CN1663978A - Process for preparing polycarbonate with optical activity - Google Patents
Process for preparing polycarbonate with optical activity Download PDFInfo
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- CN1663978A CN1663978A CN 200510046092 CN200510046092A CN1663978A CN 1663978 A CN1663978 A CN 1663978A CN 200510046092 CN200510046092 CN 200510046092 CN 200510046092 A CN200510046092 A CN 200510046092A CN 1663978 A CN1663978 A CN 1663978A
- Authority
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- Prior art keywords
- optically active
- preparation
- salt
- polycarbonate
- catalyst
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- 239000004417 polycarbonate Substances 0.000 title claims abstract description 27
- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 27
- 230000003287 optical effect Effects 0.000 title abstract description 6
- 238000004519 manufacturing process Methods 0.000 title abstract 2
- 239000003054 catalyst Substances 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 22
- 150000004753 Schiff bases Chemical class 0.000 claims abstract description 9
- 239000002262 Schiff base Substances 0.000 claims abstract description 8
- 150000003839 salts Chemical class 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims description 19
- 239000004593 Epoxy Substances 0.000 claims description 11
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 10
- 235000011089 carbon dioxide Nutrition 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 10
- 230000003197 catalytic effect Effects 0.000 claims description 7
- -1 diamine compounds Chemical class 0.000 claims description 7
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical class [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 4
- 229910020366 ClO 4 Inorganic materials 0.000 claims description 3
- IKWKJIWDLVYZIY-UHFFFAOYSA-M butyl(triphenyl)phosphanium;bromide Chemical group [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCCC)C1=CC=CC=C1 IKWKJIWDLVYZIY-UHFFFAOYSA-M 0.000 claims description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical group [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 3
- GMRIOAVKKGNMMV-UHFFFAOYSA-N tetrabutylazanium;azide Chemical compound [N-]=[N+]=[N-].CCCC[N+](CCCC)(CCCC)CCCC GMRIOAVKKGNMMV-UHFFFAOYSA-N 0.000 claims description 3
- SSJXIUAHEKJCMH-PHDIDXHHSA-N (1r,2r)-cyclohexane-1,2-diamine Chemical compound N[C@@H]1CCCC[C@H]1N SSJXIUAHEKJCMH-PHDIDXHHSA-N 0.000 claims description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000005466 alkylenyl group Chemical group 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- 229940107816 ammonium iodide Drugs 0.000 claims description 2
- 229910052785 arsenic Chemical group 0.000 claims description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical group [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- VJGNLOIQCWLBJR-UHFFFAOYSA-M benzyl(tributyl)azanium;chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CC1=CC=CC=C1 VJGNLOIQCWLBJR-UHFFFAOYSA-M 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- MFIUDWFSVDFDDY-UHFFFAOYSA-M butyl(triphenyl)phosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCCC)C1=CC=CC=C1 MFIUDWFSVDFDDY-UHFFFAOYSA-M 0.000 claims description 2
- RQNCKGZETNCAMA-UHFFFAOYSA-M butyl(triphenyl)phosphanium;iodide Chemical compound [I-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCCC)C1=CC=CC=C1 RQNCKGZETNCAMA-UHFFFAOYSA-M 0.000 claims description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- REPWBKQJAMXHFL-UHFFFAOYSA-N phenylphosphane;hydrobromide Chemical class [Br-].[PH3+]C1=CC=CC=C1 REPWBKQJAMXHFL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Chemical group 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 2
- RKHXQBLJXBGEKF-UHFFFAOYSA-M tetrabutylphosphanium;bromide Chemical compound [Br-].CCCC[P+](CCCC)(CCCC)CCCC RKHXQBLJXBGEKF-UHFFFAOYSA-M 0.000 claims description 2
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 2
- PONXTPCRRASWKW-KBPBESRZSA-N diphenylethylenediamine Chemical compound C1([C@H](N)[C@@H](N)C=2C=CC=CC=2)=CC=CC=C1 PONXTPCRRASWKW-KBPBESRZSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 9
- 239000001569 carbon dioxide Substances 0.000 abstract description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 6
- 238000007334 copolymerization reaction Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000004215 Carbon black (E152) Substances 0.000 abstract 3
- 229930195733 hydrocarbon Natural products 0.000 abstract 3
- 150000002430 hydrocarbons Chemical class 0.000 abstract 3
- 102220231544 rs281865209 Human genes 0.000 abstract 1
- 239000004743 Polypropylene Substances 0.000 description 13
- 125000005587 carbonate group Chemical group 0.000 description 13
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 150000005676 cyclic carbonates Chemical class 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- UFBJCMHMOXMLKC-UHFFFAOYSA-N 2,4-dinitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O UFBJCMHMOXMLKC-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical group CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- UOHBMRODJBFDPN-UHFFFAOYSA-N C(C)(C)(C)O.[Li] Chemical compound C(C)(C)(C)O.[Li] UOHBMRODJBFDPN-UHFFFAOYSA-N 0.000 description 1
- 229920000858 Cyclodextrin Polymers 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000001116 FEMA 4028 Substances 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 description 1
- 235000011175 beta-cyclodextrine Nutrition 0.000 description 1
- 229960004853 betadex Drugs 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention provides a method for preparing polycarbonate with optical activity by catalyzing asymmetric alternative copolymerization with racemic oxiraneic hydrocarbon and carbon dioxide, employing bi-component catalyst with chirality catalyzing the antimer of the racemic oxiraneic hydrocarbon selectively at the temperature of 0~80 DEG C, and copolymarizating with carbon dioxide to preparepolycarbonate with optical activity. The bi-component catalyst consists of host catalyst, the chirality quadridentate schiff bases metallic complexe, SalenMX; and the catalyst promoter, the salt of R1R23YX1 or (R13P)2YX1, with the proportion in moles 0.2~10:1. The proportion between catalyst and oxiranic hydrocarbon is 1:500~10000 in moles, the initial pressure of carbon dioxide is 0.1~4.0 Mpa, and the reacting for 0.5~24 hours. The method is characterized by the temperate reaction condition and the simple process; the simple synthesis of the chirality catalyst and low production cost and high reactive and suitable for industrial application.
Description
Technical field
The present invention relates to the comparatively gentle method for preparing optically active polycarbonate of a kind of efficient, easy, reaction conditions.
Background technology
Carbonic acid gas is the main gas that causes Greenhouse effect, and it is again one of carbon source the abundantest on the earth simultaneously.The chemical fixation of carbonic acid gas is an important research field of Green Chemistry.Wherein, utilizing a main direction of carbonic acid gas is to be raw material and epoxy alkane copolymerization polycarbonate under the effect of catalyzer with it.This superpolymer both can photodegradation, and was also biodegradable; The performance that also has good blocking oxygen and water simultaneously.Therefore, polycarbonate can be used as engineering plastics, biodegradable nonpollution material, disposable medicine and packaging material for food, tackiness agent and matrix material etc.Optically active polycarbonate is expected in this high-tech area of optical selective biomaterial important application is arranged.
The patent report for preparing polycarbonate about carbonic acid gas and epoxy alkane copolymerization is arranged at present much both at home and abroad.Obtain molecular weight as U.S. Pat 3585168, US 3900424 and US 3953383 usefulness based on the bicomponent catalyst of zinc alkyl(s) and be higher than 20000 polycarbonate, urethane and polyethers.Day disclosure laid-open patent JP 02142824 and JP 02575199 adopt expensive metalloporphyrin complex catalysis carbonic acid gas and epoxy alkane polycarbonate synthesis, catalytic efficiency reaches 103 ~ 104 gram polymkeric substance/mol catalysts, but polymericular weight has only about 5000, and the reaction times needs more than 10 days.Chinese patent application CN 89100701.6 and CN 91109459.8 disclose the bimetallic catalytic system of polymkeric substance load anion binding, also can obtain the catalytic efficiency of 104 gram polymkeric substance/mol catalysts, but carrier is difficult to separate with the polycarbonate that generates.Chinese patent application CN 98125654.6, CN 00136189.9 and CN03105023.9 have reported that zinc alkyl(s)/glycerine/rare-earth salts three-element catalytic system is used to prepare molecular weight and is higher than 20000 polycarbonate, and alternating structure is greater than 95%.At U.S. Pat 6133402 and J.Am.Chem.Soc., (2002,124,14284) in, Coates has described a kind of highly active single-activity point organic zinc catalyzer, the catalytic activity of its catalysis carbonic acid gas and propylene oxide reaction is up to 235 product of moles/mol catalyst hour, obtains molecular weight between 20000 ~ 40000 and be the poly-propylene carbonate of narrow distribution, but also produces 13 ~ 25% cyclic carbonate propylene ester by product synchronously.
There is low, the long reaction time of catalyst activity mostly in above-mentioned preparation polycarbonate method, and pressure is higher, and needs organic solvent; It is lower to supervene in cyclic carbonate by product or the polymerisate carbonate unit; Problems such as product and catalyst separating difficulty.What is more important, these documents do not relate to the synthetic of optically active polycarbonate as yet.
Summary of the invention
Purpose of the present invention just provide a kind of under low pressure or middle pressure selectivity catalysis racemation epoxy alkane and carbon dioxide reaction directly prepare the method for optically active polycarbonate.
Technical scheme of the present invention is, as reactant, the asymmetric copolyreaction of bicomponent catalyst selectivity catalysis by chirality prepares respective optical activity polycarbonate with the racemation epoxy paraffins mixture that contains dextrorotation (R) and left-handed (S) and carbonic acid gas.Can represent with following reaction formula:
The used bicomponent catalyst of this method is by Primary Catalysts chirality tetradentate schiff base metal complexes SalenMX and promotor R
1R
2 3YX
1Or (R
1 3P)
2YX
1Salt form.
The present invention, is Primary Catalysts and is R with the chemical formula with chirality tetradentate schiff base metal complexes SalenMX as reactant with racemation epoxy alkane and carbonic acid gas
1R
2 3YX
1Or (R
1 3P)
2YX
1Salt be promotor when carrying out the catalytic selectivity copolyreaction, help, the mol ratio of Primary Catalysts is 0.2～10: 1, Primary Catalysts and epoxy alkane mol ratio are 1: 500～10000; CO
2Original pressure be 0.1～4.0MPa; Temperature of reaction is 0～80 ℃; Reacted 0.5～24 hour.
The general structure of used reactant racemation epoxy alkane is during the preparation optically active polycarbonate:
Wherein R is CH
3, CH
2Cl, CH
2CH
3, Ph, CH
2(CH
2)
nCH
3Or CH
2(CH
2)
nCHCH
2, wherein n is 1～12.
The general structure of used Primary Catalysts chirality tetradentate schiff base metal complexes SalenMX is during the preparation optically active polycarbonate:
In the formula: M is Fe
3+, Co
3+, Ni
3+, Cr
3+, Mn
3+, Al
3+Or Ru
3+Trivalent metal ion; R
1, R
2Be H, C
1～C
6Alkyl, C
1～C
6Alkoxyl group, Cl, Br or NO
2Group; R
3, R
4For-(CH
2)
4-, CH
3, Ph or-CH
2N (R) CH
2-, wherein R is H, C
1～C
6Alkyl; X is Cl
-1, Br
-1, I
-1, NO
3 -1, CH
3COO
-1, ClO
-1, BF
4 -1, BPh
4 -1Or N
3 -1The monovalence negative ion.
In the Primary Catalysts, with metal ions M coordinate chirality tetradentate schiff base be by halogen, nitro, C by 3,5
1～C
6Salicylic aldehyde that the alkoxyl group or the tertiary butyl replace and the reaction of chiral diamine compounds make.
The chiral diamine compounds be (1R, 2R)-cyclohexanediamine, (1S, 2S)-cyclohexanediamine, (1R, 2R)-diphenyl ethylene diamine, (1S, 2S)-diphenyl ethylene diamine, (R)-1,2-propylene diamine or (S)-1, the 2-propylene diamine, (3R, 4R)-Domistan or (3S, 4S)-Domistan.Here, R represents dextrorotation in the bracket, and S represents left-handed, the position of numeral chiral carbon.
The general formula of promotor is R
1R
2 3YX
1Or (R
1 3P)
2YX
1Salt, in the formula: R
1Be C
1～C
16Alkyl, R
2Be C
1～C
6Alkyl or phenyl; Y is nitrogen, phosphorus or arsenic element; X
1Be Cl
-1, Br
-1, I
-1, NO
3 -1, CH
3COO
-1, ClO
4 -1, BF
4 -1, BPh
4 -1Or N
3 -1The monovalence negative ion.
Quaternary ammonium salt is Tetrabutyl amonium bromide, tetrabutylammonium chloride, tetrabutylammonium iodide, tetrabutyl ammonium azide, 4-propyl bromide, tetraethylammonium bromide, benzyl tributyl ammonium chloride, benzyl tributyl brometo de amonio, two-triphenyl phosphorus brometo de amonio, two-triphenyl phosphorus ammonium chloride, two-triphenyl phosphorus ammonium iodide or two-triphenyl phosphorus ammonium azide; Quaternary alkylphosphonium salt is butyl triphenyl phosphonium bromide, butyl triphenyl phosphonium iodide, butyl triphenyl phosphonium chloride, propyl group three phenyl phosphonium bromides; Season, arsine salt was the tetrabutyl phosphonium bromide arsine.
The chiral schiff base part that the present invention is used and the synthetic method of metal complexes thereof be referring to document: J.F.Larrow, E.N.Jacobsen, Y.Gao, et al., J.Org.Chem., 1994,59,1939; S.E.Schaus, B.D.Brandes, J.F.Larrow, et al., J.Am.Chem.Soc., 2002,124,1307.
The present invention relatively has the following advantages with the method that the document of reporting prepares polycarbonate:
(1) reaction conditions gentleness, process is easy;
(2) catalyst activity height, polymerisate selectivity height;
(3) the polycarbonate alternating structure is higher than 99%, has optical activity, and molecular weight distribution is narrower and adjustable;
(4) need not to add any organic solvent.
Embodiment
Embodiment 1
In effective volume is to add in the following order under envrionment temperature in the stainless steel autoclave of 75ml: 0.1 * 10
-3(1R, 2R) SalenCoX (sees structural formula, R in the formula to the mole chirality
1=R
2=
tBu, R
3, R
4For-(CH
2)
4-, X is 2, the 2, 4-dinitrophenol negative oxygen ion), 0.1 * 10
-3The mole tetrabutylammonium iodide, 0.2 mole of propylene oxide feeds carbon dioxide then and keeps the 2.0MPa constant voltage.Temperature is controlled at 25 ℃, stir reaction down after 4 hours in magnetic, slowly bleed off unreacted carbonic acid gas in the autoclave, decompression is down with collecting unreacted propylene oxide in-20 ℃ of cold-traps, add a certain amount of methyl alcohol/chloroform mixture then and make the superpolymer dissolving, add a large amount of ether sedimentations again and go out polycarbonate.Filter, and with the ether washing for several times, vacuum-drying obtains the poly-propylene carbonate white solid of 7.5 grams to constant weight.Molecular-weight average by this polymkeric substance of gel permeation chromatography is 28900, and molecular weight distribution is 1.35; Carry out it with Varian INOVA-400MHz nuclear magnetic resonance analyser
1H-NMR characterizes, and finds that its alternating structure is higher than 99%.This poly-propylene carbonate is dissolved in the tetrahydrofuran (THF), is degraded to cyclic carbonate propylene ester with trimethyl carbinol lithium, (30m * 0.25mm * 0.25mm) its e.e. value of mensuration is 45% on the HP6890 chromatogram by γ-butyl modification beta-cyclodextrin gas chromatographic column.
Embodiment 2
With embodiment 1 in the same equipment that uses, under the same conditions, just replace tetrabutylammonium iodide with tetrabutyl ammonium azide.After 4 hours, obtain the poly-propylene carbonate of 9.0 grams 25 ℃ of reactions, its molecular weight is 36300, and molecular weight distribution is 1.47, and carbonate unit is higher than 99% in the polymkeric substance, and the e.e. value is 45%.
Embodiment 3
With embodiment 1 in the same equipment that uses, under the same conditions, just replace tetrabutylammonium iodide with tetra-n-butyl ammonium bromide.After 4 hours, obtain the poly-propylene carbonate of 7.9 grams 25 ℃ of reactions, its molecular weight is 31500, and molecular weight distribution is 1.41, and carbonate unit is higher than 99% in the polymkeric substance, and the e.e. value is 47%.
Embodiment 4
With embodiment 1 in the same equipment that uses, under the same conditions, just with two-triphenyl phosphorus brometo de amonio replacement tetrabutylammonium iodide.After 4 hours, obtain the poly-propylene carbonate of 9.5 grams 25 ℃ of reactions, its molecular weight is 33400, and molecular weight distribution is 1.38, and carbonate unit is higher than 99% in the polymkeric substance, and the e.e. value is 41%.
Embodiment 5
With embodiment 1 in the same equipment that uses, under the same conditions, just change temperature of reaction into 40 ℃ by 25 ℃, after reacting 3 hours under this temperature, obtain the poly-propylene carbonate of 8.2 grams, its molecular weight is 28100, and molecular weight distribution is 1.29, carbonate unit is higher than 99% in the polymkeric substance, and the e.e. value is 43%.
Embodiment 6
With embodiment 3 in the same equipment that uses, under the same conditions, just with (1S, 2S) SalenCo (CCl
3COO) replace (1R, 2R) SalenCo (CCl
3COO).After 4 hours, obtain the poly-propylene carbonate of 6.6 grams 25 ℃ of reactions, its molecular weight is 30900, and molecular weight distribution is 1.37, and carbonate unit is higher than 99% in the polymkeric substance, and the e.e. value is 54%.
Embodiment 7
With embodiment 1 in the same equipment that uses, under the same conditions, just change pressure carbon dioxide into 0.4MPa by 2.0MPa.After 4 hours, obtain the poly-propylene carbonate of 6.5 grams 25 ℃ of reactions, its molecular weight is 27900, and molecular weight distribution is 1.39, and carbonate unit is higher than 99% in the polymkeric substance, and the e.e. value is 47%.
Embodiment 8
With embodiment 1 in the same equipment that uses, under the same conditions, just replace tetrabutylammonium iodide with the butyl triphenyl phosphonium bromide.After 5 hours, obtain the poly-propylene carbonate of 5.7 grams 25 ℃ of reactions, its molecular weight is 25800, and molecular weight distribution is 1.19, and carbonate unit is higher than 99% in the polymkeric substance, and the e.e. value is 51%.
Embodiment 9
With embodiment 1 in the same equipment that uses, under the same conditions, just with 1,2-butylene oxide ring replacement propylene oxide., obtain 8.5 grams and gather 1 after 8 hours 25 ℃ of reactions, the 2-butylene, its molecular weight is 19500, and molecular weight distribution is 1.21, and carbonate unit is higher than 99% in the polymkeric substance, and its e.e. value is 47%.
Embodiment 10
With embodiment 3 in the same equipment that uses, under the same conditions, just replace propylene oxide with the cyclohexene ring oxide compound., obtain 9.3 grams and gather 1 after 15 hours 80 ℃ of reactions, the 2-butylene, carbonate unit surpasses 99% in the polymkeric substance.
Embodiment 11
With embodiment 1 in the same equipment that uses, under the same conditions, just with (1R, 2R) SalenCoX ((R
1=R
2=
tBu, R
3, R
4For-CH
2N (H) CH
2-, X is 2, the 2, 4-dinitrophenol negative oxygen ion) be Primary Catalysts, two-triphenyl phosphorus ammonium azide is a promotor.After 3 hours, obtain the poly-propylene carbonate of 9.6 grams 25 ℃ of reactions, its molecular weight is 41900, and molecular weight distribution is 1.35, and carbonate unit surpasses 99% in the polymkeric substance, and the e.e. value is 48%.
Embodiment 12
With embodiment 1 in the same equipment that uses, under the same conditions, just with (1R, 2R) SalenCrCl ((R
1=R
2=
tBu, R
3, R
4For-CH
2N (H) CH
2-) be Primary Catalysts, two-triphenyl phosphorus ammonium azide is a promotor.After 6 hours, obtain the poly-propylene carbonate of 7.1 grams 25 ℃ of reactions, its molecular weight is 30900, and molecular weight distribution is 1.25, and carbonate unit surpasses 99% in the polymkeric substance.
Embodiment 13
With embodiment 1 in the same equipment that uses, under the same conditions, just with (1R, 2R) SalenAlCl ((R
1=R
2=
tBu, R
3, R
4For-(CH
2)
4-) be Primary Catalysts, two-triphenyl phosphorus ammonium azide is a promotor.After 8 hours, obtain the poly-propylene carbonate of 5.1 grams 25 ℃ of reactions, its molecular weight is 14900, and molecular weight distribution is 1.29, and carbonate unit surpasses 99% in the polymkeric substance, and the e.e. value is 33%.
Claims (6)
1, a kind of preparation method of optically active polycarbonate is characterized in that, be with racemation epoxy alkane and carbonic acid gas as reactant, be Primary Catalysts and be R with chirality tetradentate schiff base metal complexes SalenMX with the chemical formula
1R
2 3YX
1Or (R
1 3P)
2YX
1Salt be promotor, when carrying out the catalytic selectivity copolyreaction, help, the mol ratio of Primary Catalysts is 0.2～10: 1; Primary Catalysts and epoxy alkane mol ratio are 1: 500～10000; CO
2Original pressure be 0.1～4.0MPa; Temperature of reaction is 0～80 ℃; Reacted 0.5～24 hour.
According to the preparation method of the described a kind of optically active polycarbonate of claim 1, it is characterized in that 2, the general structure of described racemation epoxy alkane is:
Wherein R is CH
3, CH
2Cl, CH
2CH
3, Ph, CH
2(CH
2)
nCH
3Or CH
2(CH
2)
nCHCH
2, wherein n is 1～12.
According to the preparation method of the described a kind of optically active polycarbonate of claim 1, it is characterized in that 3, the general structure of described Primary Catalysts chirality tetradentate schiff base metal complexes SalenMX is:
In the formula: M is Fe
3+, Co
3+, Ni
3+, Cr
3+, Mn
3+, Al
3+Or Ru
3+Trivalent metal ion; R
1, R
2Be H, C
1～C
6Alkyl, C
1～C
6Alkoxyl group, Cl, Br or NO
2Group; R
3, R
4For-(CH
2)
4-, CH
3, Ph or-CH
2N (R) CH
2-, wherein R is H, C
1～C
6Alkyl; X is Cl
-1, Br
-1, I
-1, NO
3 -1, CH
3COO
-1, ClO
4 -1, BF
4 -1, BPh
4 -1Or N
3 -1The monovalence negative ion.
4, according to the preparation method of the described a kind of optically active polycarbonate of claim 1, it is characterized in that, in the described Primary Catalysts, with metal ions M coordinate chirality tetradentate schiff base be by halogen, nitro, C by 3,5
1～C
6Salicylic aldehyde that the alkoxyl group or the tertiary butyl replace and the reaction of chiral diamine compounds make.
5, according to the preparation method of the described a kind of optically active polycarbonate of claim 4, it is characterized in that, described chiral diamine compounds be (1R, 2R)-cyclohexanediamine, (1S, 2S)-cyclohexanediamine, (1R, 2R)-diphenyl ethylene diamine, (1S, 2S)-and diphenyl ethylene diamine, (R)-1,2-propylene diamine, (S)-1,2-propylene diamine, (3R, 4R)-Domistan or (3S, 4S)-Domistan.
According to the preparation method of the described a kind of optically active polycarbonate of claim 1, it is characterized in that 6, described promotor is that general formula is R
1R
2 3YX
1Or (R
1 3P)
2YX
1Salt, in the formula: R
1Be C
1～C
16Alkyl, R
2Be C
1～C
6Alkyl or phenyl; Y is nitrogen, phosphorus or arsenic element; X
1Be Cl
-1, Br
-1, I
-1, NO
3 -1, CH
3COO
-1, ClO
4 -1, BF
4 -1, BPh
4 -1Or N
3 -1The monovalence negative ion.Quaternary ammonium salt is Tetrabutyl amonium bromide, tetrabutylammonium chloride, tetrabutylammonium iodide, tetrabutyl ammonium azide, 4-propyl bromide, tetraethylammonium bromide, benzyl tributyl ammonium chloride, benzyl tributyl brometo de amonio, two-triphenyl phosphorus brometo de amonio, two-triphenyl phosphorus ammonium chloride, two-triphenyl phosphorus ammonium iodide or two-triphenyl phosphorus ammonium azide; Quaternary alkylphosphonium salt is butyl triphenyl phosphonium bromide, butyl triphenyl phosphonium iodide, butyl triphenyl phosphonium chloride, propyl group three phenyl phosphonium bromides; Season, arsine salt was the tetrabutyl phosphonium bromide arsine.
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|---|---|---|---|
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100355804C (en) * | 2006-03-06 | 2007-12-19 | 浙江大学 | Method for preparing high-molecular-weight polycarbonate |
| CN104059221A (en) * | 2013-07-01 | 2014-09-24 | 郑州裕昌有机硅化工有限公司 | Polycarbonate with optical activity and preparation method thereof |
| CN105566623A (en) * | 2016-03-09 | 2016-05-11 | 中国科学院长春应用化学研究所 | Polycarbonate material and preparation method thereof |
| CN106543423A (en) * | 2016-11-25 | 2017-03-29 | 河南大学 | Fatty poly-ester carbonate composite and preparation method thereof |
| CN106543424A (en) * | 2016-11-25 | 2017-03-29 | 河南大学 | A kind of poly (propylene carbonate)/POSS hybrid materials and preparation method thereof |
| CN109456471A (en) * | 2018-07-31 | 2019-03-12 | 大连理工大学 | A kind of method of simultaneously synthesizing chiral polyester and the chiral end position epoxyalkane of reservation |
-
2005
- 2005-03-21 CN CN 200510046092 patent/CN1663978A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100355804C (en) * | 2006-03-06 | 2007-12-19 | 浙江大学 | Method for preparing high-molecular-weight polycarbonate |
| CN104059221A (en) * | 2013-07-01 | 2014-09-24 | 郑州裕昌有机硅化工有限公司 | Polycarbonate with optical activity and preparation method thereof |
| CN105566623A (en) * | 2016-03-09 | 2016-05-11 | 中国科学院长春应用化学研究所 | Polycarbonate material and preparation method thereof |
| CN106543423A (en) * | 2016-11-25 | 2017-03-29 | 河南大学 | Fatty poly-ester carbonate composite and preparation method thereof |
| CN106543424A (en) * | 2016-11-25 | 2017-03-29 | 河南大学 | A kind of poly (propylene carbonate)/POSS hybrid materials and preparation method thereof |
| CN106543424B (en) * | 2016-11-25 | 2018-11-30 | 河南大学 | A kind of poly (propylene carbonate)/POSS hybrid material and preparation method thereof |
| CN106543423B (en) * | 2016-11-25 | 2018-12-28 | 河南大学 | Fatty poly-ester carbonate composite material and preparation method |
| CN109456471A (en) * | 2018-07-31 | 2019-03-12 | 大连理工大学 | A kind of method of simultaneously synthesizing chiral polyester and the chiral end position epoxyalkane of reservation |
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