CN115612074A - Preparation method of biodegradable polyester - Google Patents
Preparation method of biodegradable polyester Download PDFInfo
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- CN115612074A CN115612074A CN202211265136.6A CN202211265136A CN115612074A CN 115612074 A CN115612074 A CN 115612074A CN 202211265136 A CN202211265136 A CN 202211265136A CN 115612074 A CN115612074 A CN 115612074A
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- catalyst
- biodegradable polyester
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- adipic acid
- terephthalic acid
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- 229920000229 biodegradable polyester Polymers 0.000 title claims abstract description 26
- 239000004622 biodegradable polyester Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims abstract description 78
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 76
- 239000003054 catalyst Substances 0.000 claims abstract description 76
- 235000011037 adipic acid Nutrition 0.000 claims abstract description 39
- 239000001361 adipic acid Substances 0.000 claims abstract description 39
- 230000000694 effects Effects 0.000 claims abstract description 28
- 238000005886 esterification reaction Methods 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 21
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 230000007062 hydrolysis Effects 0.000 claims description 15
- 238000006460 hydrolysis reaction Methods 0.000 claims description 15
- 238000006068 polycondensation reaction Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 10
- 239000003963 antioxidant agent Substances 0.000 claims description 7
- 230000003078 antioxidant effect Effects 0.000 claims description 7
- 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 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 238000007599 discharging Methods 0.000 claims description 7
- 239000012153 distilled water Substances 0.000 claims description 7
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical group C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 7
- KQIQJFPCKQNXSA-UHFFFAOYSA-N butane-1,1-diol;titanium Chemical compound [Ti].CCCC(O)O KQIQJFPCKQNXSA-UHFFFAOYSA-N 0.000 claims description 5
- 238000013329 compounding Methods 0.000 claims description 3
- KRXBVZUTZPDWQI-UHFFFAOYSA-N ethane-1,2-diol;titanium Chemical group [Ti].OCCO KRXBVZUTZPDWQI-UHFFFAOYSA-N 0.000 claims description 3
- 150000000190 1,4-diols Chemical class 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 abstract description 12
- 239000004970 Chain extender Substances 0.000 abstract description 7
- 238000009833 condensation Methods 0.000 abstract description 5
- 230000005494 condensation Effects 0.000 abstract description 5
- 238000010924 continuous production Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000007086 side reaction Methods 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 239000003431 cross linking reagent Substances 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract 1
- 230000001502 supplementing effect Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 230000032050 esterification Effects 0.000 description 8
- 229920001896 polybutyrate Polymers 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- 238000013459 approach Methods 0.000 description 5
- 150000002148 esters Chemical group 0.000 description 5
- 238000011049 filling Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
- 235000013539 calcium stearate Nutrition 0.000 description 2
- 239000008116 calcium stearate Substances 0.000 description 2
- VILAVOFMIJHSJA-UHFFFAOYSA-N dicarbon monoxide Chemical group [C]=C=O VILAVOFMIJHSJA-UHFFFAOYSA-N 0.000 description 2
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical group CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- -1 polybutylene Polymers 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 229920001634 Copolyester Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 230000000655 anti-hydrolysis Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000001627 detrimental effect Effects 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
- ONIHPYYWNBVMID-UHFFFAOYSA-N diethyl benzene-1,4-dicarboxylate Chemical compound CCOC(=O)C1=CC=C(C(=O)OCC)C=C1 ONIHPYYWNBVMID-UHFFFAOYSA-N 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
-
- 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
- C08G63/78—Preparation processes
-
- 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
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
-
- 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
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/87—Non-metals or inter-compounds thereof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses a preparation method of biodegradable polyester, in particular to a preparation method of a biodegradable polyester system taking terephthalic acid, adipic acid and 1, 4-butanediol as main raw materials, and different catalyst components are designed according to different reaction stages. Particularly, in the esterification reaction stage, the compound catalyst A with a proper proportion is added, so that the activity required by the catalytic effect can be met, and a large amount of side reactions caused by too high activity can be avoided; in the condensation stage, the activity of continuous polymerization of the prepolymer with higher molecular weight at the early stage is further ensured by supplementing the high-activity catalyst B; the high molecular weight and the color phase of the product are further ensured by adding the catalyst passivator with a specific amount ratio. Meanwhile, the method is simple and efficient, and the biodegradable polyester with good color phase, adjustable melt index, high molecular weight and excellent mechanical property can be obtained through a conventional production line without using a chain extender, a cross-linking agent or other polyfunctional group aids, so that the method is very convenient for industrial continuous production.
Description
Technical Field
The invention relates to a preparation method of biodegradable polyester, in particular to a preparation method of biodegradable polyester convenient for continuous production, belonging to the field of polymer synthesis.
Background
With the international society reaching a consensus in enhancing the environmental protection aspects such as garbage classification, recycling and utilization, the forbidden laws and regulations of products which are disposable, not easy to recycle and easy to pollute are gradually strict, and more attention is paid to the research and development and application of biodegradable materials.
Aliphatic-aromatic copolyester is a biodegradable polyester, of which polybutylene terephthalate-co-adipate (hereinafter abbreviated as PBAT) is a representative. The PBAT chain segment has the flexibility of long-chain aliphatic hydrocarbon and the rigidity of aromatic ring, and has excellent flexibility and processing performance. The preparation of PBAT usually takes terephthalic acid, adipic acid and butanediol as monomers, and the synthesis is carried out according to a certain proportion, and the technical process focuses on strictly controlling the esterification mode of the reaction, such as: co-esterification, partial esterification and tandem esterification, esterification times and condensation conditions, such as: condensation polymerization temperature, condensation time, etc. The key factors influencing the esterification and condensation processes are the activity, hydrolysis resistance, dosage, addition time and the like of the catalyst.
According to the polymerization chemical reaction mechanism, the ester exchange reaction in the esterification process is a reaction for generating oligomer diethyl terephthalate by ester exchange between ester and alcohol under the action of a catalyst (such as acetates of Zn, mn, co, mg and the like). Firstly, a metal catalyst reacts with alcohol to generate a metal alcoholate, and then the metal on the metal alcoholate provides an empty orbit and lone-pair electron coordination combination of carbonyl oxygen on ester. The coordination enhances the polarity of the original polar group carbonyl group, and the electropositivity of the carbonyl carbon atom is increased, so that-CH 2CH2OH on MOR Or (MOR) HOR is easily combined with the carbonyl carbon to complete the ester exchange reaction. There are various metal compounds that can be used as catalysts for polyesters. Among them, titanium catalysts have high activity, less side reactions and low degree of promotion to the thermal degradation reaction of polyester, and are widely used at present. Tetrabutyl titanate is used most in titanium metal compounds, but is sensitive to water when being catalyzed by tetrabutyl titanate alone, is easy to inactivate in the esterification process, has low activity in the esterification process, cannot synthesize polyester products with high characteristic viscosity, and usually needs to be added with a chain extender in the condensation reaction process, which increases difficulty for the continuity of actual production and the compatibility of equipment.
In order to improve the influence of the catalyst on the synthesis reaction, recently, a compound catalyst system is selected as a hotspot, and antimony acetate and tetrabutyl titanate are selected to be compounded to form a compound catalyst, such as Wangxiao, so as to accelerate the reaction rate and improve the performance of the polyester product. However, the product obtained by the reaction is poor in hue and reddish in color through verification.
In order to ensure the color, it is often necessary to add low activity or to reduce the amount of catalyst, but this is disadvantageous in increasing the viscosity of the final product. In order to obtain a high-viscosity product and ensure later-stage mechanical and processing properties, recently, polyfunctional polybasic acid or polyhydric alcohol is often added to enable a certain chemical crosslinking point to exist in a high-molecular product, or a chain extender is added at the later stage or a tackifying method is used for carrying out the later-stage mechanical and processing properties. For example, basf patent CN 102007159B discloses a method for continuously producing biodegradable polyester, wherein tetrabutyl titanate is used as a catalyst, polyfunctional monomers such as glycerol are added in the reaction process in order to ensure the viscosity and mechanical strength of the product, and a chain extender is added in the later reaction period. CN 102007159B is a method and apparatus for continuously preparing high-quality PBAT, in which a set of viscosity-increasing apparatus is added separately in the later stage of the reaction to ensure the viscosity of the product. These undoubtedly add difficulty to the production, and the introduction of multifunctional groups is detrimental to the melt flowability and macroscopic tensile properties of the product.
Disclosure of Invention
The present invention is directed to solving the above problems and providing a method for preparing biodegradable polyester, which can obtain biodegradable polyester with good color and excellent mechanical properties without adding a polyfunctional reaction aid and without using a chain extender and a viscosity increasing device.
The technical scheme adopted by the invention is as follows: a preparation method of biodegradable polyester comprises the following steps:
(1) Adding terephthalic acid, adipic acid, 1, 4-butanediol and a catalyst A into a reaction kettle according to a proportion and stirring; then carrying out esterification reaction at 160-230 ℃, and finishing the esterification reaction when the distilled water amount is more than 98% of the theoretical water yield;
(2) Adding a catalyst B and a catalyst deactivator into the product in the step (1) according to a ratio, stirring, carrying out reduced pressure polycondensation reaction at 230-240 ℃ under the conditions of 50Pa-100Pa, and finishing the polycondensation reaction after 1 h-3h;
(3) And (4) relieving vacuum, discharging into cold water while the material is hot, and pelletizing under water to obtain the finished product.
In the present invention, the sum of the amounts of terephthalic acid and adipic acid added is: 1, 4-diol in a molar ratio of 1:1.4 to 1.6, and terephthalic acid: the molar ratio of adipic acid is 0.45-0.55, and the molar ratio of adipic acid is 0.45-0.55;
in the step (1), the catalyst A is an anti-hydrolysis catalyst, and the addition amount of the catalyst A is 0.01 to 0.5 percent of the total mass of the terephthalic acid and the adipic acid;
meanwhile, the catalyst A is formed by compounding a low-activity hydrolysis-resistant catalyst and a high-activity hydrolysis-resistant catalyst, and the mass ratio of the low-activity hydrolysis-resistant catalyst to the high-activity hydrolysis-resistant catalyst is preferably 0.5 to 2;
the hydrolysis-resistant catalyst with low activity specifically comprises: titanium glycol or titanium butanediol; the high-activity hydrolysis-resistant catalyst is specifically as follows: TYZOR 436 or DuPont PC-64.
In the step (1), the hydrolysis-resistant catalyst is designed and selected, so that the catalyst can be prevented from being inactivated in the esterification reaction stage; the low-activity and high-activity catalysis is designed in proper proportion and dosage for compounding, so that the side reaction can be reduced as much as possible while the esterification reaction rate is ensured.
In the step (2), the catalyst B is a high-activity catalyst, and specifically comprises: one of TYZOR 436, duPont PC-64 or tetrabutyl titanate, the addition amount of which is 0.1-0.25 percent of the total mass of terephthalic acid and adipic acid; the high-activity catalyst B with a proper proportion can avoid hue deterioration while ensuring the viscosity of the product;
the catalyst passivator is triphenyl phosphate, and the addition amount of the catalyst passivator is half of that of the catalyst B; the final color phase of the product is further ensured by adding a proper amount ratio of the catalyst passivator.
In the step (2), an antioxidant and a slipping agent can be synchronously added according to requirements; the addition amount of the antioxidant is 0.1-0.3 percent of the total mass of the terephthalic acid and the adipic acid, and the brand number is 1010, 168 or S-682; the addition amount of the slipping agent is 0.1-0.3% of the total mass of terephthalic acid and adipic acid, and specifically is erucamide or calcium stearate.
The invention has the advantages that: aiming at a biodegradable polyester system, different catalyst components are designed according to different reaction stages and starting from a reaction mechanism, and particularly, a proper amount of compound catalyst A is added in the esterification reaction stage, so that the activity required by the catalytic effect can be met, and the side reaction caused by too high activity can be avoided; in the condensation stage, the high-activity catalyst B is added, so that the continuous polymerization activity of the prepolymer with higher molecular weight at the early stage is further ensured, and the hue of the product is prevented from being poor; the viscosity and the color phase of the product are further ensured by adding the catalyst passivator with a specific amount ratio. Meanwhile, the method is simple and efficient, and the biodegradable polyester with good color phase, adjustable melt index, high molecular weight and excellent mechanical property can be obtained through a conventional production line without using a chain extender, a cross-linking agent or other polyfunctional group aids, so that the method is very convenient for industrial continuous production.
Detailed Description
The present invention will be further specifically described with reference to the following examples, but the present invention is not limited thereto.
Example 1
A preparation method of biodegradable polyester comprises the following steps:
(1) Sequentially adding 9mol of terephthalic acid, 10mol of adipic acid, 32mol of 1, 4-butanediol and a compound catalyst A (specifically, the compound catalyst A is prepared by mixing titanium butanediol with a mass ratio of 0.5; when the temperature approaches 160 ℃, starting to collect the initial fraction; continuously heating to 230 ℃, and finishing the esterification reaction when the distilled water amount is more than 98% of the theoretical water yield;
(2) Adding catalyst B (specifically tetrabutyl titanate) accounting for 0.1% of the total mass of terephthalic acid and adipic acid and triphenyl phosphate accounting for 0.05% of the total mass of terephthalic acid and adipic acid into a reaction kettle, and stirring for 5min; then vacuumizing, carrying out reduced pressure polycondensation reaction at 230-240 ℃ under the conditions of 50Pa-100Pa, wherein the viscosity of the system rises quickly after reacting for 30min, and after the system reaches a preset viscosity through intermittent sampling and monitoring, finishing the polycondensation reaction;
(3) And (3) filling nitrogen to remove vacuum, discharging into cold water while the nitrogen is hot, and underwater granulating to obtain the finished product.
The sample obtained in example 1 was labeled PBAT-1.
Example 2
A preparation method of biodegradable polyester comprises the following steps:
(1) Sequentially adding 11mol of terephthalic acid, 9mol of adipic acid, 30mol of 1, 4-butanediol and a compound catalyst A (specifically, the compound catalyst A is formed by mixing titanium butanediol and DuPont PC-64 in a mass ratio of 2; when the temperature approaches 160 ℃, starting to collect the initial fraction; continuously heating to 230 ℃, and finishing the esterification reaction when the distilled water amount is more than 98% of the theoretical water yield;
(2) Adding catalyst B (specifically: TYZOR 436) accounting for 0.2% of the total mass of the terephthalic acid and the adipic acid, triphenyl phosphate accounting for 0.1% of the total mass of the terephthalic acid and the adipic acid, an antioxidant (1010) accounting for 0.3% of the total mass of the terephthalic acid and the adipic acid, and a slipping agent (erucamide) accounting for 0.3% of the total mass of the terephthalic acid and the adipic acid into a reaction kettle, and stirring for 5min; then vacuumizing, carrying out reduced pressure polycondensation reaction at 230-240 ℃ under the condition of 50Pa-100Pa, wherein the viscosity of the system rises quickly after reacting for 30min, and after the system is intermittently sampled and monitored to reach the preset viscosity, finishing the polycondensation reaction;
(3) And (4) filling nitrogen to relieve vacuum, discharging into cold water while the nitrogen is hot, and performing underwater granulation to obtain the product.
The sample obtained in example 2 was labeled PBAT-2.
Example 3
A preparation method of biodegradable polyester comprises the following steps:
(1) Sequentially adding 9mol of terephthalic acid, 11mol of adipic acid, 32mol of 1, 4-butanediol and a compound catalyst A (specifically, the compound catalyst A is formed by mixing ethylene glycol titanium and TYZOR 436 in a mass ratio of 2; when the temperature approaches 160 ℃, starting to collect the initial fraction; continuously heating to 230 ℃, and finishing the esterification reaction when the distilled water amount is more than 98% of the theoretical water yield;
(2) Adding catalyst B (specifically DuPont PC-64) accounting for 0.25% of the total mass of the terephthalic acid and the adipic acid, triphenyl phosphate accounting for 0.125% of the total mass of the terephthalic acid and the adipic acid, antioxidant (168) accounting for 0.2% of the total mass of the terephthalic acid and the adipic acid and slipping agent (calcium stearate) accounting for 0.1% of the total mass of the terephthalic acid and the adipic acid into a reaction kettle, and stirring for 5min; then vacuumizing, carrying out reduced pressure polycondensation reaction at 230-240 ℃ under the conditions of 50Pa-100Pa, wherein the viscosity of the system rises quickly after reacting for 30min, and after the system reaches a preset viscosity through intermittent sampling and monitoring, finishing the polycondensation reaction;
(3) And (3) filling nitrogen to remove vacuum, discharging into cold water while the nitrogen is hot, and underwater granulating to obtain the finished product.
The sample obtained in example 3 was designated PBAT-3.
Example 4
A preparation method of biodegradable polyester comprises the following steps:
(1) Sequentially adding 10mol of terephthalic acid, 10mol of adipic acid, 28mol of 1, 4-butanediol and a compound catalyst A (specifically, a mixture of ethylene glycol titanium and TYZOR 436 with the mass ratio of 1; when the temperature approaches 160 ℃, starting to collect the primary fraction; continuously heating to 230 ℃, and finishing the esterification reaction when the distilled water amount is more than 98% of the theoretical water yield;
(2) Adding catalyst B (specifically: TYZOR 436) accounting for 0.2% of the total mass of the terephthalic acid and the adipic acid, triphenyl phosphate accounting for 0.1% of the total mass of the terephthalic acid and the adipic acid, an antioxidant accounting for 0.1% of the total mass of the terephthalic acid and the adipic acid and a slipping agent accounting for 0.2% of the total mass of the terephthalic acid and the adipic acid into a reaction kettle, and stirring for 5min; then vacuumizing, carrying out reduced pressure polycondensation reaction at 230-240 ℃ under the condition of 50Pa-100Pa, wherein the viscosity of the system rises quickly after reacting for 30min, and after the system is intermittently sampled and monitored to reach the preset viscosity, finishing the polycondensation reaction;
(3) And (3) filling nitrogen to remove vacuum, discharging into cold water while the nitrogen is hot, and underwater granulating to obtain the finished product.
The sample obtained in example 4 was designated PBAT-4.
Example 5
A preparation method of biodegradable polyester comprises the following steps:
(1) Sequentially adding 10mol of terephthalic acid, 9mol of adipic acid, 30mol of 1, 4-butanediol and a compound catalyst A (specifically, a mixed catalyst A prepared by mixing titanium butanediol with a mass ratio of 1.5 to 1 and Dupont PC-64) accounting for 0.35 percent of the total mass of the terephthalic acid and the adipic acid into a reaction kettle, gradually heating to 130 ℃, and starting stirring; when the temperature approaches 160 ℃, starting to collect the initial fraction; continuously heating to 230 ℃, and finishing the esterification reaction when the distilled water amount is more than 98% of the theoretical water yield;
(2) Adding catalyst B (specifically: TYZOR 436) accounting for 0.15% of the total mass of terephthalic acid and adipic acid and triphenyl phosphate accounting for 0.075% of the total mass of terephthalic acid and adipic acid into a reaction kettle, and stirring for 5min; then vacuumizing, carrying out reduced pressure polycondensation reaction at 230-240 ℃ under the condition of 50Pa-100Pa, wherein the viscosity of the system rises quickly after reacting for 30min, and after the system is intermittently sampled and monitored to reach the preset viscosity, finishing the polycondensation reaction;
(3) And (4) filling nitrogen to relieve vacuum, discharging into cold water while the nitrogen is hot, and performing underwater granulation to obtain the product.
The sample obtained in example 5 was designated PBAT-5.
Performance test
The properties PBAT-1 to PBAT-5 of the samples obtained in the above examples were compared with those of a commercially available conventional PBAT product (galvanostatic PBAT-HL), and the specific results are shown below.
Wherein: the structural composition of the product is referred to the standard GB/T6040; density reference standard GB/T1033; the fused finger reference standard GB/T3682; melting point reference standard GB/T19466; the elongation at break adopts a universal tensile testing machine, and is in reference to the standard GB/T1040; acid value reference standard: DIN EN 12634.
Table 1: results of performance tests on each sample and a commercially available conventional product (PBAT-HL)
From table 1 above, it is evident that the PBAT prepared by the present invention has a wide range of melt indices. For example, the PBAT-1 fuse finger 4.6 can meet the requirement of direct blow molding and can be directly used as resin; and the melt index of PBAT-4 is 25.5, and the PBAT-4 can be compounded with degradable materials such as PLA, starch and the like which are sold in markets for use. In addition, the color and acid value of the PBAT prepared by the method are equivalent to those of the products sold in the market. Most importantly, the invention can simply and efficiently obtain the target product by adjusting the type and the dosage of the catalyst in the esterification reaction and the polycondensation reaction without adding a polyfunctional reagent, a chain extender, a tackifier and the like, and is very convenient for industrial continuous production.
Claims (7)
1. A preparation method of biodegradable polyester is characterized by comprising the following steps:
(1) Adding terephthalic acid, adipic acid, 1, 4-butanediol and a catalyst A into a reaction kettle according to a proportion and stirring; then carrying out esterification reaction at 160-230 ℃, and finishing the esterification reaction when the distilled water amount is more than 98% of the theoretical water yield;
(2) Adding a catalyst B and a catalyst deactivator into the product obtained in the step (1) according to a certain proportion, stirring, and carrying out reduced pressure polycondensation reaction for 1h to 3h under the conditions of 230-240 ℃ and 50Pa to 100Pa;
(3) Removing vacuum, discharging into cold water while hot, and underwater granulating;
in the step (1), the catalyst A is an hydrolysis-resistant catalyst, the addition amount of the catalyst A is 0.01 to 0.5 percent of the total mass of the terephthalic acid and the adipic acid, and the catalyst A is prepared by compounding a low-activity hydrolysis-resistant catalyst and a high-activity hydrolysis-resistant catalyst;
in the step (2), the catalyst B is a high-activity catalyst, and the addition amount of the catalyst B is 0.1-0.25% of the total mass of the terephthalic acid and the adipic acid; the amount of catalyst deactivator added was half of that of catalyst B.
2. The process for producing a biodegradable polyester according to claim 1, wherein: in the catalyst A, the mass ratio of a low-activity hydrolysis-resistant catalyst to a high-activity hydrolysis-resistant catalyst is 0.5 to 2.
3. The process for producing a biodegradable polyester according to claim 2, wherein: the low-activity hydrolysis-resistant catalyst is ethylene glycol titanium or titanium butanediol, and the high-activity hydrolysis-resistant catalyst is TYZOR 436 or DuPont PC-64.
4. The process for producing biodegradable polyester according to claim 1, characterized in that: the catalyst B is one of TYZOR 436, duPont PC-64 or tetrabutyl titanate.
5. The process for producing biodegradable polyester according to claim 4, wherein: the catalyst passivator is triphenyl phosphate.
6. The process for producing a biodegradable polyester according to claim 1, wherein: in the step (1), the sum of the addition amounts of terephthalic acid and adipic acid is as follows: 1, 4-diol in a molar ratio of 1.4 to 1.6, wherein the molar ratio of terephthalic acid: the molar ratio of adipic acid is 0.45-0.55.
7. The process for producing a biodegradable polyester according to claim 6, wherein: in the step (2), an antioxidant and a slipping agent are synchronously added, wherein the addition amount of the antioxidant is 0.1-0.3% of the total mass of the terephthalic acid and the adipic acid, and the addition amount of the slipping agent is 0.1-0.3% of the total mass of the terephthalic acid and the adipic acid.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117417514A (en) * | 2023-12-18 | 2024-01-19 | 康辉新材料科技有限公司 | Anthracene-2, 6-dicarboxylic acid modified PBAT degradation material, preparation method and application thereof |
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| CN103130992A (en) * | 2013-03-25 | 2013-06-05 | 山东汇盈新材料科技有限公司 | Preparation method of polyadipic acid-butylene terephthalate with high molecular weight |
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| CN112266471A (en) * | 2020-11-13 | 2021-01-26 | 营口康辉石化有限公司 | Preparation method of polybutylene adipate-terephthalate |
| CN113549306A (en) * | 2021-07-09 | 2021-10-26 | 万华化学集团股份有限公司 | PBAT resin composition and preparation method thereof |
| CN113667103A (en) * | 2021-08-30 | 2021-11-19 | 万华化学集团股份有限公司 | Preparation method of PBAT resin |
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| DE2705230A1 (en) * | 1977-02-08 | 1978-08-17 | Bayer Ag | High mol polyester prodn. - by reacting di:carboxylic acids with diol(s) in presence of manganese, magnesium, titanium and germanium cpds. as catalyst |
| CN103649168A (en) * | 2011-07-15 | 2014-03-19 | 沙特基础工业公司 | Color-stabilized biodegradable aliphatic-aromatic copolyesters, methods of manufacture, and articles thereof |
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| CN117417514A (en) * | 2023-12-18 | 2024-01-19 | 康辉新材料科技有限公司 | Anthracene-2, 6-dicarboxylic acid modified PBAT degradation material, preparation method and application thereof |
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