WO2023071796A1 - 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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WO2023071796A1
WO2023071796A1 PCT/CN2022/124852 CN2022124852W WO2023071796A1 WO 2023071796 A1 WO2023071796 A1 WO 2023071796A1 CN 2022124852 W CN2022124852 W CN 2022124852W WO 2023071796 A1 WO2023071796 A1 WO 2023071796A1
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Prior art keywords
acid
semi
aromatic polyester
reaction
component
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PCT/CN2022/124852
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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 JP2024526880A priority Critical patent/JP2024539401A/ja
Priority to US18/704,468 priority patent/US20240425639A1/en
Priority to KR1020247017308A priority patent/KR20240090920A/ko
Priority to EP22885675.3A priority patent/EP4421106A4/en
Publication of WO2023071796A1 publication Critical patent/WO2023071796A1/zh
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
    • C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
    • C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
    • C08G18/4219—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from aromatic dicarboxylic acids and dialcohols in combination with polycarboxylic acids and/or polyhydroxy compounds which are at least trifunctional
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    • 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
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    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
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    • C08G18/4216—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from mixtures or combinations of aromatic dicarboxylic acids and aliphatic dicarboxylic acids and dialcohols
    • C—CHEMISTRY; METALLURGY
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    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
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    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
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    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
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    • C08L2205/00—Polymer mixtures characterised by other features
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Definitions

  • the invention relates to the field of biodegradable polyesters, in particular to a semi-aromatic polyester with specific hydroxyl content and its preparation method and application.
  • thermoplastic aromatic polyesters which are widely used in industry and daily life, have excellent thermal stability and mechanical properties, are easy to process and low in price.
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • these aromatic polyesters are difficult to degrade after being used and discarded, and no obvious direct degradation of aromatic polyesters such as PET and PBT by microorganisms has been observed so far.
  • those skilled in the art have devoted themselves to the research of synthesizing aliphatic-aromatic copolyesters, that is, introducing aromatic segments into aliphatic polyesters.
  • the representative of aromatic polyester is PBAT, but its tensile strength is low and its modulus is low.
  • Polylactic acid is an aliphatic polyester obtained by biological fermentation and chemical synthesis of biological-based raw materials such as potatoes, cassava, and corn starch. It has good biocompatibility and biodegradability, excellent mechanical strength, Transparency and processability, so it is widely used in medicine, packaging film, disposable daily necessities and other fields.
  • polylactic acid is brittle and has poor toughness, so it is difficult to popularize and apply it in many fields.
  • PBAT and PLA exhibit completely different mechanical properties, so the two are often used as complementary materials for blending and modification, that is, PLA is used as a matrix to toughen and modify polylactic acid with PBAT, or PBAT is used as a matrix to strengthen and modify PBAT with PLA. .
  • the final modification effect depends on the compatibility of the two.
  • these toughening modifiers can only slightly improve the impact strength of PLA, and it is often difficult to improve the ductility of PLA at the same time.
  • the object of the present invention is to provide a semi-aromatic polyester, which can significantly improve the compatibility of semi-aromatic polyester with materials such as polylactic acid because of its specific hydroxyl content. , so as to obtain high-strength, tear-resistant film materials.
  • 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 1,4-butanediol
  • the content of the hydroxyl group connected with the aliphatic dicarboxylic acid in the semi-aromatic polyester is 17-40mmol/kg; the content of the hydroxyl group connected with the aromatic dicarboxylic acid in the semi-aromatic polyester is 17-40mmol/kg kg; and, the total hydroxyl content is 35-80mmol/kg.
  • the present invention finds through research that the amount of hydroxyl groups in the semi-aromatic polyester can affect the compatibility of the semi-aromatic polyester with materials such as polylactic acid. If the hydroxyl content is too high or too low, the compatibility of semi-aromatic polyester with materials such as polylactic acid is poor.
  • the present invention finds unexpectedly through research, by controlling the hydroxyl content in the semi-aromatic polyester, especially the content of the hydroxyl group connected with the aliphatic dicarboxylic acid in the semi-aromatic polyester is controlled to 17% in the semi-aromatic polyester. -40mmol/kg, the content of the hydroxyl group connected to the aromatic dicarboxylic acid in the semi-aromatic polyester is controlled at 17-40mmol/kg, and the total content of the hydroxyl group is controlled at 35-80mmol/kg, which can significantly improve the semi-aromatic Compatibility of polyester with polylactic acid and other materials, so as to obtain high-strength, tear-resistant film materials.
  • 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 semi-aromatic polyester also contains a third component C, and in the third component C, it is preferably a compound containing at least three functional groups, preferably three to six functional compound.
  • a compound containing at least three functional groups preferably three to six functional compound.
  • the content of the third component C is 0.01-5.0 mol%, preferably 0.02-2.0 mol%.
  • the semi-aromatic polyester may also include a fourth component D, which is a chain extender.
  • the chain extender is isocyanate, isocyanurate, peroxide, epoxy, oxazoline, oxazine, lactam, carbodiimide or polycarbodiimide containing two or more functional groups One or more mixtures of amines.
  • 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 epoxy groups, and the epoxy groups are preferably methacrylic acid shrinkage Glycerides.
  • 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 copolymers is preferably 150 to 3000 g/equivalent, more preferably 200 to 500 g/equivalent.
  • the weight average molecular weight Mw of the copolymer is preferably 2,000 to 25,000, more preferably 3,000 to 8,000.
  • the number average molecular weight Mn of the copolymer 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 or 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 content of the fourth component D is 0.01-5 mol% based on the total molar weight of the first component A.
  • 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 5-50 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 pressures described in the process of the present invention are all absolute pressures (absolute pressures).
  • 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 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-Ba1 polyester, 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 Poly-Ba1 and Poly-Ba1 polyester after 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 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 invention provides a semi-aromatic polyester, by controlling the hydroxyl content in the semi-aromatic polyester, especially the content of the hydroxyl group connected with the aliphatic dicarboxylic acid in the semi-aromatic polyester in the semi-aromatic polyester Controlled to 17-40mmol/kg, the content of the hydroxyl group connected to the aromatic dicarboxylic acid in the semi-aromatic polyester is controlled to 17-40mmol/kg, and the total content of the hydroxyl group is controlled to 35-80mmol/kg, which can significantly improve
  • the compatibility of semi-aromatic polyester with materials such as polylactic acid can obtain high-strength, tear-resistant film materials.
  • Fig. 1 is the 1H NMR that the PBAT obtained by the reaction of terephthalic acid, adipic acid and 1,4-butanediol adopts Bruker company AV 500 nuclear magnetic resonance spectrometer to measure;
  • Figure 2 is the peak corresponding to CH2 in the hydroxyl group connected with adipic acid and the hydroxyl group connected with terephthalic acid in PBAT.
  • Adipic acid molar content in PBAT IA/(IT+IA) ⁇ 100%
  • the content XA (unit mmol/kg) of the hydroxyl group connected to the aliphatic dicarboxylic acid (adipic acid) in the semi-aromatic polyester PBAT is:
  • the content XT (unit mmol/kg) of the hydroxyl group connected to the aromatic dicarboxylic acid (terephthalic acid) in the semi-aromatic polyester PBAT is:
  • the total hydroxyl content X is:
  • I1 is the integrated area of the two hydrogen atom peaks on the adjacent CH of the hydroxyl group connected to terephthalic acid;
  • I2 is the integral area of the two hydrogen atom peaks on the adjacent CH of the hydroxyl group connected to adipic acid;
  • IT is the integral area of 4 hydrogen atoms on the benzene ring of the terephthalic acid repeating unit
  • IA 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;
  • MPBT is the PBT repeating unit molecular weight of 220g/mol
  • MPBA is the PBA repeating unit molecular weight of 200g/mol
  • the average molecular weight M of the semi-aromatic polyester PBAT repeating unit 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, with a solvent volume of 100 ml.
  • DMSO dimethyl methoxysulfoxide
  • 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 obtained polyester composition is blown on a double air ring blown film machine, the film thickness is 20 ⁇ m, the air volume of the inner air ring and the outer air ring is controlled between 1:1 and 1:3, and the inflation ratio is 2.5 ⁇ 4.0.
  • the esterified product Ba1 was moved into the first precondensation reactor, and at the same time, 0.077kg/h of n-butyl titanate and 0.198kg/h of triphenyl phosphate were added, the temperature was 200°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 45ml/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 3-4 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 146ml/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 3-4 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 135ml/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 4.2 kg/h of hexamethylene diisocyanate (HDI) were metered in at a set temperature of 250°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, 0.077kg/h of n-butyl titanate and 0.198kg/h of triphenyl phosphate were added, the temperature was 200°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 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 3-4 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 151ml/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 20Pa
  • the reaction time is 3-4h.
  • 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 132ml/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 4.2 kg/h of hexamethylene diisocyanate (HDI) were metered in at a set temperature of 250°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, 0.077kg/h of n-butyl titanate and 0.198kg/h of triphenyl phosphate were added, the temperature was 200°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 33ml/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 3-4 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 134ml/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 3-4 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 128ml/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 4.2 kg/h of hexamethylene diisocyanate (HDI) were metered in at a set temperature of 250°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, 0.077kg/h of n-butyl titanate and 0.198kg/h of triphenyl phosphate were added, the temperature was 200°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 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 3-4 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 142ml/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 3-4 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 133ml/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 5.03 kg/h of hexamethylene diisocyanate (HDI) with a set temperature of 250°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 reaction kettle, and at the same time, 0.077kg/h of n-butyl titanate and 0.198kg/h of triphenyl phosphate were added, the temperature was 200°C, the pressure of the reaction kettle was 8kPa, 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 31ml/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 300 Pa
  • the reaction time is 3-4 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 116ml/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 200 Pa
  • the reaction time is 3-4 hours.
  • the reaction product Poly-Ba2 reaches GB/T 17931-1999, and the viscosity 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 105ml/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 4.2 kg/h of hexamethylene diisocyanate (HDI) were metered in at a set temperature of 250°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 6 is a diagrammatic representation of Embodiment 6
  • the esterified product Ba1 was moved into the first precondensation reactor, and at the same time, 0.077kg/h of n-butyl titanate and 0.198kg/h of triphenyl phosphate were added, the temperature was 200°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 28ml/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 3-4 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 96ml/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 3-4 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 83ml/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 4.2 kg/h of hexamethylene diisocyanate (HDI) were metered in at a set temperature of 250°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 was moved into the first precondensation reactor, and at the same time, 0.077kg/h of n-butyl titanate and 0.198kg/h of triphenyl phosphate were added, the temperature was 200°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 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 3-4 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 3-4 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 129ml/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. Then, the obtained polyester was introduced into a twin-screw extruder, and the polyester was pelletized with an underwater pelletizer, and then dried to obtain a final polyester product.
  • Embodiment 8 is a diagrammatic representation of Embodiment 8
  • the esterified product Ba1 was moved into the first precondensation reactor, and at the same time, 0.077kg/h of n-butyl titanate and 0.198kg/h of triphenyl phosphate were added, the temperature was 200°C, the pressure of the reactor was 2kPa, 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 51ml/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 80 Pa
  • the reaction time is 3-4 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 163ml/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 10 Pa
  • the reaction time is 3-4 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 147ml/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 with simultaneous metering of 4.2 kg/h of hexamethylene diisocyanate (HDI) and a set temperature of 250°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 9 is a diagrammatic representation of Embodiment 9:
  • the esterified product Ba1 was moved into the first precondensation reactor, and at the same time, 0.077kg/h of n-butyl titanate and 0.198kg/h of triphenyl phosphate were added, the temperature was 200°C, the pressure of the reactor was 4kPa, and the residence time was 2 -2.5h, the excess butanediol was drawn out, and the reaction product Pre-Ba1 reached the constant temperature of 25 ⁇ 0.05°C in the phenol/o-dichlorobenzene solution with a weight ratio of 1:1 specified in GB/T 17931-1999 The viscosity measured in the water bath is 29ml/g;
  • the esterified product Ba2 is moved into the second precondensation reactor, and at the same time, 0.142 kg/h of n-butyl titanate and 0.356 kg/h of triphenyl phosphate are added, the temperature is 250 ° C, the pressure of the reactor is 2 kPa, and the residence time is 2-2.5 h, the excess butanediol is drawn out, and the reaction product Pre-Ba2 reaches 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 measured viscosity number is 18ml/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 2-3 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 106ml/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 2-3 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 95ml/g;
  • Poly-Ba1 and Poly-Ba2 two end polymers are continuously fed into the mixer, the temperature of the mixer is 250°C, and the residence time is 1h.
  • the resulting polyester was then introduced into a twin-screw extruder while 4.2 kg/h of hexamethylene diisocyanate (HDI) were metered in at a set temperature of 250°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
  • esterification product BA into the pre-condensation reaction kettle by gravity, add 0.22kg/h of n-butyl titanate, 0.55kg/h of triphenyl phosphate 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 35ml/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 3- 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 is introduced into a twin-screw extruder, and at the same time, 4.2 kg/h of hexamethylene diisocyanate (HDI) is metered in, and the temperature is set at 250°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.
  • Comparative example 2 hexamethylene diisocyanate
  • the esterified product Ba1 was moved into the first precondensation reactor, and at the same time, 0.077kg/h of n-butyl titanate and 0.198kg/h of triphenyl phosphate were added, the temperature was 200°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 15ml/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 3-4 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 83ml/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 3-4 hours.
  • the reaction product Poly-Ba2 reaches the viscosity number 62ml/g specified in 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 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 4.2 kg/h of hexamethylene diisocyanate (HDI) were metered in at a set temperature of 250°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 reaction kettle, and 0.077kg/h of n-butyl titanate and 0.198kg/h of triphenyl phosphate are added at the same time, the temperature is 200°C, the pressure of the reaction kettle is 4kPa, and the residence time is 1 -2h, 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 25ml/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 30-60 minutes.
  • 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 95ml/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 30-60 minutes.
  • 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 76ml/g;
  • Poly-Ba1 and Poly-Ba2 two end polymers are continuously fed into the mixer, the temperature of the mixer is 250°C, and the residence time is 30-60min.
  • the resulting polyester was then introduced into a twin-screw extruder while 4.2 kg/h of hexamethylene diisocyanate (HDI) were metered in at a set temperature of 250°C. After a residence time of 2 minutes, the polyester was pelletized using an underwater pelletizer and then dried to obtain the final polyester product.
  • HDI hexamethylene diisocyanate
  • Comparative Example 1 uses a mixed esterification step throughout the process, and the polymerization temperature is relatively high, which makes the part of the semi-aromatic polyester derived from the aliphatic polyester prone to thermal degradation, resulting in more side reactions and the generation of carboxyl groups and other The non-hydroxyl carboxyl terminal (such as double bond, etc.), the hydroxyl content of the semi-aromatic polyester is low;
  • the alkyd ratio is only 1.0, resulting in very low viscosity number of prepolymerization and polycondensation products, difficult chain extension, and the obtained semi-aromatic polyester has very low hydroxyl groups, very high carboxyl groups, and low viscosity number;
  • the reaction time in the polymerization process is shorter, so that the semi-aromatic polyester has a higher hydroxyl content and a lower viscosity number. Due to the shorter reaction time, the thermal degradation is less and the carboxyl content is lower.
  • Embodiment 10-18, comparative example 4-6 Compare example 4-6:
  • Semi-aromatic polyester 67; PLA: 10;
  • Epoxy copolymer 0.5;
  • the above-mentioned materials are mixed and put into a twin-screw extruder, extruded and granulated at 170-210° C. to obtain a semi-aromatic polyester composition.
  • PLA was purchased from Natureworks, USA, brand 4060D;
  • Calcium carbonate was purchased from Jiangsu Yifeng Powder Material Co., Ltd., brand YF-2350;
  • Epoxy copolymer is purchased from BASF company, the grade ADR 4370;
  • Erucamide was purchased from Jiangxi Weike Oleochemical Co., Ltd., brand WK1890.
  • Examples 10-18 use PBAT resins with suitable hydroxyl groups, the tensile strength of the obtained semi-aromatic polyester composition is above 300MPa, and the tear strength is above 1000mN, which can meet the requirements of use; Comparative Example 4
  • the hydroxyl content of the PBAT resin used in and 5 is relatively low, resulting in poor compatibility of PBAT with PLA, and the tensile strength and tear strength of the semi-aromatic polyester composition are seriously reduced; the hydroxyl content of the PBAT resin used in Comparative Example 6 is too high. High, the tensile strength and tear strength of the resulting semi-aromatic polyester composition are also very low.

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
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