CN116355187A - Polyester material and preparation method thereof - Google Patents
Polyester material and preparation method thereof Download PDFInfo
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- CN116355187A CN116355187A CN202310347415.5A CN202310347415A CN116355187A CN 116355187 A CN116355187 A CN 116355187A CN 202310347415 A CN202310347415 A CN 202310347415A CN 116355187 A CN116355187 A CN 116355187A
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- polyester material
- aromatic dibasic
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- 229920000728 polyester Polymers 0.000 title claims abstract description 76
- 239000000463 material Substances 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 125000003118 aryl group Chemical group 0.000 claims abstract description 38
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 claims abstract description 34
- PMMYEEVYMWASQN-IMJSIDKUSA-N cis-4-Hydroxy-L-proline Chemical compound O[C@@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-IMJSIDKUSA-N 0.000 claims abstract description 22
- QYMFNZIUDRQRSA-UHFFFAOYSA-N dimethyl butanedioate;dimethyl hexanedioate;dimethyl pentanedioate Chemical compound COC(=O)CCC(=O)OC.COC(=O)CCCC(=O)OC.COC(=O)CCCCC(=O)OC QYMFNZIUDRQRSA-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002253 acid Substances 0.000 claims abstract description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 16
- -1 alkylene glycols Chemical class 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 59
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 claims description 48
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 34
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 16
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 12
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 10
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 10
- 238000006068 polycondensation reaction Methods 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 9
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 9
- 238000005809 transesterification reaction Methods 0.000 claims description 9
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 8
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 8
- 239000003963 antioxidant agent Substances 0.000 claims description 7
- 230000003078 antioxidant effect Effects 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 claims description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 4
- 229940043375 1,5-pentanediol Drugs 0.000 claims description 3
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 claims description 3
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 3
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- CMPQUABWPXYYSH-UHFFFAOYSA-N phenyl phosphate Chemical compound OP(O)(=O)OC1=CC=CC=C1 CMPQUABWPXYYSH-UHFFFAOYSA-N 0.000 claims description 2
- 150000008301 phosphite esters Chemical class 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 7
- 229910019142 PO4 Inorganic materials 0.000 claims 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims 1
- 239000010452 phosphate Substances 0.000 claims 1
- 150000003606 tin compounds Chemical class 0.000 claims 1
- 230000009477 glass transition Effects 0.000 abstract description 14
- 230000000379 polymerizing effect Effects 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 36
- 150000002009 diols Chemical class 0.000 description 32
- 238000010438 heat treatment Methods 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 14
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 14
- 238000007599 discharging Methods 0.000 description 12
- 239000012299 nitrogen atmosphere Substances 0.000 description 12
- 238000010992 reflux Methods 0.000 description 12
- 239000000178 monomer Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 8
- 238000002834 transmittance Methods 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- AXPZIVKEZRHGAS-UHFFFAOYSA-N 3-benzyl-5-[(2-nitrophenoxy)methyl]oxolan-2-one Chemical compound [O-][N+](=O)C1=CC=CC=C1OCC1OC(=O)C(CC=2C=CC=CC=2)C1 AXPZIVKEZRHGAS-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 3
- 238000004383 yellowing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- WSXIMVDZMNWNRF-UHFFFAOYSA-N antimony;ethane-1,2-diol Chemical compound [Sb].OCCO WSXIMVDZMNWNRF-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 2
- 239000012780 transparent material Substances 0.000 description 2
- FRBVRHSIYZBJMH-UHFFFAOYSA-N 4,5-dimethyl-3,6-dioxabicyclo[6.2.2]dodeca-1(10),8,11-triene-2,7-dione Chemical compound O=C1OC(C)C(C)OC(=O)C2=CC=C1C=C2 FRBVRHSIYZBJMH-UHFFFAOYSA-N 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- 229920001634 Copolyester Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 229920013724 bio-based polymer Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000011846 petroleum-based material Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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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
- C08G63/02—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
- C08G63/199—Acids or hydroxy compounds containing cycloaliphatic 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention provides a polyester material and a preparation method thereof, wherein the polyester material is prepared by polymerizing aromatic dibasic acid or aromatic dibasic ester and aliphatic dihydric alcohol, and the aliphatic dihydric alcohol is 1, 4-cyclohexanediol, 2, 3-butanediol and C 2 ～C 6 Mixtures of linear alkylene glycols. The polyester material provided by the invention is a polyester material with high transparency, high glass transition temperature, high molecular weight and amorphous.
Description
Technical Field
The invention relates to the technical field of high polymer material synthesis, in particular to a polyester material and a preparation method thereof.
Background
In recent years, as the crisis of fossil energy becomes more serious, the world has paid more attention to the development and utilization of biomass monomers, and accordingly, the variety of bio-based materials is also being developed at a high speed, and the application of various bio-based materials is also becoming more and more widespread, and the use of the bio-based materials is gradually replacing petroleum-based materials.
The bio-based material is a green environment-friendly material, and part of raw materials are renewable biomass raw materials, so that the use of non-renewable fossil energy sources is effectively reduced, the environmental pressure is greatly relieved, the current sustainable development trend is met, and the environment protection is facilitated.
Nowadays, bio-based polymers are more and more classified, and bio-based polyester materials are one of them. Polyester materials are widely applied to various fields such as films, fibers, plates and the like due to good mechanical properties, molding processability, easy degradation characteristics and the like, and are one of the most important and largest-amount synthetic materials in the world. With the continuous development of polyester materials, the types of polyester are also expanding continuously so as to adapt to various application environments. Among the numerous polyester products, the products having both high glass transition temperature and high light transmittance characteristics are rare, and are one of the short plates of the polyester family.
The 2, 3-butanediol is an isomer of 1, 4-butanediol, is diol with two branched chains having asymmetric methyl groups, and the asymmetric methyl groups can inhibit the rotation of polyester molecular chains, destroy the regular structure of the molecular chains, have strong inhibition capability on the movement of molecular chain segments, and are beneficial to improving the glass transition temperature and inhibiting crystallization. For example, chinese patent No. 102093543A discloses a preparation method of poly (2, 3-butylene terephthalate) and its copolyester, which is prepared by using dicarboxylic acid monomer or dimethyl ester monomer, 2, 3-butylene glycol and other reaction monomers. The reaction is divided into three steps: firstly, an aromatic diacid or an aromatic dibasic ester and linear diol are subjected to esterification or transesterification to prepare a prepolymer 1, then the aromatic diacid or the aromatic dibasic ester is subjected to reaction with 2, 3-butanediol to prepare a prepolymer 2, and finally the two prepolymers are subjected to transesterification to prepare the product. The method adds linear diol and adopts a prepolymer reaction mode to relieve the problem of difficult polymerization of 2, 3-butanediol to a certain extent. However, this polymerization method is complicated in steps, and first, it is necessary to synthesize two prepolymers separately, and the continuity is poor, and the molecular weight and the glass transition temperature cannot be balanced only by the linear diol, and this is considered to be the case.
The invention of China is patent CN103159907A discloses a high molecular weight polyester plastic based on 2, 3-butanediol and a preparation method thereof, the patent utilizes aromatic dibasic acid or aromatic dibasic ester and 2, 3-butanediol to prepare 2, 3-butanediol-based polyester plastic by assisting one or more of aliphatic dibasic acid, aliphatic dibasic alcohol and alicyclic dibasic alcohol, the polyester weight average molecular weight prepared by esterification and transesterification is extremely low, only can reach below 5000, the product with certain molecular weight can be obtained only by taking isocyanate as chain extender to continue reaction in a double screw extruder, the steps are also complicated, the temperature of the transesterification stage is as high as 240-280 ℃, and the phenomenon of yellowing of the product is inevitably accompanied by severe side reaction when the polyester reaction is subjected to long-time high temperature, so that the aesthetic degree and the light transmittance of the product are affected.
In summary, 2, 3-butanediol is an excellent bio-based monomer for preparing a polyester material with high glass transition temperature and high transparency, helps to relieve the problem of energy exhaustion in the prior art, and helps to make up for the deficiency of the polyester material in the field of high Tg transparent materials, but as two hydroxyl groups of the 2, 3-butanediol are secondary hydroxyl groups, the reactivity is lower, and meanwhile, the asymmetric methyl groups increase steric hindrance, so that the polymerization is difficult, the polyester with high molecular weight is difficult to obtain, and the development of the polyester is limited.
Disclosure of Invention
In order to solve the problems, the invention provides a polyester material and a preparation method thereof. The polyester material provided by the invention is an amorphous polyester material with high transparency, high glass transition temperature and high molecular weight, and the variety of polyester products is further enriched and optimized.
First, it is an object of the present invention to provide a polyester material.
Specifically, the polyester material is obtained by polymerizing aromatic dibasic acid or aromatic dibasic ester and aliphatic dihydric alcohol, and has a structural general formula:
wherein,,
R 1 one or a combination of aromatic rings, preferably
One or a combination of the above; and/or the number of the groups of groups,
R 2 is C 2 ～C 6 One or a combination of linear, straight-chain alkane diols, preferably C 4 ～C 6 One or a combination of linear straight chain alkane diols;
x is 0.30 to 0.80 mole fraction, preferably 0.35 to 0.65 mole fraction; y is 0.08 to 0.40 mole fraction, preferably 0.15 to 0.30 mole fraction; z is 0 to 0.40 mole fraction, preferably 0.10 to 0.35 mole fraction.
It is a further object of the present invention to provide a process for the preparation of a polyester material according to one of the above objects.
The method comprises the following steps:
fully mixing aromatic dibasic acid or aromatic dibasic ester, aliphatic dibasic alcohol, catalyst and antioxidant, performing transesterification reaction to obtain prepolymer, and performing polycondensation reaction to obtain the polyester material.
Specifically, the preparation method comprises the following steps:
s1, transesterification reaction
The aromatic dibasic acid or the aromatic dibasic ester, the aliphatic dibasic alcohol, the catalyst and the antioxidant are added into a reaction kettle to be fully mixed, the reaction system is slowly heated to 180-220 ℃ in 2-4 h, preferably 200-220 ℃ under the condition of protective gas, the temperature is kept for 2-6 h, and the slow heating process can also effectively prevent a large amount of glycol monomers from being evaporated and discharged under the high temperature condition.
It is worth mentioning that this device adds the wei fractionation column on traditional condensing equipment basis, and its effect is that the temperature of control wei fractionation column makes diol monomer material can flow back to the reation kettle and continue to take part in the reaction, and the micromolecule that the reaction produced gets rid of outside the reation kettle to make the reaction temperature can promote to monomer boiling point more, and effectively reduce monomer loss.
Further, the molar ratio of the aromatic dibasic acid or aromatic dibasic ester to the aliphatic diol is 1:1.2 to 1:2, preferably 1:1.4 to 1:1.8.
Further, the dosage of the catalyst is 0.05 to 1.0 percent of the total mass of the aromatic dibasic acid or the aromatic dibasic ester and the aliphatic dihydric alcohol; preferably 0.2 to 0.6%.
Further, the dosage of the antioxidant is 0.01 to 0.2 percent of the total mass of the aromatic dibasic acid or the aromatic dibasic ester and the aliphatic dibasic alcohol; more preferably 0.01 to 0.1%.
Preferably, in a preferred embodiment of the present invention, the aromatic diacid or aromatic diester is one or a combination of terephthalic acid, isophthalic acid, phthalic acid, dimethyl terephthalate.
Preferably, in a preferred embodiment of the present invention, the aliphatic diol is 1, 4-cyclohexanediol, 2, 3-butanediol, C 2 ～C 6 And a mixture of linear alkylene glycols, wherein in the aliphatic diol, 1, 4-cyclohexanediol accounts for 8-40% of the total mole ratio of the aliphatic diol, 2, 3-butanediol accounts for 30-80% of the total mole ratio of the aliphatic diol, and the linear alkylene glycol accounts for 0-40% of the total mole ratio of the aliphatic diol.
Preferably, in a preferred embodiment of the invention, C 2 ～C 6 The linear straight chain alkylene glycol is one or a combination of ethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 5-pentanediol and 1, 6-hexanediol.
Preferably, in a preferred embodiment of the present invention, the catalyst is one or a combination of selenium dioxide, antimony trioxide, ethylene glycol antimony, p-toluenesulfonic acid, acetate, alkyl aluminum with 1-12 carbon atoms, organotin compounds and titanate; stannous octoate is preferred.
Preferably, in a preferred embodiment of the present invention, the antioxidant is one or a combination of phosphoric acid, phosphorous acid, phosphate esters, phosphite esters, phenyl phosphate esters.
S2, polycondensation reaction
Firstly, raising the temperature of a reaction system to 200-240 ℃, preferably 210-230 ℃, and pre-condensing for 1-4 hours under 3-10 kPa; then the reaction system is vacuumized to below 500Pa, and finally polycondensation is carried out for 2-12 h, thus completing the reaction. The polycondensation reaction temperature can ensure the equivalent reaction speed of the reaction system and prevent a large amount of thermal degradation reaction of the system.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention prepares the polyester material by using the bio-based 2, 3-butanediol and the bio-based linear diol as raw materials, responds to the national double-carbon strategy, and relieves the problem of exhaustion of petrochemical energy.
2. The invention optimizes the reaction process, adds the Welch fractionating column and improves the reaction temperature, effectively improves the reaction efficiency, inhibits the yellowing phenomenon, and obviously improves the molecular weight and the aesthetic degree of the material.
3. According to the invention, 1, 4-cyclohexanediol and linear diol are simultaneously introduced into the polyester material, and the polyester material is successfully prepared with 2, 3-butanediol, so that the problem of difficult polymerization of 2, 3-butanediol is solved, the relationship between the molecular weight and the glass transition temperature is balanced, the polyester material with higher molecular weight and high Tg is obtained, and the types of the polyester material are enriched and optimized.
4. The invention prepares the polyester material by replacing part of 2, 3-butanediol with 1, 4-cyclohexanediol, utilizes the reactivity of the 1, 4-cyclohexanediol higher than that of the 2, 3-butanediol, and further improves the glass transition temperature and the appearance.
5. The polyester material prepared from the aromatic dibasic acid or dibasic ester, the 2, 3-butanediol, the 1, 4-cyclohexanediol and the linear diol has high glass transition temperature and high upper limit of use temperature, and is sufficient for meeting the high-temperature use requirements in most of daily life, and has wide application prospect.
6. The polyester material obtained by the invention is an amorphous material, has good light transmittance, low haze, no obvious yellowing phenomenon and good aesthetic degree, and can be applied to transparent packaging and other fields with higher requirements on transparency and use temperature.
Drawings
FIG. 1 is a nuclear magnetic spectrum of a polyester material prepared in the preferred embodiment 1 of the present invention;
Detailed Description
The present invention is described in detail below with reference to the specific drawings and examples, and it is necessary to point out that the following examples are given for further illustration of the present invention only and are not to be construed as limiting the scope of the present invention, since numerous insubstantial modifications and adaptations of the invention to those skilled in the art will still fall within the scope of the present invention.
The raw materials, reagents and the like used in the following examples were all from commercial products.
Example 1
Dimethyl terephthalate, 2, 3-butanediol, 1, 4-cyclohexanediol and ethylene glycol are added into a reaction kettle, wherein the molar ratio of the dimethyl terephthalate to the diols is 1:1.2, and the molar ratio of the three diols is 0.35:0.3:0.35. Stannous octoate (0.3% of total mass) and triphenyl phosphite (0.03% of total mass) were added to the reaction kettle with reflux condenser and thoroughly mixed under nitrogen atmosphere.
Slowly heating the system to 200 ℃ within 2h, keeping normal pressure, reacting for 4h at 200 ℃, and discharging methanol; and then heating the system to 220 ℃, reducing the air pressure to 5kPa, continuing to pre-polymerize for 2 hours, and finally continuously vacuumizing the system, and continuing to polycondense until the reaction is finished, wherein the structure of the obtained polyester material is as follows, and x=0.35, y=0.30 and z=0.35.
FIG. 1 is a nuclear magnetic resonance spectrum of a polyester material prepared in this example, showing that 5.39ppm (d, d') corresponds to-O-CH (CH) in 2,3-BDO of different chiralities in the molecular chain 3 ) -absorbance peak, -CH of different chiral 2,3-BDO building blocks in the corresponding molecular chain and at the molecular chain end at 1.44ppm (c, i, i') 3 Characteristic absorption peaks, HO-CH (CH) in 2,3-BDO at the corresponding chain ends at 3.92ppm and 4.03ppm (h, h') 3 ) Absorption peaks at 4.52ppm and 4.57ppm (g, g') for HO-CH (CH) in 2,3-BDO at the corresponding chain ends 3 )-CH(CH 3 ) Characteristics ofThe absorption peak was 8.05ppm (a) corresponding to the characteristic absorption peak on the benzene ring (CH), and 4.69ppm (b) corresponding to-O-CH in EG 2 -CH 2 Characteristic absorption peak of-O-at 5.18ppm (e) corresponding to the absorption peak of-O-CH-in the 1,4-CHD monomer, 2.17ppm to 1.80ppm of the corresponding six-membered ring-CH at (f) 2 -an absorption peak.
Example 2
Dimethyl terephthalate, 2, 3-butanediol, 1, 4-cyclohexanediol and ethylene glycol are added into a reaction kettle, wherein the molar ratio of the dimethyl terephthalate to the diols is 1:1.5, and the molar ratio of the three diols is 0.65:0.08:0.27. Stannous octoate (0.05% of total mass) and phosphorous acid (0.1% of total mass) were added to the reaction kettle with reflux condenser and thoroughly mixed under nitrogen atmosphere.
Slowly heating the system to 180 ℃ within 2h, keeping normal pressure, reacting for 3h at 180 ℃, and discharging methanol; and then heating the system to 200 ℃, reducing the air pressure to 5kPa, continuing to pre-polymerize for 2 hours, and finally continuously vacuumizing the system, and continuing to polycondense until the reaction is finished, wherein the structure of the obtained polyester material is as follows, and x=0.65, y=0.08 and z=0.27.
Example 3
Terephthalic acid, 2, 3-butanediol, 1, 4-cyclohexanediol and 1, 4-butanediol are added into a reaction kettle, wherein the molar ratio of dimethyl terephthalate to diol is 1:1.5, and the molar ratio of the three diols is 0.5:0.2:0.3. Tetrabutyl titanate (1.0% of the total mass) and triethyl phosphate (0.2% of the total mass) were added to a reaction kettle with a reflux condenser tube and thoroughly mixed under nitrogen atmosphere.
Slowly heating the system to 200 ℃ within 2h, keeping normal pressure, reacting for 4h at 200 ℃, and discharging methanol; and then heating the system to 220 ℃, reducing the air pressure to 5kPa, continuing to pre-polymerize for 3 hours, and finally continuously vacuumizing the system, and continuing to polycondense until the reaction is finished, wherein the structure of the obtained polyester material is as follows, and x=0.5, y=0.2 and z=0.3.
Example 4
Phthalic acid, dimethyl terephthalate, 2, 3-butanediol, 1, 4-cyclohexanediol, 1, 6-hexanediol are added to the reactor, wherein the molar ratio of phthalic acid, dimethyl terephthalate to diol is 1:1.5 (wherein the molar ratio of phthalic acid to dimethyl terephthalate is 1:2), and the molar ratio of the three diols is 0.65:0.3:0.05. Antimony trioxide (1.0% of the total mass) and trimethyl phosphite (0.1% of the total mass) were added to a reaction kettle with a reflux condenser and thoroughly mixed under nitrogen atmosphere.
Slowly heating the system to 220 ℃ within 2h, keeping normal pressure, reacting for 3h at 220 ℃, and discharging methanol; then heating the system to 240 ℃, reducing the air pressure to 5kPa, continuing to pre-polymerize for 4 hours, finally continuously vacuumizing the system, and continuing to polycondense until the reaction is finished, wherein the obtained polyester material has the structure as follows, x=0.65, y=0.3, z=0.05, and R is
Example 5
Isophthalic acid, 2, 3-butanediol, 1, 4-cyclohexanediol and 1, 5-pentanediol are added into a reaction kettle, wherein the molar ratio of the isophthalic acid to the diol is 1:1.7, and the molar ratio of the three diols is 0.55:0.3:0.15. Ethylene glycol antimony (0.6% of the total mass) and triphenyl phosphite (0.2% of the total mass) were added to a reaction vessel with a reflux condenser and thoroughly mixed under nitrogen atmosphere.
Slowly heating the system to 220 ℃ within 2h, keeping normal pressure, reacting for 4h at 220 ℃, and discharging methanol; and then heating the system to 220 ℃, reducing the air pressure to 5kPa, continuing to pre-polymerize for 4 hours, and finally continuously vacuumizing the system, and continuing to polycondense until the reaction is finished, wherein the structure of the obtained polyester material is as follows, and x=0.55, y=0.3 and z=0.15.
Example 6
Terephthalic acid, dimethyl terephthalate, 2, 3-butanediol, 1, 4-cyclohexanediol and 1, 4-butanediol are added into a reaction kettle, wherein the molar ratio of the terephthalic acid to the dimethyl terephthalate to the diols is 1:1.5, and the molar ratio of the terephthalic acid to the dimethyl terephthalate is 1:1, and the molar ratio of the three diols is 0.35:0.3:0.35. Stannous octoate (0.3% of total mass) and triphenyl phosphite (0.1% of total mass) were added to the reaction kettle with reflux condenser and thoroughly mixed under nitrogen atmosphere.
Slowly heating the system to 200 ℃ within 2h, keeping normal pressure, reacting for 3h at 200 ℃, and discharging methanol; and then heating the system to 220 ℃, reducing the air pressure to 5kPa, continuing to pre-polymerize for 2 hours, and finally continuously vacuumizing the system, and continuing to polycondense until the reaction is finished, wherein the structure of the obtained polyester material is as follows, and x=0.35, y=0.3 and z=0.35.
Example 7
Terephthalic acid, 2, 3-butanediol, 1, 4-cyclohexanediol and 1, 4-butanediol are added into a reaction kettle, wherein the mol ratio of terephthalic acid to diol is 1:1.7, and the mol ratio of the three diols is 0.42:0.28:0.3. Tetraethyl titanate (0.5% of the total mass) and trimethyl phosphite (0.1% of the total mass) were added to a reaction vessel with a reflux condenser and thoroughly mixed under nitrogen atmosphere.
Slowly heating the system to 210 ℃ within 2 hours, keeping normal pressure, reacting for 3 hours at 210 ℃, and discharging methanol; and then heating the system to 220 ℃, reducing the air pressure to 5kPa, continuing to pre-polymerize for 2 hours, and finally continuously vacuumizing the system, and continuing to perform polycondensation until the reaction is finished, wherein the obtained polyester material has the structure as follows, and x=0.42, y=0.28 and z=0.3.
Example 8
Dimethyl terephthalate, 2, 3-butanediol, 1, 4-cyclohexanediol and ethylene glycol are added into a reaction kettle, wherein the molar ratio of the dimethyl terephthalate to the diols is 1:2, and the molar ratio of the three diols is 0.42:0.28:0.3. Selenium dioxide (0.05% of the total mass) and trimethyl phosphite (0.1% of the total mass) were added to a reaction kettle with a reflux condenser and thoroughly mixed under nitrogen atmosphere.
Slowly heating the system to 200 ℃ within 2h, keeping normal pressure, reacting for 2h at 200 ℃, and discharging methanol; and then heating the system to 220 ℃, reducing the air pressure to 5kPa, continuing to pre-polymerize for 2 hours, and finally continuously vacuumizing the system, and continuing to perform polycondensation until the reaction is finished, wherein the obtained polyester material has the structure as follows, and x=0.42, y=0.28 and z=0.3.
Example 9
Dimethyl terephthalate, 2, 3-butanediol and 1, 4-cyclohexanediol are added into a reaction kettle, wherein the molar ratio of the dimethyl terephthalate to the diols is 1:1.5, and the molar ratio of the two diols is 0.7:0.3. Stannous octoate (0.3% of total mass) and triphenyl phosphite (0.03% of total mass) were added to the reaction kettle with reflux condenser and thoroughly mixed under nitrogen atmosphere.
Slowly heating the system to 200 ℃ within 2h, keeping normal pressure, reacting for 3h at 200 ℃, and discharging methanol; and then heating the system to 220 ℃, reducing the air pressure to 5kPa, continuing to pre-polymerize for 4 hours, and finally continuously vacuumizing the system, and continuing to perform polycondensation until the reaction is finished, wherein the structure of the obtained polyester material is as follows, and x=0.7 and y=0.3.
Comparative example 1
And adding dimethyl terephthalate, 2, 3-butanediol and ethylene glycol into a reaction kettle, wherein the molar ratio of the dimethyl terephthalate to the glycol is 1:1.5, and the molar ratio of the two glycols is 0.5:0.5. Stannous octoate (0.3% of total mass) and triphenyl phosphite (0.03% of total mass) were added to the reaction kettle with reflux condenser and thoroughly mixed under nitrogen atmosphere.
Slowly heating the system to 200 ℃ within 2h, keeping normal pressure, reacting for 2h at 200 ℃, and discharging methanol; and then heating the system to 220 ℃, reducing the air pressure to 5kPa, continuing to pre-polymerize for 2 hours, finally continuously vacuumizing the system, and continuing to polycondense until the reaction is finished, wherein the structure of the obtained polyester material is as follows, and x=0.5 and z=0.5.
Comparative example 2
Dimethyl terephthalate, 1, 4-cyclohexanediol and ethylene glycol are added into a reaction kettle, wherein the molar ratio of the dimethyl terephthalate to the diol is 1:1.5, and the molar ratio of the two diols is 0.5:0.5. Stannous octoate (0.3% of total mass) and triphenyl phosphite (0.03% of total mass) were added to the reaction kettle with reflux condenser and thoroughly mixed under nitrogen atmosphere.
Slowly heating the system to 200 ℃ within 2h, keeping normal pressure, reacting for 2h at 200 ℃, and discharging methanol; then heating the system to 220 ℃, reducing the air pressure to 5kPa, continuing to pre-polymerize for 2 hours, finally continuously vacuumizing the system, and continuing to polycondense until the reaction is finished, wherein the structure of the obtained polyester material is as follows, and y=0.5 and z=0.5
Comparative example 3
Dimethyl terephthalate, 2, 3-butanediol, 1, 4-cyclohexanediol and ethylene glycol are added into a reaction kettle, wherein the molar ratio of the dimethyl terephthalate to the diols is 1:1.5, and the molar ratio of the three diols is 0.2:0.2:0.6. Stannous octoate (0.3% of total mass) and triphenyl phosphite (0.02% of total mass) were added to the reaction kettle with reflux condenser and thoroughly mixed under nitrogen atmosphere.
Slowly heating the system to 200 ℃ within 2h, keeping normal pressure, reacting for 4h at 200 ℃, and discharging methanol; and then heating the system to 220 ℃, reducing the air pressure to 5kPa, continuing to pre-polymerize for 2 hours, and finally continuously vacuumizing the system, and continuing to polycondense until the reaction is finished, wherein the structure of the obtained polyester material is as follows, and x=0.2, y=0.2 and z=0.6.
Comparative example 4
The comparative example is prepared by the preparation method and the proportion provided by Chinese patent CN 103159907A. 46.6g of dimethyl terephthalate, 32.4g of 2, 3-butanediol, 41.8g of 1, 4-cyclohexanediol, 0.12g of tetra-n-butyl titanate were introduced into a three-necked flask and the reaction was carried out under nitrogen. Heating to 220 ℃, controlling the reaction temperature to 220 ℃ after the reactants form a homogeneous system, and reacting for 3 hours, wherein water is distilled out of the reaction mixture as a byproduct in the process until the amount of distillate reaches 92% of the theoretical calculated amount. 0.12g of antimony trioxide and 0.10g of trimethyl phosphate were added to the reaction mixture as a catalyst for polycondensation reaction (i.e., second catalyst) and a heat stabilizer, respectively. The polymerization reaction is carried out at the temperature of 250 ℃, vacuumizing to less than 500Pa, stirring for 3 hours, and stopping the reaction, wherein the structure of the obtained polyester material is as follows, x=0.5, and y=0.5.
Table 1 is used to illustrate the properties of the polyester materials produced in examples 1 to 9 and comparative examples 1 to 4, and is specifically as follows:
| Mw(g/mol) | Tg(℃) | Tm(℃) | transmittance (%) | |
| Example 1 | 20600 | 113 | n.d. | 91 |
| Example 2 | 22200 | 118 | n.d. | 91 |
| Example 3 | 23600 | 104 | n.d. | 89 |
| Example 4 | 16600 | 97 | n.d. | 89 |
| Example 5 | 26600 | 95 | n.d. | 90 |
| Example 6 | 21700 | 112 | n.d. | 91 |
| Example 7 | 19600 | 109 | n.d. | 91 |
| Example 8 | 17100 | 110 | n.d. | 90 |
| Example 9 | 19800 | 121 | n.d. | 89 |
| Comparative example 1 | 21500 | 100 | n.d. | 81 |
| Comparative example 2 | 18400 | 77 | 218 | n.d. |
| Comparative example 3 | 26000 | 90 | 232 | n.d. |
| Comparative example 4 | 3300 | 52 | n.d. | 47 |
The data in table 1 can be seen: the glass transition temperature of the series of polyester materials prepared by the invention is above 95 ℃, the glass transition temperature is at a higher level, the light transmittance is kept above 89%, and the polyester materials are very excellent. The glass transition temperature of the polyester material prepared in the embodiment 9 can reach 121 ℃, the light transmittance can reach 91%, and the glass transition temperature is higher than that of most polyester materials. As is clear from comparative example 1, in the case where 1, 4-cyclohexanediol is not added, the light transmittance of the polyester material is greatly reduced due to a more stable six-membered ring structure, side reactions are less likely to occur during the reaction, the system is more uniform, and the crystallization ability of the polyester is further deteriorated by the strong rigid structure thereof; as is clear from comparative example 2, the polyester material is crystallized without adding 2, 3-butanediol, so that the glass transition temperature is greatly reduced, and the 2, 3-butanediol unit has extremely strong crystallization breaking capability and segment movement inhibiting capability and is important for preparing a high Tg transparent material; as is clear from comparative example 3, when the amount of the linear diol is too large, the polyester material is crystallized, and thus, it is necessary to strictly control the amount of the linear diol in the preparation of the polyester material; as can be seen from comparative example 4, the present application provides a method for preparing a polyester material having a superior molecular weight, tg, and light transmittance.
Claims (10)
1. The polyester material is characterized by comprising an aromatic dibasic acid or aromatic dibasic ester and aliphatic dihydric alcohol, wherein the polyester material is obtained by polymerization of the aromatic dibasic acid or the aromatic dibasic ester and the aliphatic dihydric alcohol and has a structural general formula:
wherein,,
R 1 is one or a combination of aromatic rings; and/or the number of the groups of groups,
R 2 is C 2 ～C 6 One or a combination of linear straight chain alkane diols;
x is 0.30 to 0.80 mole fraction;
y is 0.08 to 0.40 mole fraction;
z is 0 to 0.40 mole fraction.
2. The polyester material according to claim 1, wherein in the structural formula,
R 1 is that
One or a combination of the above; and/or the number of the groups of groups,
R 2 is C 4 ～C 6 One or a combination of linear straight chain alkane diols;
x is 0.35 to 0.65 mole fraction;
y is 0.15 to 0.30 mole fraction;
z is 0.10 to 0.35 mole fraction.
3. A process for the preparation of a polyester material as claimed in claim 1 or 2, comprising the steps of:
fully mixing aromatic dibasic acid or aromatic dibasic ester, aliphatic dibasic alcohol, catalyst and antioxidant, performing transesterification reaction to obtain prepolymer, and performing polycondensation reaction to obtain the polyester material.
4. A process for preparing a polyester material as claimed in claim 3, wherein,
the aromatic dibasic acid or the aromatic dibasic ester is one or the combination of terephthalic acid, isophthalic acid, phthalic acid and dimethyl terephthalate; and/or the number of the groups of groups,
the aliphatic dihydric alcohol is 1, 4-cyclohexanediol, 2, 3-butanediol, C 2 ～C 6 Mixtures of linear alkylene glycols.
5. The method for producing a polyester material according to claim 4, wherein,
in the aliphatic diol, the 1, 4-cyclohexanediol accounts for 8-40% of the total mole ratio of the aliphatic diol, the 2, 3-butanediol accounts for 30-80% of the total mole ratio of the aliphatic diol, and the linear chain alkanediol accounts for 0-40% of the total mole ratio of the aliphatic diol.
6. The method for producing a polyester material according to claim 4, wherein,
the C is 2 ～C 6 The linear straight chain alkylene glycol is one or a combination of ethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 5-pentanediol and 1, 6-hexanediol.
7. A process for preparing a polyester material as claimed in claim 3, wherein,
the molar ratio of the aromatic dibasic acid or aromatic dibasic ester to the aliphatic dihydric alcohol is 1:1.2-1:2, preferably 1:1.4-1:1.8.
8. A process for preparing a polyester material as claimed in claim 3, wherein,
the catalyst is one or a combination of selenium dioxide, antimonous oxide, ethylene glycol antimon, p-toluenesulfonic acid, acetate, alkyl aluminum with 1-12 carbon atoms, organic tin compounds and titanate; stannous octoate is preferred;
the dosage of the catalyst is 0.05-1.0% of the total mass of the aromatic dibasic acid or the aromatic dibasic ester and the aliphatic dihydric alcohol; preferably 0.2 to 0.6%.
9. A process for preparing a polyester material as claimed in claim 3, wherein,
the antioxidant is one or a combination of phosphoric acid, phosphorous acid, phosphate ester, phosphite ester and phenyl phosphate;
the dosage of the antioxidant is 0.01-0.2% of the total mass of the aromatic dibasic acid or the aromatic dibasic ester and the aliphatic dihydric alcohol; preferably 0.01 to 0.1%.
10. A process for preparing a polyester material as claimed in claim 3, wherein,
the transesterification is carried out under the condition of protective gas, and the transesterification system needs to be heated to 180-220 ℃ within 2-4 h, preferably 200-220 ℃, and kept at the temperature for 2-6 h;
when the polycondensation reaction is carried out, the reaction system is firstly heated to 200-240 ℃, preferably 210-230 ℃, and pre-polycondensed for 1-4 hours under 3-10 kPa; then the reaction system is vacuumized to below 500Pa and polycondensed for 2-12 h.
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