CN108164690A - Method for preparing polyester - Google Patents
Method for preparing polyester Download PDFInfo
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- CN108164690A CN108164690A CN201810043792.9A CN201810043792A CN108164690A CN 108164690 A CN108164690 A CN 108164690A CN 201810043792 A CN201810043792 A CN 201810043792A CN 108164690 A CN108164690 A CN 108164690A
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- Prior art keywords
- butyl
- propyl
- solvent
- normal
- hydroxyl
- Prior art date
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- 238000000034 method Methods 0.000 title claims abstract description 39
- 229920000728 polyester Polymers 0.000 title claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 76
- -1 aliphatic phosphate esters Chemical class 0.000 claims abstract description 39
- 229920000642 polymer Polymers 0.000 claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 239000000178 monomer Substances 0.000 claims abstract description 17
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims abstract description 15
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 10
- 239000003999 initiator Substances 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 72
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 66
- 150000002148 esters Chemical class 0.000 claims description 30
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 claims description 24
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 17
- JBFHTYHTHYHCDJ-UHFFFAOYSA-N gamma-caprolactone Chemical compound CCC1CCC(=O)O1 JBFHTYHTHYHCDJ-UHFFFAOYSA-N 0.000 claims description 17
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 16
- 125000005843 halogen group Chemical group 0.000 claims description 15
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 15
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 11
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- YFHICDDUDORKJB-UHFFFAOYSA-N trimethylene carbonate Chemical compound O=C1OCCCO1 YFHICDDUDORKJB-UHFFFAOYSA-N 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- 150000001721 carbon Chemical group 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 6
- 150000002903 organophosphorus compounds Chemical class 0.000 claims description 6
- 125000003342 alkenyl group Chemical group 0.000 claims description 5
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 125000000304 alkynyl group Chemical group 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- 150000002240 furans Chemical class 0.000 claims description 4
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 150000001345 alkine derivatives Chemical class 0.000 claims description 2
- 229960005222 phenazone Drugs 0.000 claims description 2
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims 1
- VEZXCJBBBCKRPI-UHFFFAOYSA-N beta-propiolactone Chemical compound O=C1CCO1 VEZXCJBBBCKRPI-UHFFFAOYSA-N 0.000 claims 1
- 125000001309 chloro group Chemical group Cl* 0.000 claims 1
- 229910052736 halogen Inorganic materials 0.000 claims 1
- 150000002367 halogens Chemical class 0.000 claims 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims 1
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 claims 1
- 239000003960 organic solvent Substances 0.000 claims 1
- 229960000380 propiolactone Drugs 0.000 claims 1
- 238000006467 substitution reaction Methods 0.000 claims 1
- 239000008096 xylene Substances 0.000 claims 1
- 239000006185 dispersion Substances 0.000 abstract description 29
- 239000000463 material Substances 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 2
- 239000012535 impurity Substances 0.000 abstract description 2
- 230000035484 reaction time Effects 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000000746 purification Methods 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 42
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 39
- 238000005481 NMR spectroscopy Methods 0.000 description 25
- 238000006116 polymerization reaction Methods 0.000 description 22
- 238000001556 precipitation Methods 0.000 description 22
- 229910052786 argon Inorganic materials 0.000 description 21
- 239000012298 atmosphere Substances 0.000 description 21
- 239000007789 gas Substances 0.000 description 21
- 238000001035 drying Methods 0.000 description 20
- 238000001291 vacuum drying Methods 0.000 description 20
- 239000002253 acid Substances 0.000 description 17
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 15
- 239000006166 lysate Substances 0.000 description 14
- VAJVDSVGBWFCLW-UHFFFAOYSA-N 3-Phenyl-1-propanol Chemical class OCCCC1=CC=CC=C1 VAJVDSVGBWFCLW-UHFFFAOYSA-N 0.000 description 13
- 229920001610 polycaprolactone Polymers 0.000 description 10
- 239000007788 liquid Substances 0.000 description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 235000019445 benzyl alcohol Nutrition 0.000 description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 239000004632 polycaprolactone Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 4
- 229920001400 block copolymer Polymers 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001819 mass spectrum Methods 0.000 description 3
- 239000003863 metallic catalyst Substances 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 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 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- VNOCCXRFVCGUCC-UHFFFAOYSA-N O=C1CC=CP1=O Chemical class O=C1CC=CP1=O VNOCCXRFVCGUCC-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 229930188620 butyrolactone Natural products 0.000 description 2
- 150000004651 carbonic acid esters Chemical class 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 description 2
- 125000003963 dichloro group Chemical group Cl* 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007717 exclusion Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229920001596 poly (chlorostyrenes) Polymers 0.000 description 2
- 229920000747 poly(lactic acid) Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 2
- 239000004425 Makrolon Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- PYKHKJJMHQLJOH-UHFFFAOYSA-N bis(3-methylbutyl) hydrogen phosphate Chemical compound CC(C)CCOP(O)(=O)OCCC(C)C PYKHKJJMHQLJOH-UHFFFAOYSA-N 0.000 description 1
- 210000000481 breast Anatomy 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical group 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- 125000000392 cycloalkenyl group Chemical group 0.000 description 1
- 238000013501 data transformation Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N deuterated chloroform Substances [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000006561 solvent free reaction Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-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
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/87—Non-metals or inter-compounds thereof
-
- 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
- C08G63/823—Preparation processes characterised by the catalyst used for the preparation of polylactones or polylactides
-
- 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
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/30—General preparatory processes using carbonates
- C08G64/305—General preparatory processes using carbonates and alcohols
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
The invention discloses a method for preparing polyester, belonging to the technical field of polymer synthesis. The invention uses a cyclic monomer as a reaction monomer, a plurality of aliphatic phosphate esters as catalysts, and an alcohol compound as an initiator to carry out ring-opening polymerization reaction under the condition of solution or bulk, and the polyester is obtained by separation and purification. The method for preparing the high-molecular biodegradable material which has the advantages of large molecular weight, narrow dispersion degree and no metal impurities is simple in process, low in cost, high in conversion rate, short in reaction time, controllable in process and environment-friendly.
Description
Technical field
The invention belongs to macromolecule synthesising technology fields, and in particular to aliphatic organophosphorus compounds catalyst is cyclic annular
The method that compound ring-opening polymerisation prepares polyester.
Background technology
Polyester and polycarbonate-based material because its recyclability, biodegradability and it is environmentally friendly the features such as, and have
There are very far-reaching research significance and extensive prospects for commercial application, obtained extensively in fields such as food packaging, plastic films
It uses.They have fine biocompatibility simultaneously, have relatively low toxicity and rejection to organism, thus are carried in drug
Body, tissue engineering material, suture, Medical screw etc. are with a wide range of applications.
Ring-opening polymerisation is a kind of method for preparing polyester and polycarbonate polymer.In early stage ring-opening polymerization
In, catalyst generally using the metallic catalysts such as organic tin salt, organic zinc salt and organic aluminium salt, as US5235031,
JP0124651, CN1544504 and CN1814644 are largely studied in ring-opening polymerization.The medical poly- breast of commercialization
Sour material using stannous octoate, studies have found that, stannous octoate as metallic catalyst itself have bio-toxicity.
Polymer is obtained with being difficult to the metal residual removed by stannous octoate polymerisation, can limit its in biomedical sector and
The application of field of microelectronics.In contrast to metallic catalyst, select organic catalyst that can avoid this problem well.
Tommy Iversen seminars in 2004 report using propionic acid, trifluoroacetic acid, caproic acid etc. as organic monoacid and are catalyzed
Ring-opening polymerisation 6-caprolactone, δ-valerolactone and trimethylene carbonate achieve preferable effect in the solution for agent, compared to second
The features such as ethereal hydrochloric acid catalyst is efficient there are catalytic efficiency, and chemical property is stablized, and catalyst type is more.But this method remains unchanged
There is some defects, general including used catalyst effect, and resulting polymers molecular weight is relatively low, molecular weight distribution is wider
The problems such as.Toyoji Kakuchi in 2011 and 2013 et al. are reported using diphenyl phosphate as organic monoacid catalyst molten
Ring-opening polymerisation 6-caprolactone, δ-valerolactone and trimethylene carbonate achieve preferable effect in liquid, compared to other acids
Catalyst has the features such as low toxicity, chemical property is stablized.But still there is some defects, catalysis as used for this method
The problems such as agent is expensive, solvent dosage is big.Nowadays, some aliphatic phosphate has realized industrial production, cheap, has
The potentiality of commercial Application；In addition, high molecular weight can be obtained under the conditions of solvent-free reaction as weak acid catalyst, low polydispersity
Polyester, at high temperature still have excellent reactivity and controlling, in the catalysis of some monomers, relatively before report tool
There is apparent advantage, and preferably resolve the problems such as catalyst is expensive, solvent dosage is big.
Invention content
Present invention aims at providing, a kind of simple for process, of low cost, high conversion rate, reaction time is short, process control
And environmental-friendly method prepares that molecular weight is big, and dispersion degree is narrow, not metal impurities high-molecular biologic degradation materials.
The present invention it has been investigated that, the difference of the side chain substituents of organophosphorus ester will influence catalytic efficiency.Ring-opening polymerisation
Reaction need to determine suitable catalyst according to the character requirement of polymerizate and the process conditions of polymerizing reactor, fit
Suitable temperature and range of temperature ensures that polymerisation effectively carries out in certain temperature range.
The present invention is verified by experiments, and the ring-opening polymerization carried out under bulk conditions is not only on the time compared under the same terms
Solvent polymeric shorten dramatically, dispersion degree is also kept low.Ontology ring-opening polymerisation can also make under the conditions of partial solvent
Almost nonreactive monomer, can be by successful ring-opening polymerisation under bulk conditions.
Technical scheme is as follows：
The method that organophosphorus compounds catalyst cyclic monomer ring-opening polymerisation provided by the invention prepares polyester utilizes
Cyclic monomer is as reaction monomers, and a variety of aliphatic phosphate esters are as catalyst, by the use of alcohol compound as initiator, molten
Ring-opening polymerization is carried out under liquid or bulk conditions, polyester is obtained through isolating and purifying.
Shown in the structure such as formula (I) of aliphatic phosphate ester class catalyst described in method made above：
R1、R2Selected from the alkyl with 2~5 carbon atoms, alkenyl or alkynyl, have 2~5 carbon atoms and by halogen atom,
One or more substituted alkyl in hydroxyl and furans；Or R1、R2Form alkyl, alkenyl or alkynes with 3~8 carbon atoms
Base has 3~8 carbon atoms and by in cycloalkyl, halogen atom, phenyl and substituted-phenyl one or a variety of substituted alkyl, alkene
Base or alkynyl.
R1、R2Identical group in ethyl, propyl, pi-allyl, propargyl, normal-butyl, tertiary butyl or n-pentyl, choosing
From ethyl, propyl, normal-butyl, tertiary butyl or n-pentyl and by one or more substituted identical in halogen atom, hydroxyl and furans
Group；Or R1、R2Form ethyl, propyl, pi-allyl, propargyl, normal-butyl, tertiary butyl or n-pentyl, formed by cycloalkyl,
In one in cycloalkenyl group, halogen atom, phenyl and substituted-phenyl or a variety of substituted ethyls, propyl, pi-allyl, propargyl, normal-butyl,
Tertiary butyl or n-pentyl.
Representative organophosphorus compounds catalyst has the structure as shown in number 1~8：
The organophosphorus compounds catalyst that method made above uses can be left-handed organophosphorus ester, dextrorotation organic phosphoric acid
One kind in ester, meso organophosphorus ester or racemic organophosphorus ester.
The cyclic monomer that method made above uses is selected from following one or more：
(1) monomer has the structure as shown in formula (II)：
Wherein, A is [- (CR3R4)—]n, n is 2~10 integer；R3、R4Selected from H, there is the alkyl of 1~5 carbon atom
With with the identical or different group in 1~5 carbon atom and the alkyl that is replaced by halogen atom or hydroxyl；
(2) monomer has the structure as shown in formula (III)：
Wherein, A is [- (CR5R6)—]n, n is 3~10 integer；R5、R6Selected from H, there is the alkyl of 1~5 carbon atom
With with the identical or different group in 1~5 carbon atom and the alkyl that is replaced by halogen atom or hydroxyl.
It is preferred that R3、R4Be selected from ethyl, propyl, normal-butyl, tertiary butyl, n-pentyl, neopentyl or selected from by halogen atom or
Identical or different base in hydroxyl in one or more substituted ethyls, propyl, normal-butyl, tertiary butyl, n-pentyl, neopentyl
Group；
R5、R6Be selected from propyl, normal-butyl, tertiary butyl, n-pentyl or in by halogen atom or hydroxyl it is one or more
Identical or different group in substituted propyl, normal-butyl, tertiary butyl, n-pentyl.
The cyclic monomer that method made above uses is selected from following one or more：L- lactides, D- lactides,
DL- lactides, gamma-butyrolacton, δ-valerolactone, 6-caprolactone, chloro caprolactone, trimethylene carbonate, hydroxyl trimethylene
Carbonic ester, chloro trimethylene carbonate.
The reaction temperature that method made above uses is at 10~150 degrees Celsius；It is preferred that ring-opening polymerisation under solvent-free conditions
Reaction 10 minutes~24 hours controls temperature range at 50~130 degrees Celsius, preferably 80~100 degrees Celsius (L- lactides,
D- lactides or DL- lactides are preferably 120~140 degrees Celsius)；The cyclic compound and organophosphor that method made above uses
The molar ratio of acid esters catalyst is 5~500, preferably 20~300.
The initiator that method made above uses is alcohol compound, including methanol, ethyl alcohol, normal propyl alcohol, isopropanol, positive fourth
Alcohol, the tert-butyl alcohol, benzyl alcohol, benzyl carbinol, 3- phenyl-1-propanols, ethylene glycol, condensed ethandiol or pentaerythrite, preferably n-butanol,
Benzyl alcohol and 3- phenyl-1-propanols.
Isolating and purifying described in method made above refers to be sunk with the solvent that settles out again after reaction product is dissolved with good solvent
Precipitation goes out, and good solvent used is dichloromethane, chloroform, toluene, benzene, acetone or tetrahydrofuran, preferably dichloromethane, trichlorine
Methane or toluene, the solvent used that settles out is methanol or ethyl alcohol.
In the preparation method of aliphatic polyester and fatty poly-ester carbonate, the structure of polymer passes through1H H NMR spectroscopies with13C
H NMR spectroscopy identifies that the molecular weight and dispersion degree property of polymer are measured by size exclusion chromatograph and flight time mass spectrum.
Description of the drawings
1. polycaprolactone of attached drawing1H NMR spectras
2. poly- valerolactone of attached drawing1H NMR spectras
The flight time mass spectrum figure of 3. polytrimethylene carbonate of attached drawing
[6-caprolactone] of 4. different proportion of attached drawing0/ [3- phenyl-1-propanols]0SEC curves
The SEC curves of the embedding poly- valerolactone of 5. polycaprolactone of attached drawing
Specific embodiment
It can be further illustrated the present invention by the following example, embodiment is in order to illustrate being not intended to limit the present invention.
Any those of ordinary skill of this field can understand that these embodiments are not limit the invention in any way, it can be done
Appropriate modification and data transformation and without prejudice to the present invention essence and deviate the scope of the present invention.
Reaction conversion ratio in embodiment by1H H NMR spectroscopies measure, and are determining instrument and test condition is：Nuclear Magnetic Resonance
(Bruker DRX-400 spectrometer), with CDCl3For solvent.The number-average molecular weight and dispersion of polyester and makrolon
Degree is measured by size exclusion chromatograph (SEC), and experiment condition is：Column temperature：25 DEG C, solvent：THF (HPLC), flow velocity：0.7mL/min,
HPLC is pumped：Waters 515, detector：RI (Wyatt Optilab rEX), chromatographic column：HR2, standard specimen：Polystyrene (PS) MW
=900~1.74 × 106G/mol, PDI<1.1.
Embodiment 1：
By 6-caprolactone (0.55ml, 5mmol), 3- phenyl-1-propanols (13 μ L, 0.1mmol) and dibutylphosphoric acid ester (20 μ
L, 0.1mmol) it adds in the polymerization pipe of 10mL, under the atmosphere of argon gas, it is heated to 90 DEG C.Reaction adds in three second after 3.5 hours
Amine terminates reaction, by1It is 99% that H H NMR spectroscopies, which measure conversion ratio,.With just dissolving the dichloromethane of polymer meltage, will dissolve
Liquid is poured into cold methanol, and precipitation is filtered and put to vacuum drying chamber drying to constant weight, obtains 0.33g polycaprolactones, yield is
58%, number-average molecular weight MnIt is 5640, dispersion degree 1.10.The sterling for the polycaprolactone being prepared1H NMR spectras are shown in attached drawing
1。
Embodiment 2：
By 6-caprolactone (0.55ml, 5mmol), 3- phenyl-1-propanols (11 μ L, 0.1mmol) and dibutylphosphoric acid ester (20 μ
L, 0.1mmol) it adds in the polymerization pipe of 10mL, the dichloromethane of 1.25ml is added in as solvent, under the atmosphere of argon gas, heating
To 25 DEG C.Reaction adds in triethylamine after 36 hours and terminates reaction, by1It is 94% that H H NMR spectroscopies, which measure conversion ratio,.Reaction solution is poured into
In cold methanol, precipitation is filtered and is put to vacuum drying chamber drying to constant weight, obtains 0.37g polycaprolactones, yield 65%, number is
Molecular weight MnIt is 5730, dispersion degree 1.07.
Embodiment 3：
By 6-caprolactone (0.55ml, 5mmol), 3- phenyl-1-propanols (13 μ L, 0.1mmol) and dibutylphosphoric acid ester (20 μ
L, 0.1mmol) it adds in the polymerization pipe of 10mL, under the atmosphere of argon gas, it is heated to 110 DEG C.Reaction adds in triethylamine after 1 hour
Reaction is terminated, by1It is 99% that H H NMR spectroscopies, which measure conversion ratio,.With just dissolving the dichloromethane of polymer meltage, by lysate
It pours into cold methanol, precipitation is filtered and is put to vacuum drying chamber drying to constant weight, obtains 0.31g polycaprolactones, yield 58%,
Number-average molecular weight MnIt is 5500, dispersion degree 1.27.Actual molecular weight be less than theoretical molecular weight, dispersion degree it is larger (>1.20) it, produces
Object is not up to expected.
Embodiment 4：
By δ-valerolactone (0.45ml, 5mmol), 3- phenyl-1-propanols (13 μ L, 0.1mmol) and dibutylphosphoric acid ester (20 μ
L, 0.1mmol) it adds in the polymerization pipe of 10mL, under the atmosphere of argon gas, it is heated to 80 DEG C.Reaction adds in triethylamine after forty minutes
Reaction is terminated, by1It is 98% that H H NMR spectroscopies, which measure conversion ratio,.With just dissolving the dichloromethane of polymer meltage, by lysate
It pours into cold methanol, precipitation is filtered and put to vacuum drying chamber drying to constant weight, obtains the poly- valerolactone of 0.38g, yield is
76%, number-average molecular weight MnIt is 5120, dispersion degree 1.08.The sterling of poly- valerolactone being prepared1H NMR spectras are shown in attached drawing
2。
Embodiment 5：
By δ-valerolactone (0.45ml, 5mmol), 3- phenyl-1-propanols (13 μ L, 0.1mmol) and dibutylphosphoric acid ester (20 μ
L, 0.1mmol) it adds in the polymerization pipe of 10mL, under the atmosphere of argon gas, it is heated to 110 DEG C.Reaction adds in three second after ten minutes
Amine terminates reaction, by1It is 99% that H H NMR spectroscopies, which measure conversion ratio,.With just dissolving the dichloromethane of polymer meltage, will dissolve
Liquid is poured into cold methanol, and precipitation is filtered and put to vacuum drying chamber drying to constant weight, obtains the poly- valerolactone of 0.38g, yield is
76%, number-average molecular weight MnIt is 4930, dispersion degree 1.25.Actual molecular weight is less than theoretical molecular weight, and dispersion degree is larger, product
It is not up to expected.
Embodiment 6：
By trimethylene carbonate (0.26g, 2.5mmol), 3- phenyl-1-propanols (13 μ L, 0.1mmol) and di(2-ethylhexyl)phosphate fourth
Ester (20 μ L, 0.1mmol) is added in the polymerization pipe of 10mL, under the atmosphere of argon gas, is heated to 90 DEG C.Reaction adds in after 4 hours
Triethylamine terminates reaction, by1It is 96% that H H NMR spectroscopies, which measure conversion ratio,.It, will with just dissolving the dichloromethane of polymer meltage
Lysate is poured into cold methanol, and precipitation is filtered and put to vacuum drying chamber drying to constant weight, obtains 0.17g polytrimethylene carbonic acid
Ester, yield 65%, number-average molecular weight MnIt is 2690, dispersion degree 1.12.The polytrimethylene carbonate being prepared it is pure
Product flight time mass spectrum figure is shown in attached drawing 3.
Embodiment 7：
By trimethylene carbonate (0.52g, 2.5mmol), 3- phenyl-1-propanols (13 μ L, 0.1mmol) and di(2-ethylhexyl)phosphate fourth
Ester (20 μ L, 0.1mmol) is added in the polymerization pipe of 10mL, under the atmosphere of argon gas, is heated to 130 DEG C.Reaction adds in after 2 hours
Triethylamine terminates reaction, by1It is 99% that H H NMR spectroscopies, which measure conversion ratio,.It, will with just dissolving the dichloromethane of polymer meltage
Lysate is poured into cold methanol, and precipitation is filtered and put to vacuum drying chamber drying to constant weight, obtains 0.36g polytrimethylene carbonic acid
Ester, yield 69%, number-average molecular weight MnIt is 5020, dispersion degree 1.31.Actual molecular weight is less than theoretical molecular weight, dispersion degree
Larger, product is not up to expected.
Embodiment 8：
By L- lactides (0.36g, 2.5mmol), 3- phenyl-1-propanols (13 μ L, 0.1mmol) and dibutylphosphoric acid ester (20 μ
L, 0.1mmol) it adds in the polymerization pipe of 10mL, under the atmosphere of argon gas, it is heated to 120 DEG C.Reaction adds in three second after 24 hours
Amine terminates reaction, by1It is 98% that H H NMR spectroscopies, which measure conversion ratio,.With just dissolving the dichloromethane of polymer meltage, will dissolve
Liquid is poured into cold methanol, and precipitation is filtered and put to vacuum drying chamber drying to constant weight, obtains 0.23g polylactides, yield is
64%, number-average molecular weight MnIt is 3820, dispersion degree 1.15.
Embodiment 9：
By L- lactides (0.36g, 2.5mmol), 3- phenyl-1-propanols (13 μ L, 0.1mmol) and dibutylphosphoric acid ester (20 μ
L, 0.1mmol) it adds in the polymerization pipe of 10mL, under the atmosphere of argon gas, it is heated to 150 DEG C.Reaction adds in three second after 24 hours
Amine terminates reaction, by1It is 96% that H H NMR spectroscopies, which measure conversion ratio,.With just dissolving the dichloromethane of polymer meltage, will dissolve
Liquid is poured into cold methanol, and precipitation is filtered and put to vacuum drying chamber drying to constant weight, obtains 0.18g polylactides, yield is
67%, number-average molecular weight MnIt is 5500, dispersion degree 1.32.Actual molecular weight is less than theoretical molecular weight, and dispersion degree is larger, product
It is not up to expected.
Embodiment 10：
By L- lactides (0.36g, 2.5mmol), 3- phenyl-1-propanols (13 μ L, 0.1mmol) and dibutylphosphoric acid ester (20 μ
L, 0.1mmol) it adds in the polymerization pipe of 10mL, the dichloromethane dissolving of 1.25ml is added in, under the atmosphere of argon gas, is heated to 25
℃.Reaction adds in triethylamine after 72 hours and terminates reaction, by1It is almost nil that H H NMR spectroscopies measure conversion ratio, without heavy in cold methanol
Precipitation goes out, and illustrates under room temperature L- lactides in the catalyst system and catalyzing almost without conversion ratio.In addition, D- lactides and DL- lactides
With similar result.
Embodiment 11：
By 6-caprolactone (2.2ml, 20mmol), 3- phenyl-1-propanols (13 μ L, 0.1mmol) and dibutylphosphoric acid ester (20 μ
L, 0.1mmol) it adds in the polymerization pipe of 10mL, under the atmosphere of argon gas, it is heated to 90 DEG C.Reaction adds in three second after 15.5 hours
Amine terminates reaction, by1It is 94% that H H NMR spectroscopies, which measure conversion ratio,.With just dissolving the dichloromethane of polymer meltage, will dissolve
Liquid is poured into cold methanol, and precipitation is filtered and put to vacuum drying chamber drying to constant weight, obtains 1.56g polycaprolactones, yield is
71%, number-average molecular weight MnIt is 23030, dispersion degree 1.05.[6-caprolactone] of different proportion0/ [3- phenyl-1-propanols]0's
SEC curves are shown in attached drawing 4.
Embodiment 12：
By 6-caprolactone (0.28ml, 2.5mmol), benzyl alcohol (10 μ L, 0.1mmol) and dibutylphosphoric acid ester (20 μ L,
It 0.1mmol) adds in the polymerization pipe of 10mL, under the atmosphere of argon gas, is heated to 90 DEG C.6-caprolactone base after reaction 1.5 hours
This reaction was complete, then adds δ-valerolactone (0.23ml, 2.5mmol) the reaction was continued 20 minutes, obtain 6-caprolactone in δ-penta
Ester molar ratio is 1：1 block copolymer, by1H H NMR spectroscopies measure conversion ratio up to 97%.With the dichloro for just making polymer meltage
Methane dissolves, and lysate is poured into cold methanol, and precipitation is filtered and put to vacuum drying chamber drying to constant weight, and it is embedding to obtain 0.36g
Section copolymer, yield 70%, number-average molecular weight MnIt is 5680, dispersion degree 1.10.The polycaprolactone embedding poly- penta being prepared
The SEC curves of lactone are shown in attached drawing 5
Embodiment 13：
By trimethylene carbonate (0.26g, 2.5mmol), benzyl carbinol (12 μ L, 0.1mmol) and dibutylphosphoric acid ester (20 μ
L, 0.1mmol) it adds in the polymerization pipe of 10mL, under the atmosphere of argon gas, it is heated to 90 DEG C.Trimethylene carbon after reaction 4 hours
The reaction was complete substantially for acid esters, then adds 6-caprolactone (0.28ml, 2.5mmol) the reaction was continued 2 hours, obtains trimethylene carbonic acid
Ester is 1 with 6-caprolactone molar ratio：1 block copolymer, by1H H NMR spectroscopies measure conversion ratio up to 96%.With just making polymer molten
The dichloromethane dissolving of solution amount, lysate is poured into cold methanol, precipitation is filtered and put to vacuum drying chamber drying to constant weight, is obtained
To 0.34g block polymers, yield 63%, number-average molecular weight MnIt is 5180, dispersion degree 1.12.
Embodiment 14：
By trimethylene carbonate (0.26g, 2.5mmol), benzyl alcohol (10 μ L, 0.1mmol) and dibutylphosphoric acid ester (20 μ
L, 0.1mmol) it adds in the polymerization pipe of 10mL, under the atmosphere of argon gas, it is heated to 90 DEG C.Trimethylene carbon after reaction 4 hours
The reaction was complete substantially for acid esters, then adds gamma-butyrolacton (0.20ml, 2.5mmol) the reaction was continued 1 hour, obtains trimethylene carbon
Acid esters is 1 with gamma-butyrolacton molar ratio：1 block copolymer, by1H H NMR spectroscopies measure conversion ratio up to 95%.With just making polymerization
The dichloromethane dissolving of object meltage, lysate is poured into cold methanol, and precipitation is filtered and put to vacuum drying chamber drying to perseverance
Weight, obtains 0.33g block polymers, yield 72%, number-average molecular weight MnIt is 4830, dispersion degree 1.09.
Embodiment 15：
By gamma-butyrolacton (0.40ml, 5mmol), n-butanol (8 μ L, 0.1mmol) and phosphoric acid dipropyl (18 μ L,
It 0.1mmol) adds in the polymerization pipe of 10mL, under the atmosphere of argon gas, is heated to 80 DEG C.It is whole that reaction adds in triethylamine after 2 hours
Only react, by1It is 98% that H H NMR spectroscopies, which measure conversion ratio,.With just dissolving the dichloromethane of polymer meltage, lysate is fallen
Enter in cold methanol, precipitation is filtered and put to vacuum drying chamber drying to constant weight, obtains the poly- butyrolactone of 0.33g, yield 62%, number
Average molecular weight MnIt is 4530, dispersion degree 1.15.
Embodiment 16：
By 6-caprolactone (0.55ml, 5mmol), the tert-butyl alcohol (8 μ L, 0.1mmol) and di-iso-amyl phosphate (24 μ L,
It 0.1mmol) adds in the polymerization pipe of 10mL, under the atmosphere of argon gas, is heated to 80 DEG C.It is whole that reaction adds in triethylamine after 2 hours
Only react, by1It is 98% that H H NMR spectroscopies, which measure conversion ratio,.With just dissolving the dichloromethane of polymer meltage, lysate is fallen
Enter in cold methanol, precipitation is filtered and put to vacuum drying chamber drying to constant weight, obtains 0.39g polycaprolactones, yield 72%, number
Average molecular weight MnIt is 5230, dispersion degree 1.08.
Embodiment 17：
By chloro trimethylene carbonate (0.68g, 5mmol), pentaerythrite (10 μ L, 0.1mmol) and 3- hydroxyl octahydros
Benzo [e] [1,3,2] dioxo Phospholes -3- oxides (25 μ L, 0.1mmol) are added in the polymerization pipe of 10mL, in argon
Under the atmosphere of gas, it is heated to 80 DEG C.Reaction adds in triethylamine after 2 hours and terminates reaction, by1H H NMR spectroscopies measure conversion ratio
98%.With just dissolving the dichloromethane of polymer meltage, lysate is poured into cold methanol, precipitation is filtered and put to vacuum
Drying box drying obtains 0.39g polychlorostyrene for trimethylene carbonate, yield 57%, number-average molecular weight M to constant weightnIt is 7100,
Dispersion degree is 1.18.
Embodiment 18：
By chloro caprolactone (0.58ml, 5mmol), benzyl carbinol (12 μ L, 0.1mmol) and 3- hydroxyl -1,5- dihydrobenzos
[e] [1,3,2] dioxo Phospholes -3- oxides (24 μ L, 0.1mmol) are added in the polymerization pipe of 10mL, in argon gas
Under atmosphere, it is heated to 80 DEG C.Reaction adds in triethylamine after 2 hours and terminates reaction, by1It is 98% that H H NMR spectroscopies, which measure conversion ratio,.With
The dichloromethane of polymer meltage just is dissolved, lysate is poured into cold methanol, precipitation is filtered and put to vacuum drying chamber
Drying obtains 0.41g polychlorostyrene for caprolactone, yield 71%, number-average molecular weight M to constant weightnIt is 7620, dispersion degree 1.12.
Embodiment 19：
By hydroxyl trimethylene carbonate (0.55g, 5mmol), benzyl alcohol (10 μ L, 0.1mmol) and bis- (furans -2- first
Base) hydrophosphate (28 μ L, 0.1mmol) add in 10mL polymerization pipe in, under the atmosphere of argon gas, be heated to 100 DEG C.Reaction 2
Triethylamine is added in after hour and terminates reaction, by1It is 98% that H H NMR spectroscopies, which measure conversion ratio,.With the dichloro for just making polymer meltage
Methane dissolves, and lysate is poured into cold methanol, and precipitation is filtered and put to vacuum drying chamber drying to constant weight, is obtained 0.35g and is gathered
Hydroxyl trimethylene carbonate, yield 64%, number-average molecular weight MnIt is 7090, dispersion degree 1.15.
Embodiment 20：
By 6-caprolactone (0.55ml, 5mmol), pentaerythrite (10 μ L, 0.1mmol) and phosphoric acid hydrogen diallyl (18 μ L,
It 0.1mmol) adds in the polymerization pipe of 10mL, under the atmosphere of argon gas, is heated to 90 DEG C.Reaction adds in triethylamine after 2.5 hours
Reaction is terminated, by1It is 98% that H H NMR spectroscopies, which measure conversion ratio,.With just dissolving the dichloromethane of polymer meltage, by lysate
It pours into cold methanol, precipitation is filtered and is put to vacuum drying chamber drying to constant weight, obtains 0.35g polycaprolactones, yield 62%,
Number-average molecular weight MnIt is 5590, dispersion degree 1.10.
Embodiment 21：
By gamma-butyrolacton (0.40ml, 5mmol), benzyl alcohol (10 μ L, 0.1mmol) and phosphoric acid hydrogen diine propyl ester (18 μ L,
It 0.1mmol) adds in the polymerization pipe of 10mL, under the atmosphere of argon gas, is heated to 100 DEG C.It is whole that reaction adds in triethylamine after 2 hours
Only react, by1It is 96% that H H NMR spectroscopies, which measure conversion ratio,.With just dissolving the dichloromethane of polymer meltage, lysate is fallen
Enter in cold methanol, precipitation is filtered and put to vacuum drying chamber drying to constant weight, obtains the poly- butyrolactone of 0.33g, yield 74%, number
Average molecular weight MnIt is 4300, dispersion degree 1.15.
Claims (10)
- A kind of 1. method for preparing polyester, it is characterised in that：In the presence of initiator, it is catalyzed using aliphatic organophosphorus compounds The method that agent is catalyzed cyclic monomer ring-opening polymerisation, obtains polyester polymer,The initiator for methanol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol, the tert-butyl alcohol, benzyl alcohol, benzyl carbinol, 3- phenyl- 1- propyl alcohol, ethylene glycol, condensed ethandiol or pentaerythrite；Shown in the aliphatic organophosphorus compounds catalyst structure such as formula (I)：R1、R2Selected from the alkyl with 2~5 carbon atoms, alkenyl or alkynyl, there are 2~5 carbon atoms and by halogen atom, hydroxyl With substituted alkyl one or more in furans；Or R1、R2Form alkyl, alkenyl or alkynyl with 3~8 carbon atoms, tool There are 3~8 carbon atoms and by in cycloalkyl, halogen atom, phenyl and substituted-phenyl one or a variety of substituted alkyl, alkenyl or alkynes Base.The cyclic monomer is selected from following one or more：(1) monomer has the structure as shown in formula (II)：Wherein, A is [- (CR3R4)—]n, n is 2~10 integer；R3、R4Alkyl and tool selected from H, with 1~5 carbon atom Identical or different group in the alkyl for having 1~5 carbon atom and being replaced by halogen atom or hydroxyl；(2) monomer has the structure as shown in formula (III)：Wherein, A is [- (CR5R6)—]n, n is 3~10 integer；R5、R6Alkyl and tool selected from H, with 1~5 carbon atom Identical or different group in the alkyl for having 1~5 carbon atom and being replaced by halogen atom or hydroxyl.
- 2. according to the method described in claim 1, it is characterized in that：R1、R2It is selected from ethyl, propyl, pi-allyl, propargyl, just Identical group in butyl, tertiary butyl or n-pentyl, selected from ethyl, propyl, normal-butyl, tertiary butyl or n-pentyl and by halogen original One or more substituted identical groups in son, hydroxyl and furans；Or R1、R2Formed ethyl, propyl, pi-allyl, propargyl, Normal-butyl, tertiary butyl or n-pentyl are formed by one in cycloalkyl, halogen atom, phenyl and substituted-phenyl or a variety of substituted second Base, propyl, pi-allyl, propargyl, normal-butyl, tertiary butyl or n-pentyl.
- 3. method according to claim 1 or 2, it is characterised in that：The organophosphorus compounds catalyst such as number 1~ Structure shown in 8：
- 4. according to the method described in claim 1, it is characterized in that：The organophosphorus compounds catalyst that the method uses is One kind in left-handed organophosphorus ester, dextrorotation organophosphorus ester, meso organophosphorus ester or racemic organophosphorus ester.
- 5. according to the method described in claim 1, it is characterized in that：R3、R4It is selected from ethyl, propyl, normal-butyl, tertiary butyl, just Amyl, neopentyl or one or more substituted ethyls, propyl, normal-butyl, tertiary butyl, just in by halogen atom or hydroxyl Identical or different group in amyl, neopentyl；R5、R6It is selected from propyl, normal-butyl, tertiary butyl, n-pentyl or one or more substitutions in by halogen atom or hydroxyl Propyl, normal-butyl, tertiary butyl, the identical or different group in n-pentyl.
- 6. according to the method described in claim 1, it is characterized in that：The cyclic monomer is selected from following one kind or several Kind：L- lactides, D- lactides, DL- lactides, beta-propiolactone, gamma-butyrolacton, δ-valerolactone, 6-caprolactone, chloro are in oneself Ester, trimethylene carbonate, hydroxyl trimethylene carbonate, chloro trimethylene carbonate.
- 7. according to the method described in claim 1, it is characterized in that：The reaction temperature of the method is at 10~150 degrees Celsius； The method is carried out or is carried out in a solvent under solvent-free conditions；The method carries out under solvent-free conditions, nothing Reaction temperature is 50~130 degrees Celsius under solvent condition；The method carries out in a solvent, the organic solvent under solvent condition For hexamethylene, hexane, acetone, dichloromethane, chloroform, benzene,toluene,xylene or tetrahydrofuran.
- 8. according to the method described in claim 7, it is characterized in that：The method carries out under solvent-free conditions, solvent-free Under the conditions of reaction temperature be 80~100 degrees Celsius.
- 9. according to the method described in claim 6, it is characterized in that：The monomer is L- lactides, D- lactides or DL- third Lactide, reaction temperature is 120~140 degrees Celsius under condition of no solvent.
- 10. according to the method described in claim 1, it is characterized in that：The organophosphorus compounds catalyst and cyclic annular chemical combination The molar ratio of object is 1：5 to 1：500, the polymer molecular weight MnFor 0.5-50kgmol-1。
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| CN114380985A (en) * | 2021-12-28 | 2022-04-22 | 青岛科技大学 | Preparation method of high-molecular-weight recyclable bio-based polyester |
| CN114752042A (en) * | 2022-05-24 | 2022-07-15 | 烟台大学 | Preparation method of high molecular weight polyester and product |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102753600A (en) * | 2009-12-08 | 2012-10-24 | 阿克马法国公司 | Method for preparing a polymer from at least one cyclic monomer |
| CN105637011A (en) * | 2013-10-24 | 2016-06-01 | 日本曹达株式会社 | Polyol composition |
| CN107022070A (en) * | 2017-04-28 | 2017-08-08 | 南京工业大学 | Method for preparing polyester by ring-opening polymerization |
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- 2018-01-17 CN CN201810043792.9A patent/CN108164690A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102753600A (en) * | 2009-12-08 | 2012-10-24 | 阿克马法国公司 | Method for preparing a polymer from at least one cyclic monomer |
| CN105637011A (en) * | 2013-10-24 | 2016-06-01 | 日本曹达株式会社 | Polyol composition |
| CN107022070A (en) * | 2017-04-28 | 2017-08-08 | 南京工业大学 | Method for preparing polyester by ring-opening polymerization |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114380985A (en) * | 2021-12-28 | 2022-04-22 | 青岛科技大学 | Preparation method of high-molecular-weight recyclable bio-based polyester |
| CN114752042A (en) * | 2022-05-24 | 2022-07-15 | 烟台大学 | Preparation method of high molecular weight polyester and product |
| CN114752042B (en) * | 2022-05-24 | 2023-08-04 | 烟台大学 | Preparation method of high molecular weight polyester and product |
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Application publication date: 20180615 |