WO2023071646A1 - 一种半芳香族聚酯及其制备方法和应用 - Google Patents

一种半芳香族聚酯及其制备方法和应用 Download PDF

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WO2023071646A1
WO2023071646A1 PCT/CN2022/120721 CN2022120721W WO2023071646A1 WO 2023071646 A1 WO2023071646 A1 WO 2023071646A1 CN 2022120721 W CN2022120721 W CN 2022120721W WO 2023071646 A1 WO2023071646 A1 WO 2023071646A1
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acid
semi
aromatic polyester
reaction
component
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English (en)
French (fr)
Chinese (zh)
Inventor
张传辉
陈平绪
叶南飚
欧阳春平
麦开锦
董学腾
曾祥斌
卢昌利
蔡彤旻
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Zhuhai Kingfa Biomaterial Co Ltd
Kingfa Science and Technology Co Ltd
Jiangsu Kingfa New Material Co Ltd
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Zhuhai Kingfa Biomaterial Co Ltd
Kingfa Science and Technology Co Ltd
Jiangsu Kingfa New Material Co Ltd
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Application filed by Zhuhai Kingfa Biomaterial Co Ltd, Kingfa Science and Technology Co Ltd, Jiangsu Kingfa New Material Co Ltd filed Critical Zhuhai Kingfa Biomaterial Co Ltd
Priority to KR1020247017309A priority Critical patent/KR20240090921A/ko
Priority to JP2024526784A priority patent/JP7784544B2/ja
Priority to US18/704,931 priority patent/US20250043069A1/en
Publication of WO2023071646A1 publication Critical patent/WO2023071646A1/zh
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • 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
    • 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
    • C08G63/02—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
    • C08G63/20—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
    • 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
    • C08G63/785—Preparation processes characterised by the apparatus used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • C08G2230/00—Compositions for preparing biodegradable 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
    • C08G2390/00—Containers
    • 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

Definitions

  • the invention relates to the field of biodegradable polyesters, in particular to a semi-aromatic polyester with specific double bond content and its preparation method and application.
  • Biodegradable aliphatic-aromatic copolyesters can be prepared from aliphatic dibasic acids or their derivatives, aliphatic dibasic alcohols, aromatic dibasic acids or their derivatives.
  • the copolyester is represented by Ecoflex produced by German BASF company, and its raw materials are 1,6-adipic acid (AA), 1,4-butanediol (BDO), and terephthalic acid.
  • the copolyester has a low melt volume flow rate (MVR) for good processability, and also has a very low acid value, which in turn leads to good hydrolysis resistance.
  • MVR melt volume flow rate
  • semi-aromatic polyesters are more prone to thermal decomposition, and after thermal degradation, structures such as double bonds and carboxyl groups are produced, resulting in deterioration of the performance of the polymerized product, which is not conducive to later use.
  • the object of the present invention is to provide a semi-aromatic polyester, which has better melt heat retention stability and good color due to its specific double bond content.
  • Another object of the present invention is to provide a method for preparing the above-mentioned semi-aromatic polyester.
  • the first component A based on the total molar weight of the first component A, comprises:
  • the second component B includes diols with 2-12 carbon atoms
  • the double bond content in the semi-aromatic polyester is 0.55-4.5 mmol/kg, preferably 0.70-2.5 mmol/kg, more preferably 0.75-0.95 mmol/kg.
  • the polyester synthesis process due to the influence of many factors such as the structure or ratio of raw material monomers, the types of catalysts, branching agents and chain extenders, the preparation process, reaction time, polymerization temperature, etc., the final prepared There is a big difference in the molecular structure of polyester.
  • the present invention finds through research that the double bond content in the semi-aromatic polyester is closely related to the melting thermal retention stability and color of the semi-aromatic polyester.
  • the present invention unexpectedly finds through research that the double bond content in the semi-aromatic polyester is controlled within the range of 0.55-4.5mmol/kg, and the obtained semi-aromatic polyester has better melt thermal retention stability and good color.
  • said component a1) aliphatic dicarboxylic acid or its derivatives are selected from oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid , sebacic acid, 1,11-undecane dicarboxylic acid, 1,10-decane dicarboxylic acid, undecane dioic acid, 1,12-dodecane dicarboxylic acid, hexadecane dioic acid, di One or a mixture of dedecanedioic acid or tetracosanedioic acid or their ester derivatives or their anhydride derivatives.
  • the component a1) is selected from oxalic acid, dimethyl oxalate, malonic acid, dimethyl malonate, succinic acid, dimethyl succinate, methyl succinic acid, glutaric acid , dimethyl glutarate, bis(2-hydroxyethyl) glutarate, bis(3-hydroxypropyl) glutarate, bis(4-hydroxybutyl) glutarate, 2-methyl Glutaric acid, 3-methylglutaric acid, adipic acid, dimethyl adipate, bis(2-hydroxyethyl) adipate, bis(3-hydroxypropyl) adipate, Bis(4-hydroxybutyl)adipate, 3-methyladipic acid, 2,2,5,5-tetramethyladipic acid, pimelic acid, suberic acid, azelaic acid, azelaic acid dimethyl ester, sebacic acid, 1,11-undecanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1,11-und
  • the component a2) aromatic dicarboxylic acid or its derivative is selected from one of terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid or its ester derivative or its anhydride derivative or A mixture of several, preferably terephthalic acid or its ester derivatives or its anhydride derivatives.
  • the component a2) is selected from terephthalic acid, dimethyl terephthalate, bis(2-hydroxyethyl) terephthalate, bis(3-hydroxyethyl) terephthalate, Hydroxypropyl) ester, bis(4-hydroxybutyl) terephthalate, isophthalic acid, dimethyl isophthalate, bis(2-hydroxyethyl) isophthalate, isophthalic acid Bis(3-hydroxypropyl) formate, bis(4-hydroxybutyl) isophthalate, 2,6-naphthalene dicarboxylic acid, dimethyl 2,6-phthalate, 2,7-naphthalene Dicarboxylic acid, 2,7-dimethyl phthalate, 3,4'-diphenyl ether dicarboxylic acid, 3,4'-dimethyl diphenyl ether dicarboxylate, 4,4'-diphenyl ether dicarboxylate Acid, 4,4'-diphenyl ether di
  • the second component B is selected from ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1, 9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,4-cyclohexanediol, 1,4-cyclohexanediol
  • alkane dimethanols preferably ethylene glycol, 1,3-propanediol or 1,4-butanediol.
  • component a1) is adipic acid or its ester derivative or its anhydride derivative
  • component a2) is terephthalic acid or its ester derivative or its anhydride derivative
  • the second component B Use the 1,4-butanediol combination.
  • the third component C is 0.01-5.0 mol%
  • the fourth component D is 0.01-5.0 mol%.
  • the third component C is selected from tartaric acid, citric acid, malic acid, trimethylolpropane, trimethylolethane, pentaerythritol, polyether triol, glycerin, 1,3,5-trimesic acid, 1 , one or more of 2,4-trimesic acid, 1,2,4-trimesic anhydride, 1,2,4,5-pyrimellitic acid or pyromellitic dianhydride, preferably trimethylol propane, pentaerythritol, or glycerin.
  • the fourth component D is a chain extender, and the chain extender is isocyanate, isocyanurate, peroxide, epoxide, oxazoline, oxazine, One or more mixtures of lactam, carbodiimide or polycarbodiimide.
  • the isocyanate containing two or more functional groups may be aromatic isocyanate or aliphatic isocyanate, preferably aromatic diisocyanate or aliphatic diisocyanate.
  • the aromatic diisocyanate is toluene 2,4-diisocyanate, toluene 2,6-diisocyanate, diphenylmethane 2,2'-diisocyanate, diphenylmethane 2,4'-diisocyanate, diphenyl Methane 4,4'-diisocyanate, naphthalene 1,5-diisocyanate or xylene diisocyanate.
  • the aromatic diisocyanate is diphenylmethane 2,2'-diisocyanate, diphenylmethane 2,4'-diisocyanate or diphenylmethane 4,4'-diisocyanate.
  • the isocyanate containing 2 or more functional groups may also be tris(4-isocyanato-phenyl)methane with three rings.
  • the aliphatic diisocyanate is any linear or branched alkylene diisocyanate or cycloalkylene diisocyanate containing 2 to 20 carbon atoms, more preferably 3 to 12 carbon atoms.
  • the aliphatic diisocyanate may be hexamethylene 1,6-diisocyanate, isophorone diisocyanate or methylene bis(4-isocyanatocyclohexane), most preferably hexamethylene 1 , 6-diisocyanate or isophorone diisocyanate.
  • the isocyanurate containing 2 or more functional groups is an aliphatic isocyanurate derived from an alkylene group having 2 to 20 carbon atoms, preferably 3 to 12 carbon atoms Diisocyanates or cycloalkylene diisocyanates, such as isophorone diisocyanate or methylene bis(4-isocyanatocyclohexane).
  • the alkylene diisocyanate may be a linear or branched compound. Particular preference is given to isocyanurates based on n-hexamethylene diisocyanate, such as cyclic trimers, pentamers or higher oligomers of hexamethylene 1,6-diisocyanate.
  • the peroxide containing two or more functional groups is preferably benzoyl peroxide, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclo Hexane, 1,1-bis(tert-butylperoxy)methylcyclododecane, n-butyl 4,4-bis(butylperoxy)valerate, dicumyl peroxide, benzene peroxide tert-butyl formate, dibutyl peroxide, ⁇ , ⁇ -di(tert-butylperoxy)diisopropylbenzene, 2,5-dimethyl-2,5-bis(tert-butylperoxy) ) hexane, 2,5-dimethyl-2,5-di(tert-butylperoxy)hex-3-yne or cumene tert-butylperoxide.
  • benzoyl peroxide 1,1-bis(tert-butylperoxy)-3,3,
  • the epoxide containing 2 or more functional groups is preferably hydroquinone, diglycidyl ether, resorcinol diglycidyl ether, 1,6-hexanediol diglycidyl ether , Hydrogenated Bisphenol A Diglycidyl Ether, Diglycidyl Terephthalate, Diglycidyl Tetrahydrophthalate, Diglycidyl Hexahydrophthalate, Diglycidyl Terephthalate Methyl diglycidyl ester, phenylene diglycidyl ether, ethylene diglycidyl ether, trimethylene diglycidyl ether, tetramethylene diglycidyl ether, hexamethylene di Glycidyl ether, sorbitol diglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether,
  • the epoxy containing 2 or more functional groups is also preferably a copolymer based on styrene, acrylate and/or methacrylate and containing an epoxy group, the epoxy group is preferably (methyl) Glycidyl Acrylate.
  • Compounds which have proven advantageous are copolymers in which the proportion of glycidyl methacrylate in the copolymer is higher than 20% by weight, more preferably higher than 30% by weight, more preferably higher than 50% by weight.
  • the epoxy equivalent weight in these polymers is preferably 150 to 3000 g/equivalent, more preferably 200 to 500 g/equivalent.
  • the weight average molecular weight Mw of the polymer is preferably 2,000 to 25,000, more preferably 3,000 to 8,000.
  • the number average molecular weight Mn of the polymer is preferably 400 to 6000, more preferably 1000 to 4000.
  • the bisoxazoline is 2,2'-bis(2-oxazoline), bis(2-oxazolinyl)methane, 1,2-bis(2-oxazolinyl)ethane , 1,3-bis(2-oxazolinyl)propane, 1,4-bis(2-oxazolinyl)butane, 2,2'-bis(2-oxazoline), 2,2' -bis(4-methyl-2-oxazoline), 2,2'-bis(4,4'-dimethyl-2-oxazoline), 2,2'-bis(4-ethyl- 2-oxazoline), 2,2'-bis(4,4'-diethyl-2-oxazoline), 2,2'-bis(4-propyl-2-oxazoline), 2 ,2'-bis(4-butyl-2-oxazoline), 2,2'-bis(4-hexyl-2-oxazoline), 2,2'-bis(4-phenyl-2- Oxazoline), 2, 2,2
  • it is 1,4-bis(2-oxazolinyl)benzene, 1,2-bis(2-oxazolinyl)benzene or 1,3-bis(2-oxazolinyl)benzene.
  • dioxazine is 2,2'-bis(2-dioxazine), bis(2-dioxazinyl)methane, 1,2-bis(2-dioxazinyl)ethane, 1, 3-bis(2-dioxazinyl)propane, 1,4-bis(2-dioxazinyl)butane, 1,4-bis(2-dioxazinyl)benzene, 1,2-bis( 2-dioxazinyl)benzene or 1,3-bis(2-dioxazinyl)benzene.
  • the carbodiimide or polycarbodiimide containing two or more functional groups is preferably N,N'-di-2,6-diisopropylphenylcarbodiimide, N,N'- Di-o-tolylcarbodiimide, N,N'-diphenylcarbodiimide, N,N'-dioctyldecylcarbodiimide, N,N'-di-2,6- Dimethylphenylcarbodiimide, N-tolyl-N'-cyclohexylcarbodiimide, N,N'-di-2,6-di-tert-butylphenylcarbodiimide, N- Tolyl-N'-phenylcarbodiimide, N,N'-di-p-nitrophenylcarbodiimide, N,N'-di-p-aminophenylcarbodiimide, N,N' -Di-p-hydroxyphenylcarbod
  • the viscosity number of the semi-aromatic polyester measured in a phenol/o-dichlorobenzene solution with a weight ratio of 1:1 and in a constant temperature water bath at 25 ⁇ 0.05°C is 150 -350ml/g.
  • the carboxyl content of the semi-aromatic polyester is 5-60 mmol/kg, preferably 10-30 mmol/kg.
  • the present invention also provides the preparation method of above-mentioned semi-aromatic polyester, comprises the steps:
  • the esterification product Ba1 in step S1 is subjected to a primary polycondensation reaction at a reaction temperature of 170-220°C and a pressure of 1-10kPa; the esterification product Ba2 in step S1 is subjected to a primary polycondensation reaction at a reaction temperature of 230-270°C and a pressure of 1-10kPa; the two independently carry out the primary polycondensation reaction until the respective reaction products reach the requirements of GB/T 17931-1999 in a phenol/o-dichlorobenzene solution with a weight ratio of 1:1, in a constant temperature water bath at 25 ⁇ 0.05°C
  • the viscosity number 15-60ml/g measured in the medium obtains the product Pre-Ba1 and Pre-Ba2 of the primary polycondensation reaction respectively;
  • step S4 After the final polymerization product Poly-Ba1 and Poly-Ba2 obtained in step S3 are mixed and reacted by a mixer, a semi-aromatic polyester is obtained, so that it reaches GB/T 17931-1999 at a weight ratio of 1:1 phenol/ In o-dichlorobenzene solution, the viscosity measured in a constant temperature water bath at 25 ⁇ 0.05°C is 150-300ml/g.
  • the catalyst when preparing the Ba2 esterification product, 0.001-1% of the catalyst based on the weight of the final semi-aromatic polyester is added.
  • the catalyst is added in an amount of 0.02-0.2% by weight of the final semi-aromatic polyester. Controlling the amount of catalyst added can make the subsequent processing more stable.
  • the catalyst may be a tin compound, an antimony compound, a cobalt compound, a lead compound, a zinc compound, an aluminum compound or a titanium compound, more preferably a zinc compound, an aluminum compound or a titanium compound, and most preferably a titanium compound.
  • titanium compounds such as tetrabutyl orthotitanate or tetraisopropyl orthotitanate
  • tetrabutyl orthotitanate or tetraisopropyl orthotitanate over other compounds is that the residues in the product or downstream products are less toxic. This property is especially important in biodegradable polyesters as they go directly into the environment in the form of compostable bags or mulch films.
  • the pressures described in the process of the present invention are all absolute pressures (absolute pressures).
  • the total molar amount of the second component B is usually 1.1-3.0 times that of the first component A, and the excess second component B is recovered through the purification equipment (generally a rectification tower) connected to the esterification reactor into the esterification reactor.
  • the amount of recovered second component B is usually 20-50 wt% of the fresh second component B used.
  • the reaction temperature is more preferably 180-200° C.
  • the reaction pressure is more preferably 2-5 kPa.
  • the catalyst remaining in S1 can be added in step S2.
  • the reaction temperature is more preferably 240-260°C, and the reaction pressure is more preferably 2-5kPa.
  • a passivating agent can be mixed with the prepolyester.
  • Useful passivators are usually phosphorus compounds, including phosphoric acid, phosphorous acid and their esters. Based on the weight of the final polyester, the passivating agent is generally used in an amount of 0.001-0.1 wt%, preferably 0.01-0.05 wt%.
  • the reaction temperature is more preferably 190-220°C, and the reaction pressure is more preferably 50-200Pa.
  • the reaction temperature is more preferably 240-260°C, and the reaction pressure is more preferably 20-100Pa.
  • the reaction time of polycondensation is preferably 1-5h, more preferably 2-4h.
  • the produced Poly-Ba1 and Poly-Ba2 polyesters, according to GB/T 17931-1999, are measured in a phenol/o-dichlorobenzene solution with a weight ratio of 1:1 and in a constant temperature water bath at 25 ⁇ 0.05°C. The number is 50-180ml/g.
  • the carboxyl content of the Poly-Ba1 and Poly-Ba2 polyesters after the S3 reaction is generally 5-60 mmol/kg, more preferably 10-30 mmol/kg.
  • the mixing of Poly-Ba1 and Poly-Ba2 is carried out in the mixer, and described mixer comprises raw material injection system, temperature adjustment system, high-shear homogenization pump and homogenizer;
  • the described mixer The temperature range is 200°C-280°C, preferably 240°C-260°C; the residence time of Poly-Ba1 and Poly-Ba2 in the mixer is 1-4h, preferably 1.5-2h.
  • the obtained reaction product reaches the viscosity number 150-300ml/ regulated by GB/T 17931-1999 in a phenol/o-dichlorobenzene solution with a weight ratio of 1:1 and in a constant temperature water bath at 25 ⁇ 0.05°C. g.
  • step S5 is also included.
  • the semi-aromatic polyester obtained in step S4 is added to the fourth component D to carry out chain extension reaction at a reaction temperature of 200 to 270 ° C, and the reaction residence time is 0.5-15 minutes, It is preferably 2-5 minutes until the reaction product reaches the viscosity number 150- 350ml/g, that is.
  • the aliphatic diacid and the aromatic diacid are independently polymerized before the chain extension stage, and the aliphatic polyester oligomer and the aromatic polyester oligomer are not mixed until the chain extension stage.
  • the double bond content of the prepared semi-aromatic polyester is 0.55-4.5 mmol/kg, so that it has good melting heat retention stability and good color.
  • the above-mentioned semi-aromatic polyester of the present invention can also pass through other processes, such as directly copolymerizing double bond-containing compounds (such as undecylenic acid, etc.) mmol/kg.
  • the present invention also provides the application of the above-mentioned semi-aromatic polyester in the preparation of compostable degradation products, and the compostable degradation products can be fibers, films or containers.
  • the present invention also provides a semi-aromatic polyester molding composition, comprising the following components by weight ratio:
  • said additives and/or other polymers may be at least one or more selected from the group consisting of aliphatic polyesters, polycaprolactone, starch, cellulose, polyhydroxyalkanoates and polylactic acid components.
  • the present invention has the following beneficial effects:
  • the present invention provides a semi-aromatic polyester having a specific double bond content, better melt heat retention stability and good color than known semi-aromatic polyesters.
  • Fig. 1 is the gained semi-aromatic polyester of embodiment 1 1 H NMR figure
  • Figure 2 is an enlarged view of the double bond peak in the 1 HNMR spectrum of the semi-aromatic polyester obtained in Example 1.
  • test method of double bond content in semi-aromatic polyester taking the PBAT obtained by the reaction of terephthalic acid, adipic acid and 1,4-butanediol in Example 1 as an example):
  • IT is the integral area of 4 hydrogen atoms on the benzene ring of the terephthalic acid repeating unit
  • I A is the integrated area of the 4 hydrogen atoms on the 2 -CH 2 - of the adipic acid repeating unit connected to the carbonyl group;
  • M 0 is the average molecular weight of a single repeating unit of semiaromatic polyester PBAT;
  • MPBT is the molecular weight of the PBT repeating unit 220g/mol
  • MPBA is the molecular weight of the PBA repeating unit 200g/mol
  • the average molecular weight M 0 of the PBAT repeating unit of the semi-aromatic polyester in Example 1 is 209g/mol.
  • the solvent mixture used included 1 part by volume of DMSO, 8 parts by volume of isopropanol, and 7 parts by volume of toluene.
  • the semi-aromatic polyester sample was heated to 70°C to dissolve all the polymer into a clear solution, and the solution temperature was maintained at 60-70°C during the titration to avoid polymer precipitation.
  • the titration solution is tetrabutylammonium hydroxide, avoiding the use of highly toxic tetramethylammonium hydroxide.
  • the blank solvent when testing the volume of the titration solution consumed by the blank solvent, the blank solvent should be heated to 70°C and kept at a constant temperature for 0.5h, and then immediately use lye to test The titration of the blank solvent prevents the blank solvent from further absorbing CO 2 in the air after heating.
  • the esterified product Ba1 is moved into the first precondensation reactor, and at the same time, 0.096 kg/h of n-butyl titanate and 0.245 kg/h of triphenyl phosphate are added, the temperature is 200 ° C, the pressure of the reactor is 4 kPa, and the residence time is 2 -3h, the excess butanediol is drawn out, at this time the reaction product Pre-Ba1 reaches GB/T 17931-1999 regulations in a phenol/o-dichlorobenzene solution with a weight ratio of 1:1 in a constant temperature water bath at 25 ⁇ 0.05°C The viscosity measured in the medium is 44ml/g;
  • the prepolymer Pre-Ba1 is sent into the first final polymerization tank through a melt pump.
  • the temperature of the first final polymerization tank is 220° C.
  • the pressure is 120 Pa
  • the reaction time is 2-4 hours.
  • the reaction product Poly-Ba1 reaches GB/T 17931-1999, and the viscosity number measured in a phenol/o-dichlorobenzene solution with a weight ratio of 1:1 in a constant temperature water bath at 25 ⁇ 0.05°C is 138ml/g;
  • the prepolymer Pre-Ba2 is sent into the second final polymerization reactor through a melt pump.
  • the temperature of the second final polymerization reactor is 250° C.
  • the pressure is 20 Pa
  • the reaction time is 2-4 hours.
  • the reaction product Poly-Ba2 reaches GB/T 17931-1999, and the viscosity number measured in a phenol/o-dichlorobenzene solution with a weight ratio of 1:1 in a constant temperature water bath at 25 ⁇ 0.05°C is 115ml/g;
  • the two end polymers of Poly-Ba1 and Poly-Ba2 are continuously fed into the mixer, the temperature of the mixer is 250°C, and the residence time is 1.5h.
  • the resulting polyester was then introduced into a twin-screw extruder, while 5.2 kg/h of hexamethylene diisocyanate (HDI) were metered in at a set temperature of 240°C. After a residence time of 3 minutes, the polyester was pelletized using an underwater pelletizer and then dried to obtain the final polyester product.
  • HDI hexamethylene diisocyanate
  • the esterified product Ba1 was moved into the first precondensation reactor, and at the same time, 0.096 kg/h of n-butyl titanate and 0.245 kg/h of triphenyl phosphate were added, the temperature was 190°C, the pressure of the reactor was 4kPa, and the residence time was 2 -3h, the excess butanediol is drawn out, at this time the reaction product Pre-Ba1 reaches GB/T 17931-1999 regulations in a phenol/o-dichlorobenzene solution with a weight ratio of 1:1 in a constant temperature water bath at 25 ⁇ 0.05°C The viscosity measured in the medium is 46ml/g;
  • the prepolymer Pre-Ba1 is sent into the first final polymerization reactor through a melt pump.
  • the temperature of the first final polymerization reactor is 210° C.
  • the pressure is 120 Pa
  • the reaction time is 2-4 hours.
  • the reaction product Poly-Ba1 reaches GB/T 17931-1999, and the viscosity number measured in a phenol/o-dichlorobenzene solution with a weight ratio of 1:1 in a constant temperature water bath at 25 ⁇ 0.05°C is 147ml/g;
  • the prepolymer Pre-Ba2 is sent into the second final polymerization reactor through a melt pump.
  • the temperature of the second final polymerization reactor is 250° C.
  • the pressure is 20 Pa
  • the reaction time is 2-4 hours.
  • the reaction product Poly-Ba2 reaches GB/T 17931-1999, and the viscosity number measured in a phenol/o-dichlorobenzene solution with a weight ratio of 1:1 in a constant temperature water bath at 25 ⁇ 0.05°C is 119ml/g;
  • the two end polymers of Poly-Ba1 and Poly-Ba2 are continuously fed into the mixer, the temperature of the mixer is 250°C, and the residence time is 1.4h.
  • the resulting polyester was then introduced into a twin-screw extruder, while 5.2 kg/h of hexamethylene diisocyanate (HDI) were metered in at a set temperature of 240°C. After a residence time of 3 minutes, the polyester was pelletized using an underwater pelletizer and then dried to obtain the final polyester product.
  • HDI hexamethylene diisocyanate
  • the esterified product Ba1 is moved into the first precondensation reactor, and at the same time, 0.096 kg/h of n-butyl titanate and 0.245 kg/h of triphenyl phosphate are added, the temperature is 200 ° C, the pressure of the reactor is 4 kPa, and the residence time is 2 -3h, the excess butanediol is drawn out, at this time the reaction product Pre-Ba1 reaches GB/T 17931-1999 regulations in a phenol/o-dichlorobenzene solution with a weight ratio of 1:1 in a constant temperature water bath at 25 ⁇ 0.05°C The viscosity measured in the medium is 42ml/g;
  • the prepolymer Pre-Ba1 is sent into the first final polymerization tank through a melt pump.
  • the temperature of the first final polymerization tank is 220° C.
  • the pressure is 120 Pa
  • the reaction time is 2-4 hours.
  • the reaction product Poly-Ba1 reaches GB/T 17931-1999, and the viscosity number measured in a phenol/o-dichlorobenzene solution with a weight ratio of 1:1 in a constant temperature water bath at 25 ⁇ 0.05°C is 129ml/g;
  • the prepolymer Pre-Ba2 is sent into the second final polymerization tank through a melt pump.
  • the temperature of the second final polymerization tank is 250° C.
  • the pressure is 20 Pa
  • the reaction time is 2-4 hours.
  • the reaction product Poly-Ba2 reaches GB/T 17931-1999, and the viscosity number measured in a phenol/o-dichlorobenzene solution with a weight ratio of 1:1 in a constant temperature water bath at 25 ⁇ 0.05°C is 111ml/g;
  • the two end polymers of Poly-Ba1 and Poly-Ba2 are continuously fed into the mixer, the temperature of the mixer is 250°C, and the residence time is 1.5h.
  • the resulting polyester was then introduced into a twin-screw extruder, while 5.2 kg/h of hexamethylene diisocyanate (HDI) were metered in at a set temperature of 240°C. After a residence time of 3 minutes, the polyester was pelletized using an underwater pelletizer and then dried to obtain the final polyester product.
  • HDI hexamethylene diisocyanate
  • the esterified product Ba1 is moved into the first precondensation reactor, and at the same time, 0.096 kg/h of n-butyl titanate and 0.245 kg/h of triphenyl phosphate are added, the temperature is 200 ° C, the pressure of the reactor is 4 kPa, and the residence time is 2 -3h, the excess butanediol is drawn out, at this time the reaction product Pre-Ba1 reaches GB/T 17931-1999 regulations in a phenol/o-dichlorobenzene solution with a weight ratio of 1:1 in a constant temperature water bath at 25 ⁇ 0.05°C The viscosity measured in the medium is 49ml/g;
  • the prepolymer Pre-Ba1 is sent into the first final polymerization tank through a melt pump.
  • the temperature of the first final polymerization tank is 220° C.
  • the pressure is 120 Pa
  • the reaction time is 2-4 hours.
  • the reaction product Poly-Ba1 reaches GB/T 17931-1999, and the viscosity number measured in a phenol/o-dichlorobenzene solution with a weight ratio of 1:1 in a constant temperature water bath at 25 ⁇ 0.05°C is 141ml/g;
  • the prepolymer Pre-Ba2 is sent into the second final polymerization tank through a melt pump.
  • the temperature of the second final polymerization tank is 250° C.
  • the pressure is 20 Pa
  • the reaction time is 2-4 hours.
  • the reaction product Poly-Ba2 reaches GB/T 17931-1999, and the viscosity number measured in a phenol/o-dichlorobenzene solution with a weight ratio of 1:1 in a constant temperature water bath at 25 ⁇ 0.05°C is 120ml/g;
  • the two end polymers of Poly-Ba1 and Poly-Ba2 are continuously fed into the mixer, the temperature of the mixer is 250°C, and the residence time is 1.5h.
  • the resulting polyester was then introduced into a twin-screw extruder, while 5.2 kg/h of hexamethylene diisocyanate (HDI) were metered in at a set temperature of 240°C. After a residence time of 3 minutes, the polyester was pelletized using an underwater pelletizer and then dried to obtain the final polyester product.
  • HDI hexamethylene diisocyanate
  • the esterified product Ba1 is moved into the first precondensation reactor, and at the same time, 0.096 kg/h of n-butyl titanate and 0.245 kg/h of triphenyl phosphate are added, the temperature is 200 ° C, the pressure of the reactor is 4 kPa, and the residence time is 2 -3h, the excess butanediol is drawn out, at this time the reaction product Pre-Ba1 reaches GB/T 17931-1999 regulations in a phenol/o-dichlorobenzene solution with a weight ratio of 1:1 in a constant temperature water bath at 25 ⁇ 0.05°C The viscosity measured in the medium is 42ml/g;
  • the prepolymer Pre-Ba1 is sent into the first final polymerization tank through a melt pump.
  • the temperature of the first final polymerization tank is 220° C.
  • the pressure is 120 Pa
  • the reaction time is 2-4 hours.
  • the reaction product Poly-Ba1 reaches GB/T 17931-1999, and the viscosity number measured in a phenol/o-dichlorobenzene solution with a weight ratio of 1:1 in a constant temperature water bath at 25 ⁇ 0.05°C is 140ml/g;
  • the prepolymer Pre-Ba2 is sent into the second final polymerization tank through a melt pump.
  • the temperature of the second final polymerization tank is 250° C.
  • the pressure is 20 Pa
  • the reaction time is 2-4 hours.
  • the reaction product Poly-Ba2 reaches GB/T 17931-1999, and the viscosity number measured in a phenol/o-dichlorobenzene solution with a weight ratio of 1:1 in a constant temperature water bath at 25 ⁇ 0.05°C is 125ml/g;
  • the two end polymers of Poly-Ba1 and Poly-Ba2 are continuously fed into the mixer, the temperature of the mixer is 250°C, and the residence time is 1.5h. Then, the resulting polyester is introduced into a twin-screw extruder, while 11.2 kg/h N, N'-bis(2,6-diisopropylphenyl) carbodiimide (Stabaxol I) is metered in, and the set temperature is 240°C. After a residence time of 3 minutes, the polyester was pelletized using an underwater pelletizer and then dried to obtain the final polyester product.
  • Embodiment 6 is a diagrammatic representation of Embodiment 6
  • the esterified product Ba1 is moved into the first precondensation reactor, and at the same time, 0.096 kg/h of n-butyl titanate and 0.245 kg/h of triphenyl phosphate are added, the temperature is 200 ° C, the pressure of the reactor is 4 kPa, and the residence time is 2 -3h, the excess butanediol is drawn out, at this time the reaction product Pre-Ba1 reaches GB/T 17931-1999 regulations in a phenol/o-dichlorobenzene solution with a weight ratio of 1:1 in a constant temperature water bath at 25 ⁇ 0.05°C The viscosity measured in the medium is 47ml/g;
  • the prepolymer Pre-Ba1 is sent into the first final polymerization tank through a melt pump.
  • the temperature of the first final polymerization tank is 220° C.
  • the pressure is 120 Pa
  • the reaction time is 2-4 hours.
  • the reaction product Poly-Ba1 reaches GB/T 17931-1999, and the viscosity number measured in a phenol/o-dichlorobenzene solution with a weight ratio of 1:1 in a constant temperature water bath at 25 ⁇ 0.05°C is 132ml/g;
  • the prepolymer Pre-Ba2 is sent into the second final polymerization tank through a melt pump.
  • the temperature of the second final polymerization tank is 250° C.
  • the pressure is 20 Pa
  • the reaction time is 2-4 hours.
  • the reaction product Poly-Ba2 reaches GB/T 17931-1999, and the viscosity number measured in a phenol/o-dichlorobenzene solution with a weight ratio of 1:1 in a constant temperature water bath at 25 ⁇ 0.05°C is 119ml/g;
  • the two end polymers of Poly-Ba1 and Poly-Ba2 are continuously fed into the mixer, the temperature of the mixer is 250°C, and the residence time is 1.5h.
  • the resulting polyester was then introduced into a twin-screw extruder while simultaneously metering in 6.11 kg/h of hexamethylene diisocyanate (HDI), with a set temperature of 240°C. After a residence time of 3 minutes, the polyester was pelletized using an underwater pelletizer and then dried to obtain the final polyester product.
  • HDI hexamethylene diisocyanate
  • Embodiment 7 is a diagrammatic representation of Embodiment 7:
  • the esterified product Ba1 is moved into the first precondensation reactor, and at the same time, 0.096 kg/h of n-butyl titanate and 0.245 kg/h of triphenyl phosphate are added, the temperature is 200 ° C, the pressure of the reactor is 4 kPa, and the residence time is 2 -3h, the excess butanediol is drawn out, at this time the reaction product Pre-Ba1 reaches GB/T 17931-1999 regulations in a phenol/o-dichlorobenzene solution with a weight ratio of 1:1 in a constant temperature water bath at 25 ⁇ 0.05°C The viscosity measured in the medium is 40ml/g;
  • the prepolymer Pre-Ba1 is sent into the first final polymerization tank through a melt pump.
  • the temperature of the first final polymerization tank is 220° C.
  • the pressure is 120 Pa
  • the reaction time is 2-4 hours.
  • the reaction product Poly-Ba1 reaches GB/T 17931-1999, and the viscosity number measured in a phenol/o-dichlorobenzene solution with a weight ratio of 1:1 in a constant temperature water bath at 25 ⁇ 0.05°C is 130ml/g;
  • the prepolymer Pre-Ba2 is sent into the second final polymerization tank through a melt pump.
  • the temperature of the second final polymerization tank is 250° C.
  • the pressure is 20 Pa
  • the reaction time is 2-4 hours.
  • the reaction product Poly-Ba2 reaches GB/T 17931-1999, and the viscosity number measured in a phenol/o-dichlorobenzene solution with a weight ratio of 1:1 in a constant temperature water bath at 25 ⁇ 0.05°C is 114ml/g;
  • the two end polymers of Poly-Ba1 and Poly-Ba2 are continuously fed into the mixer, the temperature of the mixer is 250°C, and the residence time is 1.5h.
  • the resulting polyester was then introduced into a twin-screw extruder, while 5.2 kg/h of hexamethylene diisocyanate (HDI) were metered in at a set temperature of 240°C. After a residence time of 6 minutes, the polyester was pelletized using an underwater pelletizer and then dried to obtain the final polyester product.
  • HDI hexamethylene diisocyanate
  • Embodiment 8 is a diagrammatic representation of Embodiment 8
  • the esterified product Ba1 is moved into the first precondensation reactor, and at the same time, 0.096 kg/h of n-butyl titanate and 0.245 kg/h of triphenyl phosphate are added, the temperature is 200 ° C, the pressure of the reactor is 4 kPa, and the residence time is 2 -3h, the excess butanediol is drawn out, at this time the reaction product Pre-Ba1 reaches GB/T 17931-1999 regulations in a phenol/o-dichlorobenzene solution with a weight ratio of 1:1 in a constant temperature water bath at 25 ⁇ 0.05°C The viscosity measured in the medium is 43ml/g;
  • the prepolymer Pre-Ba1 is sent into the first final polymerization tank through a melt pump.
  • the temperature of the first final polymerization tank is 220° C.
  • the pressure is 120 Pa
  • the reaction time is 2-4 hours.
  • the reaction product Poly-Ba1 reaches GB/T 17931-1999, and the viscosity number measured in a phenol/o-dichlorobenzene solution with a weight ratio of 1:1 in a constant temperature water bath at 25 ⁇ 0.05°C is 133ml/g;
  • the prepolymer Pre-Ba2 is sent into the second final polymerization tank through a melt pump.
  • the temperature of the second final polymerization tank is 250° C.
  • the pressure is 20 Pa
  • the reaction time is 2-4 hours.
  • the reaction product Poly-Ba2 reaches GB/T 17931-1999, and the viscosity number measured in a phenol/o-dichlorobenzene solution with a weight ratio of 1:1 in a constant temperature water bath at 25 ⁇ 0.05°C is 112ml/g;
  • the two end polymers of Poly-Ba1 and Poly-Ba2 are continuously fed into the mixer, the temperature of the mixer is 250°C, and the residence time is 1.5h.
  • the resulting polyester was then introduced into a twin-screw extruder, while 5.2 kg/h of hexamethylene diisocyanate (HDI) were metered in at a set temperature of 240°C. After a residence time of 12 minutes, the polyester was pelletized using an underwater pelletizer and then dried to obtain the final polyester product.
  • HDI hexamethylene diisocyanate
  • Embodiment 9 is a diagrammatic representation of Embodiment 9:
  • the esterified product Ba1 is moved into the first precondensation reactor, and at the same time, 0.096 kg/h of n-butyl titanate and 0.245 kg/h of triphenyl phosphate are added, the temperature is 200 ° C, the pressure of the reactor is 4 kPa, and the residence time is 2 -3h, the excess butanediol is drawn out, at this time the reaction product Pre-Ba1 reaches GB/T 17931-1999 regulations in a phenol/o-dichlorobenzene solution with a weight ratio of 1:1 in a constant temperature water bath at 25 ⁇ 0.05°C The viscosity measured in the medium is 47ml/g;
  • the prepolymer Pre-Ba1 is sent into the first final polymerization tank through a melt pump.
  • the temperature of the first final polymerization tank is 220° C.
  • the pressure is 120 Pa
  • the reaction time is 2-4 hours.
  • the reaction product Poly-Ba1 reaches GB/T 17931-1999, and the viscosity number measured in a phenol/o-dichlorobenzene solution with a weight ratio of 1:1 in a constant temperature water bath at 25 ⁇ 0.05°C is 136ml/g;
  • the prepolymer Pre-Ba2 is sent into the second final polymerization tank through a melt pump.
  • the temperature of the second final polymerization tank is 250° C.
  • the pressure is 20 Pa
  • the reaction time is 2-4 hours.
  • the reaction product Poly-Ba2 reaches GB/T 17931-1999, and the viscosity number measured in a phenol/o-dichlorobenzene solution with a weight ratio of 1:1 in a constant temperature water bath at 25 ⁇ 0.05°C is 120ml/g;
  • the two end polymers of Poly-Ba1 and Poly-Ba2 are continuously fed into the mixer, the temperature of the mixer is 250°C, and the residence time is 2h.
  • the polyester was then pelletized using an underwater pelletizer and then dried to obtain the final polyester product.
  • esterification product BA into the pre-condensation reaction kettle by gravity, add n-butyl titanate 0.27kg/h, triphenyl phosphate 0.685kg/h at the same time, the temperature is 250°C, the pressure of the reaction kettle is 2kPa, the residence time For 2-3h, the excess butanediol is drawn out, and the reaction product Pre-BA reaches the temperature specified in GB/T 17931-1999 at 25 ⁇ 0.05°C in a phenol/o-dichlorobenzene solution with a weight ratio of 1:1.
  • the viscosity measured in a constant temperature water bath is 39ml/g;
  • the prepolymer Pre-BA is sent into a disc reactor (final polymerization reactor) through a melt pump.
  • the temperature of the final polymerization reactor is 250°C
  • the pressure is 20Pa
  • the reaction time is 2- 4h.
  • the reaction product Poly-BA reaches GB/T 17931-1999, and the viscosity number measured in a phenol/o-dichlorobenzene solution with a weight ratio of 1:1 in a constant temperature water bath at 25 ⁇ 0.05°C is 133ml/g;
  • the obtained polyester was introduced into a twin-screw extruder, and at the same time, 5.2 kg/h of hexamethylene diisocyanate (HDI) was metered in, and the temperature was set at 240°C. After a residence time of 3 minutes, the polyester was pelletized using an underwater pelletizer and then dried to obtain the final polyester product.
  • HDI hexamethylene diisocyanate
  • Ba1 and Ba2 esterified products are continuously fed into the mixer, the temperature of the mixer is 230°C, and the residence time is 30min.
  • the mixture flowing out from the mixer is introduced into the pre-condensation reactor by gravity, and 0.27kg/h of n-butyl titanate and 0.685kg/h of triphenyl phosphate are added at the same time, the temperature is 250°C, the pressure of the reactor is 2kPa, and the residence time For 2-3h, the excess butanediol is drawn out, and the reaction product Pre-BA reaches the temperature specified in GB/T 17931-1999 at 25 ⁇ 0.05°C in a phenol/o-dichlorobenzene solution with a weight ratio of 1:1.
  • the viscosity measured in a constant temperature water bath is 37ml/g;
  • the prepolymer Pre-BA is sent into a disc reactor (final polymerization reactor) through a melt pump.
  • the temperature of the final polymerization reactor is 250°C
  • the pressure is 20Pa
  • the reaction time is 2- 4h.
  • the reaction product Poly-BA reaches GB/T 17931-1999, and the viscosity number measured in a phenol/o-dichlorobenzene solution with a weight ratio of 1:1 in a constant temperature water bath at 25 ⁇ 0.05°C is 128ml/g;
  • the obtained polyester was introduced into a twin-screw extruder, and at the same time, 5.2 kg/h of hexamethylene diisocyanate (HDI) was metered in, and the temperature was set at 240°C. After a residence time of 3 minutes, the polyester was pelletized using an underwater pelletizer and then dried to obtain the final polyester product.
  • HDI hexamethylene diisocyanate
  • the present invention controls the double bond content of the semi-aromatic polyester within the range of 0.55-4.5mmol/kg, and has a high heat retention melt index retention rate, high Hunter whiteness, and good color.
  • Comparative example 1 uses mixed esterification steps throughout, and the polymerization temperature is relatively high, so that the part derived from aliphatic polyester in the semi-aromatic polyester is prone to thermal degradation, and the obtained double bond content is relatively high, and the thermal retention melt index retention rate is very low. Low, poor color;
  • Comparative example 2 independently esterifies the aliphatic polyester and the aromatic polyester, but the process after the esterification still mixes the two, which has a certain effect on reducing the double bond content, improving the heat retention melt index retention rate and color, but due to The reaction time in the esterification stage accounts for a relatively small proportion of the entire polymerization reaction time, and the improvement effect is limited;
  • Comparative example 3 is produced by a batch process, and the obtained double bond content is higher, the heat retention melt index retention rate is lower, and the color is poor.

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CN114957628B (zh) * 2022-05-24 2025-03-11 珠海金发生物材料有限公司 一种聚酯及其制备方法和应用
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CN115926128B (zh) * 2022-12-08 2025-07-11 金发科技股份有限公司 一种脂肪族-芳香族聚酯组合物、聚酯纤维及其制备方法和应用

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11236437A (ja) * 1998-02-20 1999-08-31 Kuraray Co Ltd ポリエステル系ブロックポリマー
CN101475690A (zh) * 2009-01-08 2009-07-08 同济大学 一种生物可降解嵌段共聚酯的制备方法
CN102020772A (zh) * 2009-09-15 2011-04-20 中国科学院化学研究所 一种可生物降解脂肪族聚酯/芳香族聚酯多嵌段共聚物及其制备方法与应用
CN102516517A (zh) * 2011-12-13 2012-06-27 金发科技股份有限公司 一种制备聚酯-聚酯嵌段共聚酯的方法
CN109666147A (zh) * 2017-10-17 2019-04-23 中国石油化工股份有限公司 一种线性无规可生物降解共聚酯以及制备方法
CN112280026A (zh) * 2020-12-31 2021-01-29 江苏金发科技新材料有限公司 一种半芳香族聚酯及其制备方法和应用
CN112521592A (zh) * 2021-02-08 2021-03-19 富海(东营)新材料科技有限公司 一种生物降解聚酯及其制备方法
CN113683763A (zh) * 2021-10-26 2021-11-23 江苏金发科技新材料有限公司 一种半芳香族聚酯及其制备方法和应用

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001026643A (ja) * 1999-07-16 2001-01-30 Mitsubishi Chemicals Corp 脂肪族芳香族ポリエステルの製造方法
JP2013007058A (ja) * 2003-02-18 2013-01-10 Mitsubishi Chemicals Corp ポリブチレンテレフタレートの製造方法
ITMI20050452A1 (it) 2005-03-18 2006-09-19 Novamont Spa Poliestere biodegradabile alifatico-aromatico
ITMI20080507A1 (it) 2008-03-26 2009-09-27 Novamont Spa Poliestere biodegradabile, suo processo di preparazione e prodotti comprendenti detto poliestere.
US8614280B2 (en) * 2008-04-15 2013-12-24 Basf Se Method for the continuous production of biodegradable polyesters
IT1395925B1 (it) 2009-09-25 2012-11-02 Novamont Spa Poliestere biodegradabile.
KR101992392B1 (ko) * 2012-12-12 2019-09-30 (주)새한폴리머 생분해성 지방족/방향족 폴리에스테르 공중합체의 연속 제조방법
JP6357795B2 (ja) * 2013-02-21 2018-07-18 三菱ケミカル株式会社 ポリエステル樹脂及びその製造方法
CN103483571B (zh) * 2013-08-28 2016-02-03 中国科学院宁波材料技术与工程研究所 一种含双键全生物基聚酯及其制备方法和应用
CN104497293A (zh) * 2014-12-01 2015-04-08 金发科技股份有限公司 一种生物降解脂肪族-芳香族共聚酯及其应用
IT201700022439A1 (it) 2017-02-28 2018-08-28 Novamont Spa Composizione polimerica per film ad elevata disintegrabilita’
CN107325272A (zh) * 2017-07-11 2017-11-07 南通协鑫热熔胶有限公司 一种含有机硅大分子嵌段的半芳香型聚酯热熔胶及其制备方法
CN110591057B (zh) 2019-09-09 2021-11-02 彤程化学（中国）有限公司 一种生物可降解脂肪族-芳香族共聚酯的合成方法
CN116023636B (zh) * 2021-10-26 2025-03-25 江苏金发科技新材料有限公司 一种半芳香族聚酯及其制备方法和应用

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11236437A (ja) * 1998-02-20 1999-08-31 Kuraray Co Ltd ポリエステル系ブロックポリマー
CN101475690A (zh) * 2009-01-08 2009-07-08 同济大学 一种生物可降解嵌段共聚酯的制备方法
CN102020772A (zh) * 2009-09-15 2011-04-20 中国科学院化学研究所 一种可生物降解脂肪族聚酯/芳香族聚酯多嵌段共聚物及其制备方法与应用
CN102516517A (zh) * 2011-12-13 2012-06-27 金发科技股份有限公司 一种制备聚酯-聚酯嵌段共聚酯的方法
CN109666147A (zh) * 2017-10-17 2019-04-23 中国石油化工股份有限公司 一种线性无规可生物降解共聚酯以及制备方法
CN112280026A (zh) * 2020-12-31 2021-01-29 江苏金发科技新材料有限公司 一种半芳香族聚酯及其制备方法和应用
CN112521592A (zh) * 2021-02-08 2021-03-19 富海(东营)新材料科技有限公司 一种生物降解聚酯及其制备方法
CN113683763A (zh) * 2021-10-26 2021-11-23 江苏金发科技新材料有限公司 一种半芳香族聚酯及其制备方法和应用

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
YUAN, RENXU; XU, YI-BIN; MAI, KAN-CHENG: "Investigation of Thermal Degradation Behavior of Biodegradable PBAT", CHINA PLASTICS INDUSTRY, vol. 40, no. 12, 31 December 2012 (2012-12-31), pages 73 - 77, XP009545747, ISSN: 1005-5770 *

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