CN107245140B - 高分子量的脂肪-芳香族共聚酯及其制备方法和应用 - Google Patents
高分子量的脂肪-芳香族共聚酯及其制备方法和应用 Download PDFInfo
- Publication number
- CN107245140B CN107245140B CN201710364534.6A CN201710364534A CN107245140B CN 107245140 B CN107245140 B CN 107245140B CN 201710364534 A CN201710364534 A CN 201710364534A CN 107245140 B CN107245140 B CN 107245140B
- Authority
- CN
- China
- Prior art keywords
- aliphatic
- aromatic copolyester
- pentanediol
- acid
- molecular weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920001634 Copolyester Polymers 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 35
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 10
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 claims description 48
- 229940043375 1,5-pentanediol Drugs 0.000 claims description 46
- 238000005886 esterification reaction Methods 0.000 claims description 26
- 230000032050 esterification Effects 0.000 claims description 21
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 10
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 6
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 6
- 229920003023 plastic Polymers 0.000 claims description 2
- 239000004033 plastic Substances 0.000 claims description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims 2
- 239000003054 catalyst Substances 0.000 abstract description 20
- 238000000034 method Methods 0.000 abstract description 11
- 150000002009 diols Chemical class 0.000 abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 5
- 150000005846 sugar alcohols Polymers 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000035484 reaction time Effects 0.000 abstract description 3
- 125000004432 carbon atom Chemical group C* 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- 125000003118 aryl group Chemical group 0.000 description 16
- 229920000728 polyester Polymers 0.000 description 16
- 239000000203 mixture Substances 0.000 description 11
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 10
- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 description 8
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- 125000001931 aliphatic group Chemical group 0.000 description 7
- 239000002131 composite material Substances 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- HQHCYKULIHKCEB-UHFFFAOYSA-N tetradecanedioic acid Natural products OC(=O)CCCCCCCCCCCCC(O)=O HQHCYKULIHKCEB-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 239000001361 adipic acid Substances 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 3
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- COGOJRKCCAQAPE-UHFFFAOYSA-N [N].[Si].[Ti] Chemical compound [N].[Si].[Ti] COGOJRKCCAQAPE-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
- 239000000600 sorbitol Substances 0.000 description 3
- 235000010356 sorbitol Nutrition 0.000 description 3
- 239000001384 succinic acid Substances 0.000 description 3
- ADDWXBZCQABCGO-UHFFFAOYSA-N titanium(iii) phosphide Chemical compound [Ti]#P ADDWXBZCQABCGO-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 229940035437 1,3-propanediol Drugs 0.000 description 2
- WTKWFNIIIXNTDO-UHFFFAOYSA-N 3-isocyanato-5-methyl-2-(trifluoromethyl)furan Chemical compound CC1=CC(N=C=O)=C(C(F)(F)F)O1 WTKWFNIIIXNTDO-UHFFFAOYSA-N 0.000 description 2
- HSSYVKMJJLDTKZ-UHFFFAOYSA-N 3-phenylphthalic acid Chemical group OC(=O)C1=CC=CC(C=2C=CC=CC=2)=C1C(O)=O HSSYVKMJJLDTKZ-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical group OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical group OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- 238000007327 hydrogenolysis reaction Methods 0.000 description 2
- 239000002932 luster Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 2
- TVIDDXQYHWJXFK-UHFFFAOYSA-N n-Dodecanedioic acid Natural products OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 2
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- -1 polybutylene Polymers 0.000 description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004904 shortening Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 230000000930 thermomechanical effect Effects 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 239000000811 xylitol Substances 0.000 description 2
- 235000010447 xylitol Nutrition 0.000 description 2
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 2
- 229960002675 xylitol Drugs 0.000 description 2
- ZWXGXPQZTIWOEK-UHFFFAOYSA-N 1,6-dioxacycloundecane-2,5-dione Chemical compound O=C1CCC(=O)OCCCCCO1 ZWXGXPQZTIWOEK-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- 229930195725 Mannitol Natural products 0.000 description 1
- ODPBVCOEAYPYMS-UHFFFAOYSA-N O1C2=C(C=C1)C(=O)OCCCCCOC2=O Chemical compound O1C2=C(C=C1)C(=O)OCCCCCOC2=O ODPBVCOEAYPYMS-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- DNXDYHALMANNEJ-UHFFFAOYSA-N furan-2,3-dicarboxylic acid Chemical compound OC(=O)C=1C=COC=1C(O)=O DNXDYHALMANNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 230000010512 thermal transition Effects 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G63/123—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/127—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
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2230/00—Compositions for preparing biodegradable polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
本发明公开了高分子量的脂肪‑芳香族共聚酯及其制备方法。所述脂肪‑芳香族共聚酯由二元醇和二元酸、选择性的加入多元醇经过酯化‑熔融缩聚过程制得。所述高分子量的脂肪‑芳香族共聚酯的二元醇组分中1,5‑戊二醇的含量较高,1,5‑戊二醇链段的碳原子数为奇数,因而具有优异的力学性能,具有广阔的应用前景。本发明提供的制备方法工艺简单;无需采用溶剂,过程环境友好;催化剂活性高、反应时间短、产物色泽好,有利于实现工业化生产。
Description
技术领域
本发明属于高分子材料及其制备技术领域,涉及聚酯及其制备方法,尤其涉及高分子量脂肪-芳香族共聚酯及其制备方法和应用。
背景技术
脂肪-芳香族共聚酯因兼具有良好的热-力学性能和在一定的组成范围内可生物降解的性质,并且结构-性能可控而被广泛关注,如聚己二酸丁二醇酯-共-对苯二甲酸丁二醇酯(PBAT)已经工业化,并用于制造农用薄膜,一次性用品等代替传统的聚烯烃材料。而传统的芳香族聚酯大多来源于化石原料,生物基单体取代石油基单体有益于减少对化石资源的依赖,而且可以合成具有新颖结构和独特性能的生物基聚酯新材料。在过去的十年中,新型生物基单体如2,5-呋喃二甲酸、1,4-丁二酸、1,9-壬二酸和1,10-癸二酸的合成技术的发展推动了生物基聚酯的合成的研究。1,5-戊二醇由糠醛催化加氢、氢解制得,糠醛是半纤维素水解、脱水环化的产物,随着糠醛一锅法合成1,5-戊二醇高效催化剂研究的深入,将以更低廉的价格获得足够高纯度的生物基1,5-戊二醇。同时,由于1,5-戊二醇碳链中的碳原子个数为奇数,使得1,5-戊二醇聚酯分子链段柔性更好,将具有不同于基于偶数碳链的二元醇的聚酯的物理和力学性能。
目前已有将1,5-戊二醇用于合成聚酯的报道,但文献中采用二元酸单体与1,5-戊二醇为原料通过酯化-缩聚方法制备的均聚酯分子量较低,如文献(Journal ofBiomaterials Science Polymer.,2012,23:1539-1551)报道了熔融缩聚法合成的聚庚二酸戊二醇酯,重均分子量为23 000g/mol;文献报道了采用丁二酸酐代替丁二酸(Journalof Macromolecular Science A.,2010,47:503-509)或者引入呋喃二甲酸作为二元酸单体(Materials Letters.,2016,178:64-67),可以获得中等分子量的聚丁二酸戊二醇酯(0.63dL/g)和聚呋喃二甲酸戊二醇酯(0.53dL/g)。与均聚脂相比,共聚酯特别是脂肪-芳香族共聚酯具有结构-性能可调的优势,并且已有高分子量的戊二醇共聚酯的报道,如文献(Macromolecular Bioscience.,2015,16:207-213)报道了采用1,5-戊二醇、1,6-己二酸和含有侧链的单体2-丁基-2-乙基-1,3-丙二醇,通过酯化-缩聚的方法合成了数均分子量最高达59000g/mol的共聚酯,但是合成过程中缩聚反应需要进行40个小时,时间长,能耗大,难以工业化生产,并且由于含有侧链单体的引入,降低了共聚酯的熔点和结晶性,使得这种聚酯材料难以在常温下使用。文献(Journal of Polymer Research.,2015,22:1-16)合成了重均分子量达50 000g/mol的聚酯-聚碳酸酯,但合成方法复杂,需要进行两次酯交换-熔融缩聚。
综上所述,为了开发具有优良热-力学性能的基于1,5-戊二醇的聚酯新材料,特别是具有可控结构和性能的脂肪-芳香族共聚酯,有必要研究开发基于1,5-戊二醇的高分子量的脂肪-芳香族共聚酯及其制备技术。
发明内容
针对现有技术中基于1,5-戊二醇的聚酯分子量较低、力学性能较差的不足,本发明的目的是提供一种高分子量的脂肪-芳香族共聚酯及其制备方法,所得脂肪-芳香族共聚酯的分子量高,具有柔性好,强度高等优良的力学性能,结构性能可控,可以满足不同应用的热-力学性能需求。
一种高分子量的脂肪-芳香族共聚酯,所述脂肪-芳香族共聚酯含有二元醇组分、二元酸组分和0~1mol%的多元醇组分;其中,
二元醇组分中含有50~100mol%的1,5-戊二醇残基;
二元酸组分中含有10~90mol%的脂肪族二元酸残基和90~10mol%的芳香族二元酸残基。
本发明脂肪-芳香族共聚酯的结构-性能可通过共聚酯组成的变化调节,芳香族组分保证了材料的强度,共聚使结晶性降低,增强了聚合物的柔性,并且在一定组成范围内,脂肪-芳香族共聚酯具有生物降解性。
所述脂肪-芳香族共聚酯的特性粘度≥0.8dL/g,本发明基于1,5-戊二醇的脂肪-芳香族共聚酯分子量高,热稳定性好,色泽优良,脂肪-芳香族共聚酯产品色泽为白色或浅黄色。
作为优选,除了1,5-戊二醇残基以外,所述二元醇组分还含有乙二醇、1,3-丙二醇、1,4-丁二醇和1,6-己二醇残基中的至少一种。
作为优选,所述脂肪族二元酸残基为1,4-丁二酸、1,5-戊二酸、1,6-己二酸,1,9-壬二酸、1,10-癸二酸、1,12-十二碳二酸和1,14-十四碳二酸残基中的至少一种。
作为优选,所述芳香族二元酸残基为对苯二甲酸、间苯二甲酸、邻苯二甲酸或酐、2,5-呋喃二甲酸、萘二甲酸和联苯二甲酸残基中的至少一种。
作为优选,所述二元酸组分中含有40~90mol%的脂肪族二元酸残基和10~60mol%的芳香族二元酸残基。芳香族组分保证了材料的强度,共聚使结晶性降低,增强了聚合物的柔性,并且在一定组成范围内,该脂肪-芳香族共聚酯的力学性能较好,且具有生物降解性。
作为优选,所述多元醇组分含有甘油、三羟甲基丙烷、季戊四醇、木糖醇、山梨醇和甘露醇残基中的至少一种。多元醇组分的引入能有效提高脂肪-芳香族共聚酯的熔体强度,当其应用于薄膜生产时,较高的熔体强度可以在降低膜厚情况下降低产品成本,同时增强成膜稳定性。
作为优选,所述脂肪-芳香族共聚酯含有二元醇组分、二元酸组分和0.1~1mol%的多元醇组分。
本发明提供了一种上述的高分子量的脂肪-芳香族共聚酯的制备方法,包括以下步骤:
(1)酯化反应:
摩尔比为120~300:100:0~1的二元醇、二元酸和多元醇在氮气保护和催化剂存在下,在160~230℃下反应2~6小时,得到酯化产物;
所述的催化剂选自钛酸正丁酯、钛酸异丙酯、钛-硅-氮复合催化剂或钛-磷复合催化剂;
(2)缩聚反应:步骤(1)所得的酯化产物在压力≤200Pa,温度为200~250℃的条件下反应2~6小时,制得所述的脂肪-芳香族共聚酯。
本发明所用1,5-戊二醇为生物基1,5-戊二醇,由糠醛催化加氢、氢解制得,有利于减少对石油资源的依赖。
所述二元醇中含有50~100mol%的1,5-戊二醇;除了1,5-戊二醇以外,所述二元醇还含有乙二醇、1,3-丙二醇、1,4-丁二醇和1,6-己二醇中的至少一种。
所述二元酸中含有10~90mol%的脂肪族二元酸和90~10mol%的芳香族二元酸;作为优选,所述二元酸中含有40~90mol%的脂肪族二元酸和10~60mol%的芳香族二元酸。
所述脂肪族二元酸为1,4-丁二酸、1,5-戊二酸、1,6-己二酸,1,9-壬二酸、1,10-癸二酸、1,12-十二碳二酸和1,14-十四碳二酸中的至少一种。
所述芳香族二元酸为对苯二甲酸、间苯二甲酸、邻苯二甲酸或酐、2,5-呋喃二甲酸、萘二甲酸和联苯二甲酸中的至少一种。
所述多元醇为有甘油、三羟甲基丙烷、季戊四醇、木糖醇、山梨醇和甘露醇中的至少一种。
作为优选,所述二元醇、二元酸和多元醇的投料摩尔比为120~300:100:0.1~1。
所述催化剂的用量为二元酸物质的量的0.02~0.2%。所用催化剂活性高,选择性好,有利于缩短反应时间,提高分子量,获得较优色泽的脂肪-芳香族共聚酯产品。
作为优选,步骤(1)中,由于芳香族二元酸的反应活性比脂肪族二元酸弱,在所述二元酸中,当芳香族二元酸的含量小于50mol%时,酯化反应在160~200℃下反应2~3小时;当芳香族二元酸的含量大于50mol%时,所述酯化反应分阶段进行,第一阶段在160~200℃下反应1小时,第二阶段在210℃下反应1小时,第三阶段在220℃下反应1小时,第四阶段在230℃下反应0~1小时。
为了得到色泽良好的高特性粘数的脂肪-芳香族共聚酯产品,作为优选,步骤(2)中,所述缩聚反应分阶段进行,在所述二元酸中,当芳香族二元酸的含量小于50mol%时,第一阶段在200℃下反应1小时,第二阶段在240℃下反应1~3小时,第三阶段在250℃下反应1小时;当芳香族二元酸的含量大于50mol%时,第一阶段在230℃下反应1小时,第二阶段在240℃下反应1~3时,第三阶段在250℃下反应1小时。
作为优选,步骤(2)中,向步骤(1)所得的酯化产物中补加催化剂再进行缩聚反应,补加的催化剂为钛酸正丁酯、钛酸异丙酯、钛-硅-氮复合催化剂或钛-磷复合催化剂;补加量为步骤(1)中二元酸物质的量的0.02~0.2%。
作为优选,所述的催化剂为钛-硅-氮复合催化剂,该催化剂稳定性好,在酯化反应中一次添加即可,无需在缩聚反应中额外补加催化剂。
本发明的另一目的是提供一种上述高分子量的脂肪-芳香族共聚酯在塑料中的应用。本发明脂肪-芳香族共聚酯的结构-性能可通过共聚酯组成的变化调节,芳香族组分保证了材料的强度,共聚使结晶性降低,增强了聚合物的柔性,并且在一定组成范围内,该脂肪-芳香族共聚酯具有生物降解性。
与现有技术相比,本发明具有以下有益效果:
(1)本发明提供的基于1,5-戊二醇的脂肪-芳香族共聚酯分子量高,其特性粘数高于0.8dL/g。
(2)本发明提供的基于1,5-戊二醇的脂肪-芳香族共聚酯中二元醇组分至少含有50mol%的1,5-戊二醇,1,5-戊二醇为奇数碳的直链二元醇,因而分子链段具有更好的柔性,和不同于基于偶数碳链的二元醇的聚酯的物理和力学性能。
(3)本发明提供的基于1,5-戊二醇的脂肪-芳香族共聚酯结构性能可控,可以满足不同应用的热-力学性能需求。
(4)本发明提供的基于1,5-戊二醇的脂肪-芳香族共聚酯色泽优良,聚酯产品色泽为白色或浅黄色。
(5)本发明提供的基于1,5-戊二醇的脂肪-芳香族共聚酯热稳定性好,具有优异的加工性能和实用性。
(6)本发明提供的基于1,5-戊二醇的脂肪-芳香族共聚酯在芳香族组分低于60mol%时具有生物降解性;
(7)本发明提供的基于1,5-戊二醇的脂肪-芳香族共聚酯,所用的1,5-戊二醇单体为生物基单体,因而是生物基聚酯;部分二元酸单体如1,4-丁二酸、1,9-壬二酸、1,10-癸二酸也可从生物质资源获得,因而可以制得全生物基聚酯,有利于减少对石油资源的依赖。
(8)本发明提供的1,5-戊二醇脂肪-芳香族共聚酯的合成方法,由于催化剂活性高,选择性好,有利于缩短反应时间,提高分子量,获得较优色泽的聚酯产品,同时工艺简单,无需采用溶剂,过程环境友好,有利于实现工业化生产。
附图说明
图1为本发明实施例1制备的高分子量的脂肪-芳香族共聚酯的核磁共振氢谱图;
图2为本发明实施例2制备的高分子量的脂肪-芳香族共聚酯的核磁共振氢谱图。
具体实施方式
下面结合附图和实施例对本发明进行具体描述,但本发明不限于这些实施例。
下述实施例中所采用的测试分析方法如下:
特性粘数:称取0.125g左右的样品溶于25mL氯仿中,在25℃恒温水浴中定容,利用杭州中旺公司IVS300自动粘数仪,粘数管选用内径0.36mm,测定样品的特性粘数。
采用美国TA公司的TA Q200型差热扫描量热仪(DSC)测试样品的热转变行为。首先称取8~10mg样品放入铝制坩埚中,然后设定温度程序,先由-100℃以10℃/min的速率升温至200℃,保温3min,然后以10℃/min的速率降温至-100℃,保温5min,再以10℃/min的速率升温至200℃,参比为空的铝制坩埚,保护气体为氮气。
核磁共振氢谱:将20mg左右的样品溶于0.5mL氘代氯仿中,采用德国BRUKER公司的AC-80核磁共振谱仪(400M)进行测试,内标为四甲基硅烷。
实施例1
(1)在250mL四口烧瓶中加入1,4-丁二酸(0.276mol,32.56g)、间苯二甲酸(0.226mol,37.57g)、1,5-戊二醇(0.75mol,78.11g)和钛酸正丁酯(0.5mmol,171mg),醇酸比为1.5,在200℃下反应3小时,得到酯化产物,酯化率达95.6%;
(2)向步骤(1)所得酯化产物中加入钛酸正丁酯(0.25mmol,85mg),在约130Pa条件下,在200℃下反应1小时,240℃下反应2.5小时,250℃下反应1小时,脱除过量的1,5-戊二醇及少量低聚物,制得所述基于1,5-戊二醇的高分子量的脂肪-芳香族共聚酯,其核磁共振氢谱图如图1所示。
经测试,本实施例制备的脂肪-芳香族共聚酯的特性粘数为1.26dL/g,玻璃化转变温度为-20.2℃;熔点为40.5℃。
实施例2
(1)在250mL四口烧瓶中加入1,4-己二酸(0.206mol,30.14g)、2,5-呋喃二甲酸(0.169mol,26.34g)、1,5-戊二醇(0.75mol,78.11g)和二氧化钛-二氧化硅-聚乙烯吡咯烷酮复合催化剂(1mmol,76mg),醇酸比为2,在200℃下反应3.5小时,得到酯化产物,酯化率达96.4%;
(2)步骤(1)所得酯化产物中不再补加催化剂,在约160Pa条件下,在200℃下反应1小时,240℃下反应3小时,250℃下反应1小时,脱除过量的1,5-戊二醇及少量低聚物,制得所述基于1,5-戊二醇的高分子量的脂肪-芳香族共聚酯,其核磁共振氢谱图如图2所示。
经测试,本实施例制备的脂肪-芳香族共聚酯的特性粘数为0.82dL/g,玻璃化转变温度为-24.7℃;熔点为42.3℃。
实施例3
(1)在250mL四口烧瓶中加入1,9-壬二酸(0.125mol,23.53g)、对苯二甲酸(0.125mol,20.77g)、1,5-戊二醇(0.7mol,72.90g)、1,4-丁二醇(0.05mol,4.51g)和钛酸异丙酯(0.5mmol,141mg),醇酸比为2.5,在200℃下反应3小时,得到酯化产物,酯化率达98.2%;
(2)向步骤(1)所得酯化产物中加入钛-磷复合催化剂(306mg,购自南京能德新材料技术公司,TCAIA10),在约160Pa条件下,在200℃下反应1小时,240℃下反应2小时,250℃下反应1小时,脱除过量的1,5-戊二醇及少量低聚物,制得所述基于1,5-戊二醇的高分子量的脂肪-芳香族共聚酯。
经测试,本实施例制备的脂肪-芳香族共聚酯的特性粘数为0.98dL/g,玻璃化转变温度为-43.7℃,熔点65.2℃。
实施例4
(1)在250mL四口烧瓶中加入1,10-癸二酸(0.125mol,25.28g)、对苯二甲酸(0.25mol,41.54g)、1,5-戊二醇(0.75mol,78.11g)、甘油(0.4mmol,0.037g)和钛酸异丙酯(0.35mmol,99.5mg),醇酸比为2,在200℃下反应1小时,210℃下反应1小时,220℃下反应1小时,220℃下反应0.5小时,得到酯化产物,酯化率达98.2%;
(2)向步骤(1)所得酯化产物中加入钛酸异丙酯(0.35mmol,99.5mg),在约100Pa条件下,在230℃下反应1小时,240℃下反应1小时,250℃下反应1小时,脱除过量的1,5-戊二醇及少量低聚物,制得所述基于1,5-戊二醇的高分子量的脂肪-芳香族共聚酯。
经测试,本实施例制备的脂肪-芳香族共聚酯的特性粘数为1.14dL/g,玻璃化转变温度为-24.5℃;熔点为90.6℃。
实施例5
(1)在250mL四口烧瓶中加入1,4-丁二酸(0.276mol,32.56g)、间苯二甲酸(0.226mol,37.57g)、1,5-戊二醇(0.75mol,78.11g)和钛酸正丁酯(0.5mmol,171mg),醇酸比为1.5,在200℃下反应3小时,得到酯化产物,酯化率达95.6%;
(2)向步骤(1)所得酯化产物中加入钛酸正丁酯(0.25mmol,85mg),在约130Pa条件下,在250℃下反应3.5小时,脱除过量的1,5-戊二醇及少量低聚物,制得所述基于1,5-戊二醇的脂肪-芳香族共聚酯。
经测试,本实施例制备的脂肪-芳香族共聚酯的特性粘数为0.56dL/g,色泽较黄。由于缩聚反应步骤没有分阶段进行,所得脂肪-芳香族共聚酯的特性粘数较低,且色泽较黄。
实施例6
(1)在250mL四口烧瓶中加入1,6-己二酸(0.25mol,36.53g)、间苯二甲酸(0.125mol,20.77g)、1,5-戊二醇(0.75mol,78.11g)、山梨醇(0.3mmol,0.055g)和钛酸正丁酯(0.5mmol,171mg),醇酸比为2,在200℃下反应3小时,得到酯化产物,酯化率达91.0%;
(2)向步骤(1)所得酯化产物中加入钛酸正丁酯(0.5mmol,171mg),在约120Pa条件下,在250℃下反应3小时,脱除过量的1,5-戊二醇及少量低聚物,制得所述基于1,5-戊二醇的脂肪-芳香族共聚酯。
经测试,本实施例制备的脂肪-芳香族共聚酯的特性粘数为0.62dL/g,色泽较黄。
Claims (1)
1.一种高分子量的脂肪-芳香族共聚酯在塑料中的应用,其特征在于,所述脂肪-芳香族共聚酯的制备方法包括如下步骤:
(1)酯化反应:在250mL四口烧瓶中加入0.125mol 1,10-癸二酸、0.25mol对苯二甲酸、0.75mol 1,5-戊二醇、0.4mmol甘油和0.35mmol钛酸异丙酯,醇酸比为2,在200℃下反应1小时,210℃下反应1小时,220℃下反应1小时,220℃下反应0.5小时,得到酯化产物;
(2)缩聚反应:向步骤(1)所得酯化产物中加入0.35mmol钛酸正丁酯,在100Pa条件下,在230℃下反应1小时,240℃下反应1小时,250℃下反应1小时,脱除过量的1,5-戊二醇及少量低聚物,制得基于1,5-戊二醇的高分子量的脂肪-芳香族共聚酯。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710364534.6A CN107245140B (zh) | 2017-05-22 | 2017-05-22 | 高分子量的脂肪-芳香族共聚酯及其制备方法和应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710364534.6A CN107245140B (zh) | 2017-05-22 | 2017-05-22 | 高分子量的脂肪-芳香族共聚酯及其制备方法和应用 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN107245140A CN107245140A (zh) | 2017-10-13 |
CN107245140B true CN107245140B (zh) | 2019-04-16 |
Family
ID=60016770
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201710364534.6A Active CN107245140B (zh) | 2017-05-22 | 2017-05-22 | 高分子量的脂肪-芳香族共聚酯及其制备方法和应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN107245140B (zh) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109705323B (zh) * | 2019-01-15 | 2020-12-15 | 南通龙达生物新材料科技有限公司 | 一种含有脂肪族碳酸酯链段的高阻隔性脂肪-芳香族共聚酯的制备方法 |
CN111269373B (zh) * | 2020-02-12 | 2022-01-04 | 浙江大学衢州研究院 | 基于共晶的可重塑形状记忆弹性体的制备方法 |
CN111592642B (zh) * | 2020-05-18 | 2022-09-23 | 浙江恒逸石化研究院有限公司 | 一种高韧性生物基聚酯的制备方法 |
CN112708115A (zh) * | 2020-06-17 | 2021-04-27 | 北京化工大学 | 一种耐高温芳香族-脂肪族生物基聚酯弹性体及制备方法 |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102850533B (zh) * | 2011-07-01 | 2015-10-14 | 上海杰事杰新材料(集团)股份有限公司 | 一种生物可降解聚酯及其制备方法 |
-
2017
- 2017-05-22 CN CN201710364534.6A patent/CN107245140B/zh active Active
Also Published As
Publication number | Publication date |
---|---|
CN107245140A (zh) | 2017-10-13 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Papageorgiou et al. | Production of bio-based 2, 5-furan dicarboxylate polyesters: Recent progress and critical aspects in their synthesis and thermal properties | |
Hong et al. | High molecular weight bio furan-based co-polyesters for food packaging applications: Synthesis, characterization and solid-state polymerization | |
Wang et al. | Modification of poly (ethylene 2, 5-furandicarboxylate)(PEF) with 1, 4-cyclohexanedimethanol: Influence of stereochemistry of 1, 4-cyclohexylene units | |
CN107245140B (zh) | 高分子量的脂肪-芳香族共聚酯及其制备方法和应用 | |
JP2015507684A (ja) | バイオマスから調製された2,5−フランジカルボン酸系ポリエステル | |
KR102438607B1 (ko) | 무수당 알코올의 고체 분산체를 이용한 생분해성 폴리에스테르 복합체 및 이의 제조 방법, 및 이를 포함하는 성형품 | |
US11306179B2 (en) | Polyester copolymer | |
KR20150002624A (ko) | 중합체, 이의 합성 방법 및 이를 포함하는 조성물 | |
Lu et al. | Biobased flexible aromatic polyester poly (1, 5-pentylene terephthalate)(PPeT): Revisiting melt crystallization behaviors and thermo-mechanical properties | |
JP2017528535A (ja) | 透明生分解性高分子 | |
CN107840948B (zh) | 一种生物基高分子化合物及其制备方法 | |
NL1040265C2 (en) | SEMI-CRYSTALLINE POLYESTER. | |
Yang et al. | Influence of asymmetric substituent group 2-methyl-1, 3-propanediol on bio-based poly (propylene furandicarboxylate) copolyesters | |
Zhang et al. | High molecular weight poly (butylene terephthalate‐co‐butylene 2, 5‐furan dicarboxylate) copolyesters: From synthesis to thermomechanical and barrier properties | |
CN107189043B (zh) | 高分子量弱结晶性的聚酯及其制备方法和应用 | |
Albanese et al. | The aliphatic counterpart of PET, PPT and PBT aromatic polyesters: effect of the molecular structure on thermo-mechanical properties. | |
JP5530490B2 (ja) | 透明共重合ポリエステル、透明共重合ポリエステルの調製方法、および、透明共重合ポリエステルを含んでなる物品 | |
JP5114993B2 (ja) | ポリエステル樹脂 | |
US11548980B2 (en) | Polyester copolymer | |
CN111072941A (zh) | 一种双环氧化合物合成线型、多官能度聚酯多元醇的方法 | |
Jin et al. | Melt polycondensation of 2, 5-tetrahydrofurandimethanol with various dicarboxylic acids towards a variety of biobased polyesters | |
Zhao et al. | Biodegradable poly (butylene succinate-co-butylene dimerized fatty acid) s: Synthesis, crystallization, mechanical properties, and rheology | |
CN115109045A (zh) | 一种生物基杂环单体及其均聚酯的制备方法 | |
KR102210711B1 (ko) | 무수당 알코올과 무수당 알코올-알킬렌 글리콜을 포함하는 생분해성 공중합 폴리에스테르 수지 및 이의 제조 방법 | |
CN114057998A (zh) | 一种2,5-呋喃二甲酸共聚酯及其制备方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |