CN102676591A - Method for preparing polyester containing 3-hydroxy glutaric acid unit - Google Patents
Method for preparing polyester containing 3-hydroxy glutaric acid unit Download PDFInfo
- Publication number
- CN102676591A CN102676591A CN2012100089035A CN201210008903A CN102676591A CN 102676591 A CN102676591 A CN 102676591A CN 2012100089035 A CN2012100089035 A CN 2012100089035A CN 201210008903 A CN201210008903 A CN 201210008903A CN 102676591 A CN102676591 A CN 102676591A
- Authority
- CN
- China
- Prior art keywords
- hydroxyglutaric acid
- polyester containing
- dibasic fatty
- add
- lipase
- 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.)
- Pending
Links
- ZQHYXNSQOIDNTL-UHFFFAOYSA-N 3-hydroxyglutaric acid Chemical group OC(=O)CC(O)CC(O)=O ZQHYXNSQOIDNTL-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 229920000728 polyester Polymers 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 21
- 239000000178 monomer Substances 0.000 claims abstract description 55
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 21
- 238000002360 preparation method Methods 0.000 claims abstract description 15
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 4
- 150000002191 fatty alcohols Chemical class 0.000 claims abstract 8
- 108090001060 Lipase Proteins 0.000 claims abstract 7
- 102000004882 Lipase Human genes 0.000 claims abstract 7
- 239000004367 Lipase Substances 0.000 claims abstract 7
- 235000019421 lipase Nutrition 0.000 claims abstract 7
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract 6
- 229930195729 fatty acid Natural products 0.000 claims abstract 6
- 239000000194 fatty acid Substances 0.000 claims abstract 6
- 150000004665 fatty acids Chemical class 0.000 claims abstract 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 32
- 239000002808 molecular sieve Substances 0.000 claims description 19
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 19
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 241001661345 Moesziomyces antarcticus Species 0.000 claims description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 241000235403 Rhizomucor miehei Species 0.000 claims description 5
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 3
- 241000223258 Thermomyces lanuginosus Species 0.000 claims description 2
- 239000006166 lysate Substances 0.000 claims description 2
- 210000000496 pancreas Anatomy 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims 3
- 101710098556 Lipase A Proteins 0.000 claims 1
- 101710099648 Lysosomal acid lipase/cholesteryl ester hydrolase Proteins 0.000 claims 1
- 102100026001 Lysosomal acid lipase/cholesteryl ester hydrolase Human genes 0.000 claims 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims 1
- 239000000706 filtrate Substances 0.000 claims 1
- 238000003760 magnetic stirring Methods 0.000 claims 1
- 238000000926 separation method Methods 0.000 claims 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims 1
- 239000008096 xylene Substances 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 abstract description 8
- 238000012643 polycondensation polymerization Methods 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 abstract description 3
- 125000002524 organometallic group Chemical group 0.000 abstract description 3
- 239000006227 byproduct Substances 0.000 abstract description 2
- 231100000419 toxicity Toxicity 0.000 abstract description 2
- 230000001988 toxicity Effects 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- 150000002148 esters Chemical class 0.000 abstract 1
- 150000004676 glycans Chemical class 0.000 abstract 1
- 229920001282 polysaccharide Polymers 0.000 abstract 1
- 239000005017 polysaccharide Substances 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- 231100000331 toxic Toxicity 0.000 abstract 1
- 230000002588 toxic effect Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 33
- 239000002253 acid Substances 0.000 description 18
- 229920000642 polymer Polymers 0.000 description 16
- 238000013019 agitation Methods 0.000 description 14
- 238000001035 drying Methods 0.000 description 14
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 8
- 150000002632 lipids Chemical class 0.000 description 7
- RWLALWYNXFYRGW-UHFFFAOYSA-N 2-Ethyl-1,3-hexanediol Chemical compound CCCC(O)C(CC)CO RWLALWYNXFYRGW-UHFFFAOYSA-N 0.000 description 5
- 229920003232 aliphatic polyester Polymers 0.000 description 5
- 229960005082 etohexadiol Drugs 0.000 description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000002939 deleterious effect Effects 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- 239000003863 metallic catalyst Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- SVTBMSDMJJWYQN-RXMQYKEDSA-N (4r)-2-methylpentane-2,4-diol Chemical compound C[C@@H](O)CC(C)(C)O SVTBMSDMJJWYQN-RXMQYKEDSA-N 0.000 description 1
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 241000282898 Sus scrofa Species 0.000 description 1
- 208000012826 adjustment disease Diseases 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008614 cellular interaction Effects 0.000 description 1
- 230000036755 cellular response Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 150000007520 diprotic acids Chemical class 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003937 drug carrier Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229920001184 polypeptide Polymers 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
本发明公开了一种制备含3-羟基戊二酸单元聚酯的方法，将单体3-羟基戊二酸与其它聚合单体在脂肪酶的催化作用下，于40～120℃反应制得含3-羟基戊二酸单元的功能聚酯；所述其它聚合单体为二元脂肪醇、或二元脂肪醇和二元脂肪酸。本发明采用含羟基三官能度的3-羟基戊二酸作为缩合聚合反应的单体之一，采用高效的脂肪酶作为催化剂使单体直接缩合聚合，制备含有3-羟基戊二酸单元的聚酯，缩合聚合反应一步完成，反应条件温和，副产物较少；避免使用有毒的有机金属催化剂。本发明的制备方法是一种反应毒性低、环境友好的聚酯合成方法。
The invention discloses a method for preparing polyester containing 3-hydroxyglutaric acid unit, which is prepared by reacting monomer 3-hydroxyglutaric acid and other polymerization monomers under the catalysis of lipase at 40-120°C Functional polyester containing 3-hydroxyglutaric acid unit; said other polymerizable monomers are dibasic fatty alcohols, or dibasic fatty alcohols and dibasic fatty acids. The present invention adopts 3-hydroxyglutarate containing hydroxyl trifunctionality as one of the monomers in the condensation polymerization reaction, uses high-efficiency lipase as a catalyst to directly condense and polymerize the monomers, and prepares polysaccharides containing 3-hydroxyglutarate units. Ester, the condensation polymerization reaction is completed in one step, the reaction conditions are mild, and the by-products are less; the use of toxic organometallic catalysts is avoided. The preparation method of the invention is a polyester synthesis method with low reaction toxicity and environmental friendliness.
Description
Technical field
The present invention relates to the method that a kind of preparation contains 3-hydroxyl pentanedioic acid unit polyester, particularly adopt enzyme catalysis direct polymerization prepared in reaction to contain the method for 3-hydroxyl pentanedioic acid unit polyester, belong to technical field of function materials.
Background technology
Aliphatic polyester is a kind of important Biodegradable material, gains great popularity owing to it has favorable biological degradability, forming process property and mechanical property.But because traditional aliphatic polyester lacks the hydrophilic polar group with cell interaction; Therefore its use range is to restriction; On the aliphatic polyester chain, introduce one side such as hydrophilic hydroxyl, carboxyl or amino can promote cell above that adhesion and sprawl the raising biocompatibility; Face can be regulated degradation rate through the content that changes backbone structure and functional group on the other hand.What need particularly point out is can medicine, protein, polypeptide etc. be had the active molecule of biospecific through these reactive groups to utilize the method for chemical bonds to be fixed on the material; Thereby cause specific cell response, be expected to as target controlling and releasing pharmaceutical carrier and intelligentized tissue engineering bracket material.
When generally using organometallic compound as the Preparation of Catalyst functional polyester; Generally need use the polyfunctionality monomer when in aliphatic polyester, introducing hydroxyl, carboxyl or amino isopolarity group; Need carry out chemoproection to its hydroxyl, carboxyl or amino group; Carry out catalyzed polymerization then, slough blocking group at last, obtain subject polymer.Reactions step is more, and yield is lower, high temperature, high vacuum condition that reaction needed is harsh, and cost is also just than higher.On the other hand, owing to have to use a large amount of organic solvents and deleterious organo-metallic catalyst in the reaction process, so can bring than the serious environmental pollution problem.When utilizing 3-hydroxyl pentanedioic acid monomer and common divalent alcohol or other diprotic acid and divalent alcohol copolymerization aliphatic polyester, also can face such problem.
Summary of the invention
The purpose of this invention is to provide the method that a kind of enzyme catalysis preparation contains 3-hydroxyl pentanedioic acid unit polyester, avoid that reactions step is loaded down with trivial details, the shortcoming of severe reaction conditions.
In order to realize above purpose; The technical scheme that the present invention adopted is: a kind of preparation contains the method for 3-hydroxyl pentanedioic acid unit polyester; Monomer 3-hydroxyl pentanedioic acid and other polymerization single polymerization monomer under the katalysis of lypase, are made in 40～120 ℃ of reactions and to contain the unitary functional polyester of 3-hydroxyl pentanedioic acid; Said other polymerization single polymerization monomer is binary aliphatic alcohol or binary aliphatic alcohol and binary lipid acid.
The carbon chain lengths of said binary aliphatic alcohol is C
2～C
16The carbon chain lengths of said binary lipid acid is C
4～C
12It is octane, normal hexane, hexanaphthene, toluene, YLENE, the trimethyl carbinol, THF, N that solvent is adopted in reaction, dinethylformamide or chloroform; The weight ratio of said solvent and monomer total amount is 1: 10～3: 1.
Concrete preparation method is: binary aliphatic alcohol and 3-hydroxyl pentanedioic acid are added in the reactor drum according to 1: 2～2: 1 molar ratio mix; Be heated to 40～120 ℃; According to adding binary aliphatic alcohol and 3-hydroxyl pentanedioic acid gross weight 100～4000U/g add lypase; Add molecular sieve, stirring reaction separated obtaining containing the unitary functional polyester of 3-hydroxyl pentanedioic acid after 12～96 hours.
Perhaps concrete preparation method is: binary aliphatic alcohol and the 3-hydroxyl pentanedioic acid molar ratio according to 1: 2～20: 1 is added in the reactor drum; Adding binary lipid acid simultaneously is 3: 2～1: 1 with the mol ratio of carboxyl and hydroxyl in the adjustment reaction system; Mixing also is heated to 40～120 ℃; According to adding binary aliphatic alcohol, 3-hydroxyl pentanedioic acid and binary lipid acid gross weight 100～4000U/g add lypase; Add molecular sieve, stirring reaction separated obtaining containing the unitary functional polyester of 3-hydroxyl pentanedioic acid after 12～96 hours.
Among the concrete preparation method, stirring reaction employing speed is the magnetic agitation of 20～400rpm.Separate and adopt the reaction back to add chloroform, THF or acetone solution product, remove by filter lypase, filtrating vacuum Rotary drying.Said lypase derives from the lypase of Candida antarctica, Thermomyces lanuginosus, Rhizomucor miehei, Mucor miehei or pig pancreas.The purpose that wherein adds molecular sieve is that the water that produces in the reaction process is removed in absorption, and molecular balance is moved to the product direction.
The 3-hydroxyl pentanedioic acid that the present invention adopts the hydroxyl three-functionality-degree is as one of monomer of condensation polymerization reaction; Adopting efficiently, lypase makes the monomer direct polymerization as catalyzer; Preparation contains the unitary polyester of 3-hydroxyl pentanedioic acid; One step of condensation polymerization reaction accomplishes, and reaction conditions is gentle, and by product is less; Avoid the use of deleterious organo-metallic catalyst.Preparing method of the present invention is low, the eco-friendly polyester compound method of a kind of reaction toxicity.
Polyester of the present invention is introduced 3-hydroxyl pentanedioic acid on the polyester long-chain, therefore can on the main chain of polyester, introduce functional group, thereby obtain containing the unitary functional polyester of 3-hydroxyl pentanedioic acid.The present invention also can introduce binary lipid acid in monomer system; Binary lipid acid can be adjusted the The Nomenclature Composition and Structure of Complexes of polymer chain; In in a big way, change the various performances that contain the unitary functional polyester of 3-hydroxyl pentanedioic acid, satisfy the performance requriements under the different service conditions better.
Description of drawings
Fig. 1 is the infrared spectrogram of Comparative Examples;
Fig. 2 is the infrared spectrogram of embodiment 1.
Embodiment
Bright specifically below in conjunction with specific embodiment to the present invention's work, but do not limit technical scheme of the present invention, the 3-hydroxyl pentanedioic acid, binary lipid acid, binary aliphatic alcohol, lypase, solvent, the molecular sieve that wherein relate to are the commercially available prod.
Embodiment 1
According to 15: 13: 2 ratios of mol ratio, in the round-bottomed flask of adding 100mL (ratio of carboxyl and hydroxyl is 16: 15), octane and monomer total amount add with 3: 1 mass ratio with monomer butyleneglycol, hexanodioic acid, 3-hydroxyl pentanedioic acid; Add the lypase that derives from Candida antarctica by the every gram monomer of 1000U/ total amount, place under 70 ℃ of oil baths, magnetic agitation speed is 200rpm; Add molecular sieve; React after 48 hours, add the dissolved in chloroform product, remove by filter lypase; Product solution for vacuum Rotary drying, molecular weight is 17000 polyester polymers.
Embodiment 2
According in the round-bottomed flask of mol ratio ratio adding in 15: 7.5: 7.5 100mL (ratio of carboxyl and hydroxyl is 5: 4), normal hexane and monomer total amount add with 3: 1 mass ratio, add the lypase that derives from Candida antarctica by the every gram monomer of 1500U/ total amount with monomer butyleneglycol, hexanodioic acid, 3-hydroxyl pentanedioic acid; Place under 80 ℃ of oil baths; Magnetic agitation speed is 200rpm, adds molecular sieve, reacts after 96 hours; Add the dissolved in chloroform product; Remove by filter lypase, product solution for vacuum Rotary drying, molecular weight is 5900 polyester polymers.
Embodiment 3
According in the round-bottomed flask of mol ratio ratio adding in 15: 13: 2 100mL (ratio of carboxyl and hydroxyl is 16: 15), hexanaphthene and monomer total amount add with 3: 1 mass ratio, add the lypase that derives from Candida antarctica by the every gram monomer of 4000U/ total amount with monomer terepthaloyl moietie, hexanodioic acid, 3-hydroxyl pentanedioic acid; Place under 40 ℃ of oil baths; Magnetic agitation speed is 200rpm, adds molecular sieve, reacts after 48 hours; Add the dissolved in chloroform product; Remove by filter lypase, product solution for vacuum Rotary drying, molecular weight is 6700 polyester polymers.
Embodiment 4
According in the round-bottomed flask of mol ratio ratio adding in 15: 13: 4 100mL (ratio of carboxyl and hydroxyl is 1: 1), toluene and monomer total amount add with 3: 1 mass ratio, add the lypase that derives from Candida antarctica by the every gram monomer of 1500U/ total amount with monomer pinakon, hexanodioic acid, 3-hydroxyl pentanedioic acid; Place under 70 ℃ of oil baths; Magnetic agitation speed is 200rpm, adds molecular sieve, reacts after 48 hours; Add the dissolved in chloroform product; Remove by filter lypase, product solution for vacuum Rotary drying, molecular weight is 17000 polyester polymers.
Embodiment 5
According in the round-bottomed flask of mol ratio ratio adding in 15: 13: 2 100mL (ratio of carboxyl and hydroxyl is 16: 15), YLENE and monomer total amount add with 3: 1 mass ratio, add the lypase that derives from Candida antarctica by the every gram monomer of 100U/ total amount with monomer ethohexadiol, hexanodioic acid, 3-hydroxyl pentanedioic acid; Place under 80 ℃ of oil baths; Magnetic agitation speed is 400rpm, adds molecular sieve, reacts after 48 hours; Add the dissolved in chloroform product; Remove by filter lypase, product solution for vacuum Rotary drying, molecular weight is 7900 polyester polymers.
Embodiment 6
Monomer ethohexadiol, hexanodioic acid, 3-hydroxyl pentanedioic acid are added according to 15: 2: 12 ratios of mol ratio in the round-bottomed flask of 100mL (ratio of carboxyl and hydroxyl is 3: 2); Add the lypase that derives from Candida antarctica by the every gram monomer of 1500U/ total amount, place under 50 ℃ of oil baths, magnetic agitation speed is 200rpm; Add molecular sieve; React after 48 hours, add the dissolved in chloroform product, remove by filter lypase; Product solution for vacuum Rotary drying, molecular weight is 8700 polyester polymers.
Embodiment 7
Monomer ethohexadiol, 3-hydroxyl pentanedioic acid are added in the round-bottomed flask of 100mL according to 1: 1 ratio of mol ratio, and pyridine and monomer total amount add with 1: 1 mass ratio, add the lypase that derives from Candida antarctica by the every gram monomer of 2500U/ total amount; Place under 60 ℃ of oil baths; Magnetic agitation speed is 20rpm, adds molecular sieve, reacts after 48 hours; Add the THF lysate; Remove by filter lypase, product solution for vacuum Rotary drying, molecular weight is 2100 polyester polymers.
Embodiment 8
According in the round-bottomed flask of mol ratio ratio adding in 2: 1: 1 100mL (ratio of carboxyl and hydroxyl is 5: 4), the trimethyl carbinol and monomer total amount add with 1: 10 mass ratio, add the lypase that derives from Candida antarctica by the every gram monomer of 2000U/ total amount with monomer terepthaloyl moietie, hexanodioic acid, 3-hydroxyl pentanedioic acid; Place under 60 ℃ of oil baths; Magnetic agitation speed is 200rpm, adds molecular sieve, reacts after 12 hours; Add the acetone solution product; Remove by filter lypase, product solution for vacuum Rotary drying, molecular weight is 1700 polyester polymers.
Embodiment 9
According in the round-bottomed flask of mol ratio ratio adding in 15: 13: 2 100mL (ratio of carboxyl and hydroxyl is 16: 15), THF and monomer total amount add with 1: 1 mass ratio, add the lypase that derives from Mucor miehei by the every gram monomer of 1500U/ total amount with monomer ethohexadiol, hexanodioic acid, 3-hydroxyl pentanedioic acid; Place under 60 ℃ of oil baths; Magnetic agitation speed is 200rpm, adds molecular sieve, reacts after 48 hours; Add the dissolved in chloroform product; Remove by filter lypase, product solution for vacuum Rotary drying, molecular weight is 2900 polyester polymers.
Embodiment 10
Monomer ethohexadiol, hexanodioic acid, 3-hydroxyl pentanedioic acid are added according to 15: 13: 2 ratios of mol ratio in the round-bottomed flask of 100mL (ratio of carboxyl and hydroxyl is 16: 15), N, dinethylformamide and monomer total amount were with 1: 1 mass ratio adding; Add the lypase that derives from PPL by the every gram monomer of 1500U/ total amount, place under 110 ℃ of oil baths, magnetic agitation speed is 200rpm; Add molecular sieve; React after 48 hours, add the dissolved in chloroform product, remove by filter lypase; Product solution for vacuum Rotary drying, molecular weight is 5100 polyester polymers.
Embodiment 11
According in the round-bottomed flask of mol ratio ratio adding in 15: 10: 5 100mL (ratio of carboxyl and hydroxyl is 7: 6), chloroform and monomer total amount add with 1: 2 mass ratio, add the lypase that derives from PPL by the every gram monomer of 1500U/ total amount with monomer terepthaloyl moietie, dodecanedioic acid, 3-hydroxyl pentanedioic acid; Place under 40 ℃ of oil baths; Magnetic agitation speed is 200rpm, adds molecular sieve, reacts after 48 hours; Add the dissolved in chloroform product; Remove by filter lypase, product solution for vacuum Rotary drying, molecular weight is 3000 polyester polymers.
Embodiment 12
Monomer n-Hexadecane glycol, Succinic Acid, 3-hydroxyl pentanedioic acid are added according to 15: 9: 6 ratios of mol ratio in the round-bottomed flask of 100mL (ratio of carboxyl and hydroxyl is 6: 5), N, dinethylformamide and monomer total amount were with 1: 1 mass ratio adding; Add the lypase that derives from PPL by the every gram monomer of 1500U/ total amount, place under 120 ℃ of oil baths, magnetic agitation speed is 200rpm; Add molecular sieve; React after 48 hours, add the dissolved in chloroform product, remove by filter lypase; Product solution for vacuum Rotary drying, molecular weight is 3400 polyester polymers.
Comparative Examples
Butyleneglycol, hexanodioic acid are added in the round-bottomed flask of 100mL according to 1: 1 ratio of mol ratio, and toluene and monomer total amount add with 2: 1 mass ratio, add the lypase that derives from Candida antarctica by the every gram monomer of 1000U/ total amount; Place under 70 ℃ of oil baths, magnetic agitation speed is 200rpm, adds molecular sieve; React after 48 hours, add the dissolved in chloroform product, remove by filter lypase; Product solution for vacuum Rotary drying, molecular weight is 24600 polyester polymers.
Product analysis:
Carry out the product IR spectroscopy, testing method with embodiment 1 prepared product: sample was descended dry 24 hours 50 ℃ of vacuum drying ovens, use the pellet technique sample preparation, measure with the German Bruker VECTOR33 of company type IR.
Fig. 1 is the infrared spectrum of the obtained product of Comparative Examples; Fig. 2 is the infrared spectrum of embodiment 1 obtained product.Contrast infrared spectrum illustrated in figures 1 and 2, discovery is on the infrared spectrum of the terpolymer of butyleneglycol, hexanodioic acid and 3-hydroxyl pentanedioic acid, at 3500cm
-1Near tangible hydroxyl absorption peak has appearred.This explanation has correspondingly been introduced hydroxyl after in comonomer, introducing 3-hydroxyl pentanedioic acid on polymer molecular chain, obtained having the functional polyester of hydroxyl.Proof has obtained required product thus.
Claims (9)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100089035A CN102676591A (en) | 2012-01-12 | 2012-01-12 | Method for preparing polyester containing 3-hydroxy glutaric acid unit |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100089035A CN102676591A (en) | 2012-01-12 | 2012-01-12 | Method for preparing polyester containing 3-hydroxy glutaric acid unit |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102676591A true CN102676591A (en) | 2012-09-19 |
Family
ID=46809142
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012100089035A Pending CN102676591A (en) | 2012-01-12 | 2012-01-12 | Method for preparing polyester containing 3-hydroxy glutaric acid unit |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102676591A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR3060009A1 (en) * | 2016-12-13 | 2018-06-15 | Saint-Gobain Isover | THERMOSHURIC ORGANIC FOAMS AND PROCESS FOR PRODUCING THE SAME |
| CN116063666A (en) * | 2021-11-02 | 2023-05-05 | 四川大学 | A kind of multifunctional polyester material and its preparation method and application |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100092705A1 (en) * | 2005-06-17 | 2010-04-15 | Eastman Chemical Company | Bottles comprising polyester compositions which comprise cyclobutanediol |
| CN101041711B (en) * | 2007-03-30 | 2011-05-18 | 华南理工大学 | Method for preparing malic acid containing unit functional polyester by biological catalysis in organic medium |
-
2012
- 2012-01-12 CN CN2012100089035A patent/CN102676591A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100092705A1 (en) * | 2005-06-17 | 2010-04-15 | Eastman Chemical Company | Bottles comprising polyester compositions which comprise cyclobutanediol |
| CN101041711B (en) * | 2007-03-30 | 2011-05-18 | 华南理工大学 | Method for preparing malic acid containing unit functional polyester by biological catalysis in organic medium |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR3060009A1 (en) * | 2016-12-13 | 2018-06-15 | Saint-Gobain Isover | THERMOSHURIC ORGANIC FOAMS AND PROCESS FOR PRODUCING THE SAME |
| WO2018109362A1 (en) * | 2016-12-13 | 2018-06-21 | Saint-Gobain Isover | Thermosetting organic foams and manufacturing method |
| CN116063666A (en) * | 2021-11-02 | 2023-05-05 | 四川大学 | A kind of multifunctional polyester material and its preparation method and application |
| CN116063666B (en) * | 2021-11-02 | 2024-04-19 | 四川大学 | A multifunctional polyester material and its preparation method and application |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Okuda et al. | Renewable biobased polymeric materials: facile synthesis of itaconic anhydride-based copolymers with poly (L-lactic acid) grafts | |
| CN107540789B (en) | Synthesis method of bioactive derivative bagasse xylan syringic acid ester-g-AM | |
| Labet et al. | Citric acid as a benign alternative to metal catalysts for the production of cellulose-grafted-polycaprolactone copolymers | |
| De Oliveira et al. | All natural cork composites with suberin-based polyester and lignocellulosic residue | |
| Wang et al. | Preparation and rheological properties of starch-g-poly (butyl acrylate) catalyzed by horseradish peroxidase | |
| Zhang et al. | A multicomponent polymerization system: click–chemoenzymatic–ATRP in one-pot for polymer synthesis | |
| Olsén et al. | Transforming technical lignins to structurally defined star-copolymers under ambient conditions | |
| CN104910284A (en) | Double bond-containing modified starch as well as preparation method and application thereof | |
| Adharis et al. | Synthesis of (meth) acrylamide-based glycomonomers using renewable resources and their polymerization in aqueous systems | |
| CN101735184A (en) | Trithiocarbonate chain transfer agent and preparation method thereof | |
| WO2023035192A1 (en) | Self-healing organosilicon polymer material, and preparation method therefor and use thereof | |
| Techie-Menson et al. | New bio-based sustainable polymers and polymer composites based on methacrylate derivatives of furfural, solketal and lactic acid | |
| Fujieda et al. | Synthesis and characterization of novel potentially biodegradable aromatic polyesters consisting of divanillic acids with free phenolic hydroxyl groups | |
| CN114685764A (en) | Polyhydroxyalkanoate and preparation method thereof | |
| CN102676591A (en) | Method for preparing polyester containing 3-hydroxy glutaric acid unit | |
| Farhat et al. | Synthesis and characterization of thermoresponsive xylan networks by Diels–Alder reaction | |
| CN112409974B (en) | An amphiphilic bio-based degradable underwater adhesive and its preparation method and application | |
| CN108129647B (en) | A kind of star polyester compound and preparation method thereof | |
| Ren et al. | A new strategy for acid anhydrides-modified xylans in ionic liquids | |
| Fujieda et al. | Synthesis and enzymatic biodegradation of co-polyesters consisting of divanillic acid with free hydroxyl groups | |
| CN107032991B (en) | A kind of fatty acid monomer, preparation method and thermoplastic polymer synthesized by application | |
| CN113045692A (en) | Method for synthesizing functionalized polymer through post-modification | |
| JP6473348B2 (en) | Method for producing (meth) acrylic lactic acid macromonomer, and method for producing polylactic acid graft polymer and polylactic acid comb polymer using (meth) acrylic lactic acid macromonomer | |
| CN108148188A (en) | A kind of combed petchem and preparation method thereof | |
| CN113292707A (en) | Preparation method of terminal group functionalized hyperbranched polyolefin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20120919 |