CN104910364B - Linear comb makrolon and preparation method thereof - Google Patents
Linear comb makrolon and preparation method thereof Download PDFInfo
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- CN104910364B CN104910364B CN201510250019.6A CN201510250019A CN104910364B CN 104910364 B CN104910364 B CN 104910364B CN 201510250019 A CN201510250019 A CN 201510250019A CN 104910364 B CN104910364 B CN 104910364B
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- makrolon
- hydroxylating
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- 238000002360 preparation method Methods 0.000 title claims abstract description 65
- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 60
- 239000004425 Makrolon Substances 0.000 title claims abstract description 59
- 239000007788 liquid Substances 0.000 claims abstract description 69
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 47
- 230000000640 hydroxylating effect Effects 0.000 claims abstract description 40
- 229920000642 polymer Polymers 0.000 claims abstract description 35
- 239000003054 catalyst Substances 0.000 claims abstract description 29
- 239000003999 initiator Substances 0.000 claims abstract description 29
- -1 cyclic carbonate ester Chemical group 0.000 claims abstract description 26
- 229910052755 nonmetal Inorganic materials 0.000 claims abstract description 8
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 239000005062 Polybutadiene Substances 0.000 claims description 29
- 229920002857 polybutadiene Polymers 0.000 claims description 29
- 239000000178 monomer Substances 0.000 claims description 25
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 22
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 15
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 14
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid group Chemical group C(C1=CC=CC=C1)(=O)O WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 229920001195 polyisoprene Polymers 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 5
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Natural products CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 4
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 150000001409 amidines Chemical class 0.000 claims description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000005711 Benzoic acid Substances 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 235000010233 benzoic acid Nutrition 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- 150000003222 pyridines Chemical class 0.000 claims description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical class ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- OKJPEAGHQZHRQV-UHFFFAOYSA-N Triiodomethane Natural products IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 claims description 2
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 2
- 239000004417 polycarbonate Substances 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 238000012545 processing Methods 0.000 abstract description 4
- 238000007151 ring opening polymerisation reaction Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000012535 impurity Substances 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 17
- 238000004458 analytical method Methods 0.000 description 16
- 230000009477 glass transition Effects 0.000 description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- 238000006735 epoxidation reaction Methods 0.000 description 9
- 239000003292 glue Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical group CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 4
- 229910001868 water Inorganic materials 0.000 description 4
- OEBXWWBYZJNKRK-UHFFFAOYSA-N 1-methyl-2,3,4,6,7,8-hexahydropyrimido[1,2-a]pyrimidine Chemical compound C1CCN=C2N(C)CCCN21 OEBXWWBYZJNKRK-UHFFFAOYSA-N 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 150000001993 dienes Chemical class 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 235000019253 formic acid Nutrition 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229910003910 SiCl4 Inorganic materials 0.000 description 2
- 150000001350 alkyl halides Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002118 epoxides Chemical class 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000013557 residual solvent Substances 0.000 description 2
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 2
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical group CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- YRTHLWRYFMFPCC-UHFFFAOYSA-N 4,5-dimethyl-1,3-di(propan-2-yl)-2h-imidazole Chemical compound CC(C)N1CN(C(C)C)C(C)=C1C YRTHLWRYFMFPCC-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- FZFAMSAMCHXGEF-UHFFFAOYSA-N chloro formate Chemical compound ClOC=O FZFAMSAMCHXGEF-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 1
- HASCQPSFPAKVEK-UHFFFAOYSA-N dimethyl(phenyl)phosphine Chemical compound CP(C)C1=CC=CC=C1 HASCQPSFPAKVEK-UHFFFAOYSA-N 0.000 description 1
- 239000003937 drug carrier Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 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 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000001225 nuclear magnetic resonance method Methods 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 description 1
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229920006132 styrene block copolymer Polymers 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention provides class Linear comb makrolon and preparation method thereof, belong to synthesis of polymer material and preparing technical field.The polymer has following structure：The number-average molecular weight of Linear comb makrolon is 1 × 104- 50 × 104, the single armed number-average molecular weight of makrolon is 0.1 × 104- 3 × 104；Linear molecule initiator is that the hydroxyl quantity in the linear liquid polymers of hydroxylating, linear molecule initiator is 8-60, and the number-average molecular weight of linear molecule initiator is 0.1 × 104- 1 × 104.By initiator of the linear liquid polymers of polyfunctional group hydroxylating, organic non-metal alkali be catalyst, the characteristics of high cladodification makrolon prepared by cyclic carbonate ester ring-opening polymerisation has HMW, narrow ditribution, no metal impurities residual；HMW is effectively improved physical and mechanical properties；High branched structure effectively improves processing characteristics.
Description
Technical field
The invention belongs to synthesis of polymer material and preparing technical field, the biodegradable poly- carbon of a class is related specifically to
Acid esters material, it is characterised in that HMW, high cladodification Linear comb makrolon and preparation method thereof, the present invention prepared by
Makrolon has excellent physical and mechanical properties and excellent processing characteristics.
Background technology
Fatty poly-ester carbonate is finally decomposed to CO due to that can degrade in the presence of water or in vivo2And water,
Can be used as degradable material, and combine its low toxicity, good biocompatibility the advantages of, medically can be used as surgical material,
Bone fixator and pharmaceutical carrier etc..But up to the present, for the preparation of fatty poly-ester carbonate, performance and application still
Await further research and development.
Fatty poly-ester carbonate has three kinds of preparation approachs：(1) contracting of dihydric alcohol and carbonic ester or dihydric alcohol and chloro-formate
It is poly-；(2)CO2With the copolymerization of epoxide in the presence of an organometallic catalyst, compare typically diethyl zinc system and urge
Agent and rare earth catalyst；(3) ring-opening polymerisation of cyclic carbonate ester.Due to ring-opening polymerization mild condition, polymer architecture holds
Easy to control, obtained polymerizate is pure and causes the growing interest of people, and can be smaller by using toxicity and be easy to
The catalyst of removing is catalyzed, the need for resulting polymerizate can meet medical science and grocery trade, so as in recent years
The study hotspot come.
The content of the invention
It is an object of the invention to provide a class Linear comb makrolon, this kind of Linear comb makrolon has branches of tall trees
The characteristics of change, HMW, narrow ditribution, while have excellent physical and mechanical properties and splendid processing characteristics, be a class without
Biomaterial for medical purpose malicious, degradable, with high biological security.It is another object of the present invention to provide one kind is above-mentioned
The simple efficient preparation method of Linear comb makrolon.The present invention's is technically characterized in that with the linear liquid polymers of hydroxylating
For polyfunctional group linear molecule initiator, prepared Linear comb makrolon is without metal residual.
One class Linear comb makrolon, it is characterised in that the polymer has following structure：Linear comb makrolon
Number-average molecular weight be 1 × 104- 50 × 104, preferably 2 × 104- 30 × 104；The single armed number-average molecular weight of makrolon is
0.1×104- 3 × 104, preferably 0.2 × 104- 2 × 104；Linear molecule initiator is the linear liquid polymeric of hydroxylating
Hydroxyl quantity in thing, linear molecule initiator is 8-60, preferably 12-40；The number of linear molecule initiator is divided equally
Son amount is 0.1 × 104- 1 × 104, preferably 0.2 × 104- 0.8 × 104。
The preparation method of one class Linear comb makrolon, it is characterised in that：Under normal pressure and inert gas shielding, inertia
Gas is selected from nitrogen, argon gas, according to the size of molecular weight of product, by catalyst organic non-metal alkali, monomer cyclic carbonate ester, organic
Solvent, the linear liquid polymers of linear molecule initiator hydroxylating are added sequentially in the reactor with stirring, are configured to
Monomer cyclic carbonate ester molar concentration is 0.5-2M solution, opens and stirs, and the mol ratio of monomer cyclic carbonate ester and hydroxyl is 8-
250, the mol ratio of organic non-metal catalyst and hydroxyl is 0.1-5, preferably 0.5-2；Polymerization reactor control is in 0.25-
15h, polymeric reaction temperature is controlled at 0-50 DEG C, terminating reaction after reaction terminates, and the mol ratio of terminator and hydroxyl is 2-
5, terminator is benzoic acid, polymer solution is post-processed, product drying, finally gives Linear comb makrolon.This
The preparation method of the involved class Linear comb makrolon of invention is compared with the synthetic method for the makrolon reported, originally
Matter difference is that initiator used in the present invention is the linear liquid polymers of polyhydroxy.
Monomer cyclic carbonate ester involved in the present invention is selected from TMC (TMC), the methylene of 2,2- dimethyl three
One or more of mixtures in basic ring carbonic ester (DTC).Organic solvent involved in the present invention is selected from aromatic hydrocarbons, alkyl halide
The one or more of mixtures of hydrocarbon, wherein aromatic hydrocarbons in benzene, toluene, ethylbenzene, dimethylbenzene, chlorobenzene, preferably toluene；Alkyl halide
One or more of mixing of the hydrocarbon in chloroform, dichloromethane, chloroform, bromoethane, iodomethane, 1,2- dichloroethanes
Thing, preferably dichloromethane.Catalyst involved in the present invention is selected from any organic non-metal alkali disclosed in prior art, wherein
Including one or more of mixtures in following organic non-metal alkali：Guanidine catalyst, amidine class catalyst, the catalysis of phosphine nitrile
Agent, Thiourea catalyst, pyridines catalyst, N-heterocyclic carbine class catalyst, phosphine compound catalyst, preferably are selected from guanidine catalysis
Agent, amidine class catalyst.Guanidine catalyst is selected from the azabicyclics of 1,5,7- tri- [4.4.0] decyl- 5- alkene (TBD), N-methyl -1,5,7-
Three azabicyclics [4.4.0] decyl- 5- alkene (MTBD)；Amidine class catalyst is selected from the carbon -7- alkene of 1,8- diazabicylos [5.4.0] 11
(DBU)；Thiourea catalyst is selected from 1- (3,5- pairs-trifluoromethyl-phenyl) -3- cyclohexyl thiocarbamides；Pyridines catalyst is selected from
4-dimethylaminopyridine (DMAP), 4- pyrollidinopyridines (PPY)；N-heterocyclic carbine class catalyst be selected from 1,3- it is double (2,4,
6- trimethylphenyls) imidazoles -2- subunits, 1,3- diisopropyl -4,5- dimethyl-imidazol -2- subunits, double (the 2,6- diisopropyls of 1,3-
Base phenyl)-imidazoles -2- subunits；Phosphine compound catalyst is selected from tri-n-butyl phosphine, tri-butyl phosphine, dimethylphenylphosphine, methyl two
Phenylphosphine, triphenylphosphine.
Linear molecule initiator involved in the present invention is selected from the linear liquid of any polyhydroxy disclosed in prior art
Polymer, including the mixed of the linear liquid polymers of one or more of polyhydroxy in the linear liquid polymers of following polyhydroxy
Compound：The linear liquid polybutadiene of hydroxylating, the linear liquid polyisoprene of hydroxylating, the linear liquid butadiene of hydroxylating/different
Pentadiene copolymer, preferably is selected from the linear liquid polybutadiene of hydroxylating, the linear liquid polyisoprene of hydroxylating.Linear molecule
The preparation method of the linear liquid polymers of initiator hydroxylating, it is characterised in that including three below part：Linear liquid polymeric
The preparation of thing, the preparation of the linear liquid polymers of epoxidation, the preparation of the linear liquid polymers of hydroxylating；Wherein liquid polymers
With the preparation method of epoxidized liquid polymer referring to Chinese invention patent ZL200710157403.7 (butadiene/isoprene/
Diolefin star comb-shaped and preparation method thereof) and ZL200810190932.1 (star-shaped comb type butadiene/styrene block
Copolymer and preparation method thereof) disclosed in preparation method, compared with the preparation method of star liquid polymers, linear liquid
The preparation method of polymer, which is a difference in that after the completion of monomer total overall reaction, no longer to be needed to add coupling agent (such as：SiCl4) enter
Row coupling reaction, and the preparation method of the linear liquid polymers of epoxidation and the preparation method of epoxidation star liquid polymers are complete
It is exactly the same；The preparation method of the linear liquid polymers of hydroxylating, it is characterised in that：By solvents tetrahydrofurane, the linear liquid of epoxidation
Body polymer is added in reactor, is stirred at room temperature or 25 DEG C -30 DEG C, and the trifluoromethanesulfonic acid aqueous solution is added dropwise, and is added dropwise
After the completion of react again 3-4 hours, add chloroform terminating reaction；Glue is washed till after neutrality with deionized water, is distilled off
Most of solvent, then residual solvent is further removed with cold-trap vacuum deep cooling and THF azeotropic, obtain transparent glue.
Now illustrate the preparation method of linear molecule initiator of the present invention by taking the linear liquid polybutadiene of hydroxylating as an example, but
The linear liquid polybutadiene of hydroxylating is not limited to, the preparation method of other linear molecule initiators is identical with following methods.
The preparation method of the linear liquid polybutadiene of hydroxylating, it is characterised in that including three below part：Linear liquid polybutadiene
Preparation, the preparation of the linear liquid polybutadiene of epoxidation, the preparation of the linear liquid polybutadiene of hydroxylating；The wherein poly- fourth of liquid
The preparation method of diene and epoxidized liquid polybutadiene is referring to Chinese invention patent ZL200710157403.7 (butadiene/different
Pentadiene/diolefin star comb-shaped and preparation method thereof) and ZL200810190932.1 (star-shaped comb type butadiene/benzene
Ethylene block copolymer and preparation method thereof) disclosed in preparation method, the preparation method phase with star liquid polybutadiene
Than the preparation method of linear liquid polybutadiene is a difference in that after the completion of butadiene total overall reaction no longer to need to add and is coupled
Agent is (such as：SiCl4) coupling reaction is carried out, and the preparation method of the linear liquid polybutadiene of epoxidation is gathered with epoxidation star liquid
The preparation method of butadiene is identical；The preparation method of the linear liquid polybutadiene of hydroxylating, it is characterised in that：40g is molten
Agent tetrahydrofuran (THF), the linear liquid polybutadiene of 5g epoxidations (epoxide number is 19.73%) are added in reactor, in room
Stirred at temperature or 25 DEG C -30 DEG C, the trifluoromethanesulfonic acid aqueous solution (TfOH is added dropwise：2.8mL；H2O：10.26g), it is added dropwise to complete
React again afterwards 3.5 hours, add 150mL chloroform terminating reactions；Glue is washed till after neutrality with deionized water, is distilled off
Most of solvent, then residual solvent is further removed with cold-trap vacuum deep cooling and THF azeotropic, obtain transparent glue.
The effect and benefit of the present invention is that：Prepared using the linear liquid polymers of linear molecule initiator hydroxylating
Biodegradable material makrolon, technological process is simply efficient, and cost is relatively low；Initiator is free of metal, and polymer is without metal
Impurity is remained；HMW, narrow ditribution are effectively improved the physical and mechanical properties of makrolon；Meanwhile, high branched structure has
Improve HMW, the processing characteristics of narrow ditribution makrolon to effect.
Embodiment
The present invention, but the not scope of limitation the claims in the present invention protection are further illustrated with reference to embodiment.Hydroxyl
The measure of base polybutadiene hydroxylating degree (E)：Hydroxylated polymer hydroxylating degree is used1H-NMR methods are tested, and calculate publicity
It is as follows：
Wherein：Hydroxyl peak position is 3.4ppm and 3.6ppm；Polybutadiene different structure peak position：1,2 structures are
4.9ppm, suitable anti-1,4 structure are 5.4ppm.
Embodiment 1
The preparation of the linear liquid polybutadiene of hydroxylating：Using classical anionic polymerisation process, by solvent of hexamethylene,
N-BuLi is that initiator, butadiene are monomer, prepares linear liquid polybutadiene, the number-average molecular weight of polybutadiene is 6700
(using gel permeation chromatograph GPC tests), molecular weight distributing index (abbreviation PDI, similarly hereinafter) is 1.11.In 250mL reactors
The middle toluene solution 150mL added dissolved with aforesaid liquid polybutadiene 3.3g, opens stirring, is added when temperature rises to 40 DEG C
1.5g 98% formic acid, drips off 2.8g 30% hydrogen peroxide in 30min, reacts 2 hours；During with deionized water, glue is washed till
Property after, most of solvent is distilled off, transparent glue is obtained, epoxy content is 19.34% (using nuclear magnetic resonance method NMR test).
The linear liquid polybutadiene of 3.2g epoxidations is taken, 82.1g tetrahydrofurans are stirred in reactor, and 2.6g trifluoromethanesulfonic acids are dissolved in
It is added drop-wise in reactor, reacts 3.5 hours in 3.1g deionized water, adds 150mL chloroform terminating reactions.Use deionization
Glue is washed till after neutrality by water, most of solvent is distilled off, then with after cold-trap vacuum deep cooling and THF azeotropic to constant weight, obtain
Transparent glue；Hydroxylating degree is 19.34%, and hydroxyl value is 48.0, and number-average molecular weight is 7000 (GPC tests), and PDI is 1.13.
Embodiment 2
The preparation of Linear comb makrolon：Normal temperature and pressure, under inert nitrogen gas protection, by 1,5,7- tri- azabicyclic
The hydroxyl synthesized in [4.4.0] decyl- 5- alkene (TBD) 0.04g (being 1 metering by the mol ratio of TBD and hydroxyl), 0.04g embodiments 1
Change linear liquid polybutadiene initiator, 1.0g TMC monomers to be added in 14ml dichloromethane, monomer three
The mol ratio of methylene cyclic carbonate ester and hydroxyl is 35, and single armed number-average molecular weight is 3200, reacts 30min.Add terminator benzene
Polymer glue is post-processed after formic acid (being 3 meterings by the mol ratio of terminator and hydroxyl), reaction terminating, drying is laggard
Row analysis test, obtains final products Linear comb makrolon.Product is through gpc analysis weight average molecular weight 4.8 × 104, number is
Molecular weight 3.2 × 104, PDI is 1.48, and glass transition temperature is -19.5 DEG C.
Embodiment 3
The preparation of Linear comb makrolon：Test recipe and preparation method be the same as Example 2, difference are monomer Sanya
The mol ratio of methyl cyclic carbonate ester and hydroxyl is 10, and single armed number-average molecular weight is 1000, TBD and the mol ratio of hydroxyl is 0.2, instead
15min is answered, product Linear comb makrolon is through gpc analysis weight average molecular weight 2.3 × 104, number-average molecular weight 1.8 × 104, PDI
For 1.28, glass transition temperature is -19.8 DEG C.
Embodiment 4
The preparation of Linear comb makrolon：Test recipe and preparation method be the same as Example 2, difference are monomer Sanya
The mol ratio of methyl cyclic carbonate ester and hydroxyl is 100, and single armed number-average molecular weight is 6500, TBD and the mol ratio of hydroxyl is 1, production
Thing Linear comb makrolon is through gpc analysis weight average molecular weight 19.0 × 104, number-average molecular weight 12.6 × 104, PDI is 1.51,
Glass transition temperature is -18.7 DEG C.
Embodiment 5
The preparation of Linear comb makrolon：Test recipe and preparation method be the same as Example 2, difference are monomer Sanya
The mol ratio of methyl cyclic carbonate ester and hydroxyl is 150, and single armed number-average molecular weight is 10000, TBD and the mol ratio of hydroxyl is 1, production
Thing Linear comb makrolon is through gpc analysis weight average molecular weight 30.9 × 104, number-average molecular weight 19.8 × 104, PDI is 1.56,
Glass transition temperature is -18.5 DEG C.
Embodiment 6
The preparation of Linear comb makrolon：Test recipe and preparation method be the same as Example 2, difference are monomer Sanya
The mol ratio of methyl cyclic carbonate ester and hydroxyl is 200, and single armed number-average molecular weight is 15200, TBD and the mol ratio of hydroxyl is 1, production
Thing Linear comb makrolon is through gpc analysis weight average molecular weight 43.1 × 104, number-average molecular weight 28.9 × 104, PDI is 1.49,
Glass transition temperature is -18.0 DEG C.
Embodiment 7
The preparation of Linear comb makrolon：Test recipe and preparation method be the same as Example 2, difference are monomer Sanya
The mol ratio of methyl cyclic carbonate ester and hydroxyl is 250, and single armed number-average molecular weight is 19800, TBD and the mol ratio of hydroxyl is 5, production
Thing Linear comb makrolon is through gpc analysis weight average molecular weight 54.2 × 104, number-average molecular weight 35.2 × 104, PDI is 1.54,
Glass transition temperature is -17.9 DEG C.
Embodiment 8
The preparation of Linear comb makrolon：Test recipe and preparation method be the same as Example 2, difference are monomer Sanya
The mol ratio of methyl cyclic carbonate ester and hydroxyl is 50, and single armed number-average molecular weight is 2100, TBD and the mol ratio of hydroxyl is 0.5, is had
Machine solvent is toluene, and product Linear comb makrolon is through gpc analysis weight average molecular weight 3.9 × 104, number-average molecular weight 3.0 ×
104, PDI is 1.30, and glass transition temperature is -19.7 DEG C.
Embodiment 9
The preparation of Linear comb makrolon：Test recipe and preparation method be the same as Example 2, difference are monomer 2,2-
The mol ratio of dimethyltrimethylene cyclic carbonate ester and hydroxyl is 50, and single armed number-average molecular weight is mole of 3000, TBD and hydroxyl
Than for 2, product Linear comb makrolon is through gpc analysis weight average molecular weight 6.0 × 104, number-average molecular weight 4.2 × 104, PDI is
1.42, glass transition temperature is -19.1 DEG C.
Embodiment 10
The preparation of Linear comb makrolon：Normal temperature and pressure, under inert nitrogen gas protection, by 1,8- diazabicylos
The hydroxyl synthesized in [5.4.0] 11 carbon -7- alkene (DBU) 0.09g (being 2 meterings by the mol ratio of DBU and hydroxyl), embodiment 1
Change linear liquid polybutadiene initiator 0.04g, TMC monomer 1.0g to be added in 7ml dichloromethane, it is single
The mol ratio of body TMC and hydroxyl is 35, and single armed number-average molecular weight is 2300, reacts 8h.Add terminator benzene
Polymer solution is post-processed after formic acid (being 3 meterings by the mol ratio of terminator and hydroxyl), reaction terminating, drying is laggard
Row analysis test, obtains final products Linear comb makrolon.Product Linear comb makrolon is through gpc analysis Weight-average molecular
Amount 3.0 × 104, number-average molecular weight 2.6 × 104, PDI is 1.14, and glass transition temperature is -19.6 DEG C.
Embodiment 11
The preparation of Linear comb makrolon：Normal temperature and pressure, under inert nitrogen gas protection, by N-methyl -1,5,7- tri-
Synthesized in azabicyclic [4.4.0] decyl- 5- alkene (MTBD) 0.09g (being 2 meterings by the mol ratio of MTBD and hydroxyl), embodiment 1
The linear liquid polybutadiene initiator 0.04g of hydroxylating, TMC monomer 1.0g be added to 7ml dichloromethane
In, the mol ratio of monomer TMC and hydroxyl is 35, and single armed number-average molecular weight is 1300, reacts 15h.Add eventually
Polymer solution is post-processed after only agent benzoic acid (being 3 meterings by the mol ratio of terminator and hydroxyl), reaction terminating, it is dry
Analysis test is carried out after dry, final products Linear comb makrolon is obtained.Product Linear comb makrolon is through gpc analysis weight
Average molecular weight 2.3 × 104, number-average molecular weight 1.8 × 104, PDI is 1.24, and glass transition temperature is -19.7 DEG C.
Embodiment 12
The preparation of the linear liquid polyisoprene of hydroxylating：Preparation method be the same as Example 1, hydroxyl value is 28.59, and number is divided equally
Son amount is 6300 (GPC tests), and PDI is 1.21.Using the linear liquid polyisoprene of hydroxylating liquid manufactured in the present embodiment as
Initiator, prepares Linear comb makrolon：Test recipe and preparation method be the same as Example 2, difference are the methylene of monomer three
The mol ratio of basic ring carbonic ester and hydroxyl is 100, and single armed number-average molecular weight is 6000, TBD and the mol ratio of hydroxyl is 0.5, production
Thing Linear comb makrolon is through gpc analysis weight average molecular weight 10.4 × 104, number-average molecular weight 7.3 × 104, PDI is 1.42, glass
Glass transition temperature is -18.4 DEG C.
Embodiment 13
The preparation of the linear liquid polybutadiene of hydroxylating liquid：Preparation method be the same as Example 1, hydroxyl value is 12.31.With this
The linear liquid polybutadiene of hydroxylating liquid prepared by embodiment is initiator, prepares Linear comb makrolon：Test recipe
With preparation method be the same as Example 2, difference is monomer 2, and the mol ratio of 2- dimethyltrimethylenes cyclic carbonate ester and hydroxyl is
50, single armed number-average molecular weight is 4800, TBD and the mol ratio of hydroxyl is 0.5, and product Linear comb makrolon is through gpc analysis
Weight average molecular weight 4.1 × 104, number-average molecular weight 3.7 × 104, PDI is 1.11, and glass transition temperature is -18.9 DEG C.
Embodiment 14
The preparation of the linear liquid polybutadiene of hydroxylating liquid：Preparation method be the same as Example 1, hydroxyl value is 56.25.With this
The linear liquid polybutadiene of hydroxylating liquid prepared by embodiment is initiator, prepares Linear comb makrolon：Test recipe
With preparation method be the same as Example 2, difference is that the mol ratio of monomer TMC and hydroxyl is 100, single armed number
Average molecular weight is 6800, TBD and the mol ratio of hydroxyl is 0.5, and product Linear comb makrolon is through gpc analysis weight average molecular weight
31.0×104, number-average molecular weight 21.7 × 104, PDI is 1.43, and glass transition temperature is -18.0 DEG C.
Claims (3)
1. a class Linear comb makrolon, it is characterised in that the polymer has following structure：Linear comb makrolon
Number-average molecular weight is 1 × 104-50×104, the single armed number-average molecular weight of makrolon is 0.1 × 104-3×104；Linear big point
Sub- initiator is that the hydroxyl quantity in the linear liquid polymers of hydroxylating, linear molecule initiator is 8-60, linear molecule
The number-average molecular weight of initiator is 0.1 × 104-1×104；Wherein the linear liquid polymers of hydroxylating is selected from the linear liquid of hydroxylating
One kind in the linear liquid butadiene/isoprene copolymer of the linear liquid polyisoprene of polybutadiene, hydroxylating, hydroxylating
Or two or more mixing；
The preparation method of a described class Linear comb makrolon, under normal pressure and inert gas shielding, according to Linear comb
The size of polycarbonate molecular weight, catalyst organic non-metal alkali, monomer cyclic carbonate ester, organic solvent, linear molecule are drawn
The hair linear liquid polymers of agent hydroxylating is added sequentially in the reactor with stirring, is configured to monomer cyclic carbonate ester mole dense
Spend the solution for 0.5-2M, stir, the mol ratio of monomer cyclic carbonate ester and hydroxyl is 8-250, catalyst organic non-metal alkali with
The mol ratio of hydroxyl is 0.1-5, and polymerization reactor control is controlled at 0-50 DEG C in 0.25-15h, polymeric reaction temperature, when reaction knot
Terminating reaction after beam；The mol ratio of terminator and hydroxyl is 2-5, and terminator is benzoic acid, polymer solution is post-processed,
Product drying, finally gives Linear comb makrolon；Wherein catalyst organic non-metal alkali is selected from guanidine catalyst, amidine class and urged
In agent, phosphine nitrile catalyst, Thiourea catalyst, pyridines catalyst, N-heterocyclic carbine class catalyst, phosphine compound catalyst
One or more kinds of mixing；The linear liquid polymers of linear molecule initiator hydroxylating is poly- selected from the linear liquid of hydroxylating
One kind in the linear liquid butadiene/isoprene copolymer of the linear liquid polyisoprene of butadiene, hydroxylating, hydroxylating or
Two or more mixing；Organic solvent is selected from the mixing of one or both of aromatic hydrocarbons, halogenated alkane；
The one kind of described monomer cyclic carbonate ester in TMC, DTC
Or two kinds of mixing；
It is mixed above that described organic solvent aromatic hydrocarbons is selected from one or both of benzene, toluene, ethylbenzene, dimethylbenzene, chlorobenzene；It is described
Organic solvent halogenated alkane in chloroform, dichloromethane, chloroform, bromoethane, iodomethane, 1,2- dichloroethanes one
Plant or two or more mixing.
2. Linear comb makrolon according to claim 1, it is characterised in that described Linear comb makrolon
Number-average molecular weight is 2 × 104-30×104, the single armed number-average molecular weight of makrolon is 0.2 × 104-2×104。
3. Linear comb makrolon according to claim 2, it is characterised in that described linear molecule initiator
Number-average molecular weight is 0.2 × 104-0.8×104, the hydroxyl quantity in linear molecule initiator is 12-40.
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