catalyst is butyl titanate, and the content is 0.2wt%; the first heat stabilizer is trimethyl phosphate, and the content of the first heat stabilizer is 0.2wt%.
The preparation raw materials of the second biodegradable polyester melt comprise PBAT, a second catalyst and a second heat stabilizer; the intrinsic viscosity of PBAT is 0.25dL/g, the content is 99.6wt%, the second catalyst is butyl titanate, and the content is 0.2wt%; the second heat stabilizer is trimethyl phosphate, and the content of the second heat stabilizer is 0.2wt%.
Example 3
Example 3 provides a method of chain extending modified biodegradable polyesters comprising the steps of:
1. after the preparation raw materials of the biodegradable polyester are completely esterified, the biodegradable polyester is pumped into a prepolymerization kettle by a melt metering gear pump for reaction;
2. pumping out a first biodegradable polyester melt from a 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 prepolymerization chain extension modified biodegradable polyester melt;
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 tackifying polyester melt;
6. mixing the pre-polymerized chain-extended modified biodegradable polyester melt obtained in the step 4 with the pre-polymerized tackifying polyester melt obtained in the step 5, then entering a tackifying kettle for tackifying reaction, obtaining the chain-extended modified biodegradable polyester melt after the reaction, cooling the chain-extended modified biodegradable polyester melt, and granulating to obtain the chain-extended modified biodegradable polyester chip.
The melting temperature was 290 ℃.
The temperature of the cooled melt pipeline 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 10min.
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 70Pa.
The reaction temperature in the tackifying kettle is 250 ℃, the reaction time is 50min, and the vacuum degree is 60Pa.
The preparation raw materials of the first biodegradable polyester melt comprise PBAT, a chain extender, a first catalyst and a first heat stabilizer; the intrinsic viscosity of PBAT is 0.1dL/g, the content is 99.6wt%, the chain extender is hexamethylene diisocyanate, the injection amount is 0.1wt%, the first catalyst is butyl titanate, and the content is 0.15wt%; the first heat stabilizer is trimethyl phosphate, and the content of the first heat stabilizer is 0.15wt%.
The preparation raw materials of the second biodegradable polyester melt comprise PBAT, a second catalyst and a second heat stabilizer; the intrinsic viscosity of PBAT is 0.1dL/g, the content is 99.7wt%, the second catalyst is butyl titanate, and the content is 0.15wt%; the second heat stabilizer is trimethyl phosphate, and the content of the second heat stabilizer is 0.15wt%.
Comparative example 1
Comparative example 1 provides a method for chain-extending modified biodegradable polyester, and the specific embodiment 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 polyesters, and the specific embodiment is the same as example 3, except that the reaction time in the tackifying kettle is 15min.
Comparative example 3
Comparative example 3 provides a method for chain-extending modified biodegradable polyester, and the specific embodiment is the same as example 3, except that the vacuum degree in the tackifying kettle is 150Pa.
Comparative example 4
Comparative example 4 provides a process for chain extending modified biodegradable polyesters, the specific embodiment being the same as example 3, except that the intrinsic viscosity of the PBAT is 0.5dL/g.
Comparative example 5
Comparative example 5 provides a method of chain extending modified biodegradable polyester, the specific embodiment is the same as example 3, wherein 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 detection criteria: ISO 14896-2009
| Tensile Strength (MPa) | Elongation at break (%) | Residual isocyanate content (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 |
The above description is only a preferred embodiment of the present invention, and is not intended to limit the invention in any way, and any person skilled in the art may make modifications or alterations to the disclosed technical content to equivalent embodiments without departing from the technical content of the present invention, and any simple modification, equivalent changes and alterations to the above embodiments according to the technical substance of the present invention still fall within the scope of the technical solution of the present invention.
Claims (8)
1. A method of chain extending modified biodegradable polyester comprising the steps of:
(1) After the preparation raw materials of the biodegradable polyester are completely esterified, pumping the biodegradable polyester into a prepolymerization kettle by a melt metering gear pump for reaction;
(2) Pumping out the first biodegradable polyester melt from the prepolymerization reactor by a melt metering gear pump, cooling a melt pipeline, and injecting a chain extender;
(3) Feeding the first biodegradable polyester melt and the chain extender into a melt mixing device;
(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 prepolymerization chain extension modified biodegradable polyester melt;
(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 tackifying polyester melt;
(6) Mixing the pre-polymerized chain-extended modified biodegradable polyester melt obtained in the step (4) with the pre-polymerized tackifying polyester melt obtained in the step (5), then entering a tackifying kettle for tackifying reaction, obtaining a chain-extended modified biodegradable polyester melt after the reaction, cooling the chain-extended modified biodegradable polyester melt, and granulating to obtain a chain-extended modified biodegradable polyester slice;
the temperature of the melt pipeline is 120-220 ℃; the mass ratio of the first biodegradable polyester melt to the second biodegradable polyester melt is 1: (1-6).
2. The method of claim 1, wherein the melt mixing device is at a temperature of 120-220 ℃.
3. The method for chain-extending modified biodegradable polyester according to claim 1, characterized in that the reaction temperature of the chain-extending homogenization reaction is 220-260 ℃ and the reaction time is 2-30min.
4. The method for chain extension modified biodegradable polyester according to claim 1, characterized in that the reaction temperature in the polycondensation reactor is 220-280 ℃, the reaction time is 40-180min, and the vacuum degree is not more than 120Pa.
5. The method for chain extension modified biodegradable polyester according to claim 1, characterized in that the reaction temperature in the tackifying kettle is 220-280 ℃, the reaction time is 20-100min, and the vacuum degree is not more than 120Pa.
6. The method of claim 1, wherein the first biodegradable polyester melt and the second biodegradable polyester melt are prepared from at least one material selected from the group consisting of PBAT, PBST, PBS, PBA, PBT, PHB, PVA, PHA, PLA, PCL, PPC.
7. The method of claim 1, wherein the intrinsic viscosity of the first and second biodegradable polyester melts is from 0.05 to 0.25dL/g.
8. Use of a method of chain extending modified biodegradable polyesters according to any of claims 1-7, characterized in that it is applied in the production of biodegradable polyesters.
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