CN103421167B - A kind of one-step synthesis method method of degradable branched polyester - Google Patents
A kind of one-step synthesis method method of degradable branched polyester Download PDFInfo
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- CN103421167B CN103421167B CN201310283031.8A CN201310283031A CN103421167B CN 103421167 B CN103421167 B CN 103421167B CN 201310283031 A CN201310283031 A CN 201310283031A CN 103421167 B CN103421167 B CN 103421167B
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- 238000000034 method Methods 0.000 title claims abstract description 14
- 229920000728 polyester Polymers 0.000 title claims abstract description 13
- 238000001308 synthesis method Methods 0.000 title claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- 239000000178 monomer Substances 0.000 claims abstract description 37
- -1 cyclic carbonate ester Chemical class 0.000 claims abstract description 27
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims abstract description 10
- 150000008065 acid anhydrides Chemical class 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 6
- 150000002596 lactones Chemical class 0.000 claims abstract description 6
- 229930013930 alkaloid Natural products 0.000 claims abstract description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 50
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 42
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 24
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-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
- 150000007514 bases Chemical class 0.000 claims description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical group O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 claims description 2
- ZMARGGQEAJXRFP-UHFFFAOYSA-N 1-hydroxypropan-2-yl 2-methylprop-2-enoate Chemical compound OCC(C)OC(=O)C(C)=C ZMARGGQEAJXRFP-UHFFFAOYSA-N 0.000 claims description 2
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 claims description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 238000012662 bulk polymerization Methods 0.000 claims description 2
- 229930188620 butyrolactone Natural products 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 31
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 22
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 20
- 238000007789 sealing Methods 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- 229910052757 nitrogen Inorganic materials 0.000 description 13
- 229920001577 copolymer Polymers 0.000 description 12
- 239000007788 liquid Substances 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 238000005406 washing Methods 0.000 description 12
- 238000006073 displacement reaction Methods 0.000 description 11
- 230000008014 freezing Effects 0.000 description 11
- 238000007710 freezing Methods 0.000 description 11
- 238000001291 vacuum drying Methods 0.000 description 11
- 229910052786 argon Inorganic materials 0.000 description 10
- 239000012300 argon atmosphere Substances 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- 239000007795 chemical reaction product Substances 0.000 description 8
- 229920001610 polycaprolactone Polymers 0.000 description 8
- 239000004632 polycaprolactone Substances 0.000 description 8
- 230000003381 solubilizing effect Effects 0.000 description 8
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 8
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical class CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 4
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 3
- VLCAYQIMSMPEBW-UHFFFAOYSA-N methyl 3-hydroxy-2-methylidenebutanoate Chemical compound COC(=O)C(=C)C(C)O VLCAYQIMSMPEBW-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 229920003232 aliphatic polyester Polymers 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000003937 drug carrier Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229920000587 hyperbranched polymer Polymers 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 231100000957 no side effect Toxicity 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
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- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses a kind of one-step synthesis method method of degradable branching polyester, belong to polymer synthesis techniques field.Described reaction monomers is lactone, acid anhydrides, cyclic carbonate ester etc., and described is crylic acid hydroxy ester, methacrylic acid hydroxyl ester compound from trigger monomer, and described catalyzer is the phosphine nitrile alkaloid compound that structure contains P=N double bond.The invention has the advantages that polyreaction raw material used commercialization all, polymeric reaction condition is gentle, is applicable to suitability for industrialized production, has good application prospect.The present invention is mainly used in polymer synthesis techniques field.
Description
Technical field
The present invention relates to the one-step synthesis method method of degradable branched polyester, belong to polymer synthesis techniques field.
Background technology
Aliphatic polyester is a class degradable, environmental friendliness, biocompatible polymkeric substance, all has a wide range of applications in the field such as medicine, agricultural, coating.But because most aliphatic polyester is partially crystalline polymer, therefore degradation speed is slow, limit its application.
Hyperbranched polymer is the highly branched macromole that a class has three-dimensional structure, in coating, pharmaceutical carrier, processing aid etc., have potential application prospect.Introduce the crystallization behavior that branched structure can control polymkeric substance effectively in the polyester, reduce the degree of crystallinity of polyester.The method of current synthesized degradable branched polyester is limited, and preparation process is loaded down with trivial details, needs to prepare in advance from trigger monomer or branched monomer, cannot realize industrialization.
Summary of the invention
The object of the invention is for the deficiencies in the prior art, a kind of one-step synthesis method method of degradable branched polyester is provided.
For achieving the above object, adopt following technical scheme herein: a kind of one-step synthesis method method of degradable branched polyester, carry out according to following step:
With one or more monomers in lactone, acid anhydrides or cyclic carbonate ester for reaction monomers, crylic acid hydroxy ester, methacrylic acid hydroxyl ester compound are from trigger monomer, at next the footwork synthesized degradable branched polyester of phosphine nitrile alkaloid compound catalysis containing P=N double bond; Described polymeric reaction temperature is at-100 DEG C to 300 DEG C, and polymerization reaction time is 0.5 ~ 48 hour.
Wherein said reaction monomers with from the mol ratio of trigger monomer be (50 ~ 300): 1; Phosphine nitrile alkali with from the mol ratio of trigger monomer be (0.1 ~ 5): 1.
Wherein said lactone monomer is butyrolactone, caprolactone, valerolactone, rac-Lactide or valerolactone etc.
Wherein said acid anhydrides is second (acid) acid anhydride or Tetra hydro Phthalic anhydride etc.
Wherein said cyclic carbonate ester class monomer is TMC or 2,2-dimethyltrimethylene cyclic carbonate ester etc.
Wherein said is simultaneously with crylic acid hydroxy ester or the methacrylic acid hydroxyl ester compound of double bond and hydroxyl from trigger monomer, comprises Hydroxyethyl acrylate, hydroxyethyl methylacrylate, Propylene glycol monoacrylate, Rocryl 410 etc.
Described catalyzer is the phosphine nitrile highly basic compounds containing P=N double bond, and its general formula is as follows:
；
Wherein n=1-3; Y=1-3; M=1-2; R is CH
3.
Wherein said polyreaction adopts mass polymerization or solution polymerization; Wherein solution polymerization solvent for use is any one or the two or more mixture in benzene,toluene,xylene, tetrahydrofuran (THF), methyl-sulphoxide, DMF, N,N-dimethylacetamide and pyridine.
The present invention compared with prior art has following advantages:
1) use range is wide: use phosphine nitrile highly basic compounds this new catalyst, can catalyzing lactone, acid anhydrides, the ring-opening polymerization of cyclic carbonate ester class monomer.
2) polymeric reaction condition is gentle: the polymerisation process being catalyzer with phosphine nitrile highly basic compounds, range of reaction temperature is-100 ~ 300 DEG C, and used catalyst is metal ion not, is easily eliminated and has no side effect to medicine and human body.
3) polymerization process is simple: with phosphine nitrile highly basic compounds for catalyzer, raw materials used monomer realizes suitability for industrialized production, and without the need to other intermediate, single stage method can synthesized degradable hyper-branched polyester.
4) polyreaction of the present invention regulates from the ratio of trigger monomer and reaction monomers the degree of branching generating polymkeric substance by regulating, and the degree of branching of product is controlled.
Embodiment
Below in conjunction with example, the present invention will be further described, but be not limited only to following examples, for the processing parameter do not indicated especially, can refer to routine techniques and carry out.
embodiment 1
Get 1.1g (10mmol) caprolactone and 24.2 μ L (0.2mmol) hydroxyethyl methylacrylates, be placed in the 25mL tube sealing with rotor, then add 0.4g toluene and make solvent, liquid nitrogen freezing, injects rapidly the t-BuP of 20 μ L (0.02mmol) under an argon atmosphere after displacement argon gas three times
4hexane solution, tube sealing, is placed in 60 DEG C of oil bath pans, reaction 2h.After reaction terminates, add the hydrochloric acid soln of 5mL10wt% and 10mL ethanol termination reaction with tetrahydrofuran (THF) solubilizing reaction product and wash branched polycaprolactone, then with 100mL normal hexane under fast stirring fully washing copolymer to remove unreacted monomer, (protonated) t-BuP
4and toluene, filter, vacuum-drying 12h at 50 DEG C, molecular weight is 1.23 ' 10
5g/mol.
embodiment 2
Get 6.6g caprolactone (60mmol) and 24.2 μ L (0.2mmol) hydroxyethyl methylacrylates, be placed in the 25mL tube sealing with rotor, then add 3.3g toluene and make solvent, liquid nitrogen freezing, injects rapidly the t-BuP of 1mL (1mol) under an argon atmosphere after displacement argon gas three times
4hexane solution, tube sealing, is placed in 60 DEG C of oil bath pans, reaction 2h.After reaction terminates, add the hydrochloric acid soln of 5mL10wt% and 20mL ethanol termination reaction with tetrahydrofuran (THF) solubilizing reaction product and wash branched polycaprolactone, then with 200mL normal hexane under fast stirring fully washing copolymer to remove unreacted monomer, (protonated) t-BuP
4and toluene, filter, vacuum-drying 0.5h at 50 DEG C, molecular weight is 2.41 ' 10
5g/mol.
embodiment 3
Get 1.1g (10mmol) caprolactone and 24.2 μ L (0.2mmol) hydroxyethyl methylacrylates, be placed in the 25mL tube sealing with rotor, then add 0.6g toluene and make solvent, liquid nitrogen freezing, after displacement argon gas three times, inject rapidly the t-BuP of 60 μ L under an argon atmosphere
4hexane solution, tube sealing, the acetone/liquid nitrogen system being placed in-100 DEG C reacts 2h.After reaction terminates, add the hydrochloric acid soln of 5mL10wt% and 10mL ethanol termination reaction with tetrahydrofuran (THF) solubilizing reaction product and wash branched polycaprolactone, then with 100mL normal hexane under fast stirring fully washing copolymer to remove unreacted monomer, (protonated) t-BuP
4and toluene, filter, vacuum-drying 48h at 50 DEG C, molecular weight is 1.51 ' 10
5g/mol.
embodiment 4
Get 1.1g (10mmol) caprolactone and 24.2 μ L (0.2mmol) hydroxyethyl methylacrylates, be placed in the 25mL tube sealing with rotor, liquid nitrogen freezing, after displacement argon gas three times, inject rapidly the t-BuP of 60 μ L under an argon atmosphere
4hexane solution, tube sealing, bulk reaction 2h at being placed in 300 DEG C.After reaction terminates, add the hydrochloric acid soln of 5mL10wt% and 10mL ethanol termination reaction with tetrahydrofuran (THF) solubilizing reaction product and wash branched polycaprolactone, then with 100mL normal hexane under fast stirring fully washing copolymer to remove unreacted monomer, (protonated) t-BuP
4and toluene, filter, vacuum-drying 12h at 50 DEG C, molecular weight is 1.89 ' 10
5g/mol.
embodiment 5
Get 0.4g rac-Lactide and 15.2 μ L hydroxyethyl methylacrylates, be placed in the 25mL tube sealing with rotor, then add 0.4g toluene and make solvent, liquid nitrogen freezing, after displacement argon gas three times, inject rapidly the t-BuP of 60 μ L under an argon atmosphere
4hexane solution, tube sealing, is placed in 70 DEG C of oil bath pans, reaction 5h.After reaction terminates, add the hydrochloric acid soln of 5mL10wt% and 10mL ethanol termination reaction with tetrahydrofuran (THF) solubilizing reaction product and wash branched polycaprolactone, then with 100mL normal hexane under fast stirring fully washing copolymer to remove unreacted monomer, (protonated) t-BuP
4and tetrahydrofuran (THF), filter, vacuum-drying 12h at 50 DEG C, molecular weight is 4.47 ' 10
5g/mol.
embodiment 6
In 25mL reaction flask, add 1.0g diacetyl oxide, 0.06g hydroxyethyl methylacrylate, stir magneton and 10mLTHF solution, liquid nitrogen freezing, after displacement nitrogen three times, inject 80 μ Lt-BuP in a nitrogen atmosphere
4tetrahydrofuran solution, 100 DEG C reaction 24h.Reaction terminates rear with being added with the hydrochloric acid termination reaction of 10mL10wt% and washing copolymer, then with 200mL normal hexane under fast stirring abundant washing copolymer to remove unreacted monomer, (protonated) t-BuP
4and tetrahydrofuran (THF), filter, vacuum-drying 12h at 50 DEG C, molecular weight is 4.19 ' 10
5g/mol.
embodiment 7
Add 10g NSC 11801,0.2g Hydroxyethyl acrylate at the 50mL tube sealing of drying, 10gN, dinethylformamide, liquid nitrogen freezing, after displacement argon gas three times, add rapidly 200 μ Lt-BuP under an argon atmosphere
4normal hexane solution, 180 DEG C reaction 8h.After reaction terminates, wash branching gather NSC 11801 by the hydrochloric acid termination reaction being added with 10mL10wt%, then use 2 × 100mL methyl alcohol under fast stirring fully washing copolymer to remove unreacted monomer, (protonated) t-BuP
4and DMF, filter, vacuum-drying 12h at 50 DEG C, molecular weight is 3.65 ' 10
5g/mol.
embodiment 8
Get 0.2g caprolactone, 0.2g rac-Lactide and 15.2 μ L hydroxyethyl methylacrylates, be placed in the 25mL tube sealing with rotor, then add 0.4g toluene and make solvent, liquid nitrogen freezing, injects rapidly the t-BuP of 60 μ L after displacement argon gas three times under an argon atmosphere
4hexane solution, tube sealing, is placed in 60 DEG C of oil bath pans, reaction 2h.After reaction terminates, add the hydrochloric acid soln of 5mL10wt% and 10mL ethanol termination reaction with tetrahydrofuran (THF) solubilizing reaction product and wash branched polycaprolactone, then with 100mL normal hexane under fast stirring fully washing copolymer to remove unreacted monomer, (protonated) t-BuP
4and toluene, filter, vacuum-drying 12h at 50 DEG C, molecular weight is 2.23 ' 10
5g/mol.
embodiment 9:
Get 0.4g caprolactone and 12.4 μ L Hydroxyethyl acrylates, be placed in the 25mL tube sealing with rotor, then add 0.4g toluene and make solvent, liquid nitrogen freezing, after displacement argon gas three times, inject rapidly the t-BuP of 60 μ L under an argon atmosphere
4hexane solution, tube sealing, is placed in 60 DEG C of oil bath pans, reaction 2h.After reaction terminates, add the hydrochloric acid soln of 5mL10wt% and 10mL ethanol termination reaction with tetrahydrofuran (THF) solubilizing reaction product and wash branched polycaprolactone, then with 100mL normal hexane under fast stirring fully washing copolymer to remove unreacted monomer, (protonated) t-BuP
4and toluene, filter, vacuum-drying 12h at 50 DEG C, molecular weight is 1.43 ' 10
5g/mol.
embodiment 10
Get 2g caprolactone and 0.4g hydroxyethyl methylacrylate, be placed in the 25mL tube sealing with rotor, liquid nitrogen freezing, after displacement argon gas three times, inject rapidly the t-BuP of 100 μ L under an argon atmosphere
2hexane solution, tube sealing, is placed in 60 DEG C of oil bath pans, reaction 2h.After reaction terminates, add the hydrochloric acid soln of 8mL10wt% and 20mL ethanol termination reaction with tetrahydrofuran (THF) solubilizing reaction product and wash branched polycaprolactone, then with 200mL normal hexane under fast stirring fully washing copolymer to remove unreacted monomer, (protonated) t-BuP
2, filter, vacuum-drying 12h at 50 DEG C, molecular weight is 4.32 ' 10
5g/mol.
embodiment 11
Add 10g NSC 11801,0.2g Hydroxyethyl acrylate at the 50mL tube sealing of drying, 10gN, dinethylformamide, liquid nitrogen freezing, after displacement argon gas three times, add rapidly 200 μ Lt-BuP under an argon atmosphere
4normal hexane solution, 180 DEG C reaction 8h.After reaction terminates, wash branching gather NSC 11801 by the hydrochloric acid termination reaction being added with 10mL10wt%, then use 2 × 100mL methyl alcohol under fast stirring fully washing copolymer to remove unreacted monomer, (protonated) t-BuP
4and DMF, filter, vacuum-drying 12h at 50 DEG C, molecular weight is 3.71 ' 10
5g/mol.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (1)
1. an one-step synthesis method method for degradable branched polyester, is characterized in that carrying out according to following step:
With one or more monomers in lactone, acid anhydrides or cyclic carbonate ester for reaction monomers, crylic acid hydroxy ester, methacrylic acid hydroxyl ester compound are from trigger monomer, at next the footwork synthesized degradable branched polyester of phosphine nitrile alkaloid compound catalysis containing P=N double bond; Described polymeric reaction temperature is at-100 DEG C to 300 DEG C, and polymerization reaction time is 0.5 ~ 48 hour;
Wherein said reaction monomers with from the mol ratio of trigger monomer be (50 ~ 300): 1; Phosphine nitrile alkali with from the mol ratio of trigger monomer be (0.1 ~ 5): 1;
Wherein said lactone monomer is butyrolactone or valerolactone;
Wherein said from trigger monomer be Propylene glycol monoacrylate or Rocryl 410;
Wherein said polyreaction adopts mass polymerization or solution polymerization; Wherein solution polymerization solvent for use is any one or the two or more mixture in benzene,toluene,xylene, tetrahydrofuran (THF), methyl-sulphoxide, DMF, N,N-dimethylacetamide and pyridine;
Wherein said acid anhydrides is second (acid) acid anhydride or Tetra hydro Phthalic anhydride;
Wherein said cyclic carbonate ester class monomer is TMC or 2,2-dimethyltrimethylene cyclic carbonate ester;
Described catalyzer is the phosphine nitrile highly basic compounds containing P=N double bond, and its general formula is as follows:
；
Wherein n=1-3; Y=1-3; M=1-2; R is CH
3.
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| CN104629020B (en) * | 2015-01-23 | 2017-10-20 | 常州大学 | A kind of synthetic method of macromonomer |
| CN106633006B (en) * | 2016-10-19 | 2021-12-03 | 安徽红太阳新材料有限公司 | Synthesis method of cyclic polylactone polymer |
| CN106496538B (en) * | 2016-10-19 | 2021-12-03 | 安徽红太阳新材料有限公司 | Synthesis method of high molecular weight polycaprolactone |
| CN107698745A (en) * | 2017-11-01 | 2018-02-16 | 常州大学 | A kind of synthetic method of copolyesters |
| CN107814919A (en) * | 2017-11-07 | 2018-03-20 | 常州大学 | A kind of simple synthesis of aliphatic hyper-branched polyester |
| CN113024781B (en) * | 2021-03-03 | 2022-01-04 | 深圳市鑫元素新材料科技有限公司 | Preparation method of cyclic polylactone |
| CN113603869B (en) * | 2021-07-13 | 2022-04-26 | 华中科技大学 | Polyester brush-shaped polymer, one-pot synthesis method and application thereof |
| CN115975235A (en) * | 2022-12-23 | 2023-04-18 | 温州大学苍南研究院 | Anti-slip woven bag |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1613890A (en) * | 2003-11-04 | 2005-05-11 | 北京化工大学 | Biological degradable PES graft polyphosphonitrile copolymer and its preparation |
| CN102174128A (en) * | 2011-01-21 | 2011-09-07 | 华南理工大学 | Polymerization with strong alkali phosphazene compound as catalyst |
| CN102964557A (en) * | 2012-11-30 | 2013-03-13 | 华南理工大学 | Antifouling hydrolysis degradation resin and application thereof |
-
2013
- 2013-07-08 CN CN201310283031.8A patent/CN103421167B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1613890A (en) * | 2003-11-04 | 2005-05-11 | 北京化工大学 | Biological degradable PES graft polyphosphonitrile copolymer and its preparation |
| CN102174128A (en) * | 2011-01-21 | 2011-09-07 | 华南理工大学 | Polymerization with strong alkali phosphazene compound as catalyst |
| CN102964557A (en) * | 2012-11-30 | 2013-03-13 | 华南理工大学 | Antifouling hydrolysis degradation resin and application thereof |
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