CN100494248C - Double function catalyst for synthesizing polycarbonate - Google Patents
Double function catalyst for synthesizing polycarbonate Download PDFInfo
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- CN100494248C CN100494248C CNB2007100107066A CN200710010706A CN100494248C CN 100494248 C CN100494248 C CN 100494248C CN B2007100107066 A CNB2007100107066 A CN B2007100107066A CN 200710010706 A CN200710010706 A CN 200710010706A CN 100494248 C CN100494248 C CN 100494248C
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Abstract
The present invention relates to one kind of high activity catalyst for catalyzing and activating CO2 to react with alkane epoxide to synthesize polycarbonate. The high activity catalyst is tetradentate Schiff base metal complex with double function, i. e., it has both electrophlic center originated from the metal ion in the complex and nucleophilic center originated from the quaternary ammonium salt or quaternary phosphonium salt connected to the benzene ring in the complex. The catalyst can catalyze the reaction of CO2 and alkane epoxide effectively to prepare polycarbonate.
Description
Technical field
The present invention relates to be used for the catalyzer of polycarbonate synthesis, particularly a kind of high reactivity single component dual-function catalyst by catalytic activation carbonic acid gas and epoxy alkane reaction polycarbonate synthesis.
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.
The patent report for preparing polycarbonate about carbonic acid gas and epoxy alkane copolymerization is arranged at present much both at home and abroad.Use bicomponent catalyst based on zinc alkyl(s) to obtain molecular weight as U.S. Pat 3585168, US 3900424 and US 3953383 and be higher than 20000 polycarbonate, urethane and polyethers.Day disclosure laid-open patent JP02142824 and JP 02575199 adopt metalloporphyrin complex catalysis carbonic acid gas and epoxy alkane polycarbonate synthesis, and catalytic efficiency reaches 10
3～10
4Gram polymkeric substance/mol catalyst, 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 10
4The catalytic efficiency of gram polymkeric substance/mol catalyst, but carrier is difficult to separate with the polycarbonate that generates.Chinese patent application CN 98125654.6, CN00136189.9 and CN 03105023.9 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.The patent of application (Chinese patent application number: CN200410021316.5) before us, once report use by tetradentate schiff base metal complexes and quaternary ammonium salt or season the two-pack catalyst system formed of squama salt, can react the highly selective polycarbonate synthesis with epoxy alkane at catalysis carbonic acid gas under the relative mild conditions, catalytic efficiency reaches 10
5Gram polymkeric substance/mol catalyst.
Above-mentioned preparation polycarbonate method have low, the long reaction time of catalyst activity mostly, and pressure is higher, needs organic solvent; It is lower to supervene in cyclic carbonate by product or the polymerisate carbonate unit; The mol ratio height of catalyzer and reaction substrate in the reaction system; Problems such as product and catalyst separating difficulty.
Summary of the invention
The technical problem to be solved in the present invention provides the unit molecule dual-function catalyst of selectivity catalysis carbonic acid gas and epoxy alkane prepared in reaction high molecular under a kind of reaction conditions lower and gentle relatively at catalyst concn, high alternating structure polycarbonate.
Technical scheme of the present invention is that the dual-function catalyst that is used for polycarbonate synthesis is the tetradentate schiff base metal complexes, contains quaternary ammonium salt Huo quaternary alkylphosphonium salt group in its molecule.Metal ion in the schiff base metal complex has Electron Affinities matter, and quaternary ammonium salt that connects on its phenyl ring or quaternary alkylphosphonium salt have nucleophilic character, and it can be the alternately polycarbonate material of structure in catalysis carbonic acid gas and epoxy alkane reaction high-level efficiency preparation under the lower concentration.(Chinese patent application number: CN200410021316.5) differently be: catalyzer of the present invention is an one-component, not only contains electrophilic center but also contain nucleophilic center in its molecular structure with the bicomponent catalyst system of report before us.This dual-function catalyst has following constitutional features:
Or
Or
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, CH
3, CH
2CH
3Or Ph; R
3Be H, C
1～C
6Alkyl, C
1～C
6Alkoxyl group, Cl, Br or NO
2Group; R
4, R
5Be H, C
1～C
6Alkyl; R
6Be C
1～C
6Alkyl or Ph; N is 0～10; Z is elemental nitrogen or phosphorus; X, Y are F
-1, Cl
-1, Br
-1, I
-1, NO
3 -1, CH
3COO
-1, CCl
3COO
-1, CF
3COO
-1, ClO
4 -1, BF
4 -1, BPh
4 -1, N
3 -1, p-methylbenzoic acid root, p-methyl benzenesulfonic acid root, ONP oxygen, right-nitrophenols oxygen ,-nitrophenols oxygen, 2,2, 4-dinitrophenol oxygen, 3,5-dinitrophenol(DNP) oxygen, 2,4,6-trinitrophenol oxygen, 3,5-chlorophenesic acid oxygen, 3,5-difluorophenol oxygen, 3,5-di-trifluoromethyl phenol oxygen or pentafluranol negative oxygen ion.
In the dual-function catalyst structure, with metallic ion coordination be contain quaternary ammonium salt or season squama salt group salicylic aldehyde and the tetradentate schiff base part that obtains of diamine compounds reaction.Diamine compounds is a quadrol, 1,2-propylene diamine, 1,3-propylene diamine, 1,2-butanediamine, 2,3-butanediamine or diphenyl ethylene diamine.
When using dual-function catalyst provided by the invention, the mol ratio of catalyzer and epoxy alkane is 1:2000 to 1:200000 in the reaction system, CO
2Pressure is 0.1～6.0MPa, and temperature of reaction is 10～100 ℃, reacts 1～48 hour.
The general structure of used reactant epoxy alkane is during the preparation polycarbonate:
R wherein
1, R
2Be H, CH
3, CH
2Cl, CH
2CH
3Or CH
2(CH
2)
nCH
3, wherein n is 1～12.
The invention provides the method for preparing polycarbonate and have following effect and benefit:
(1) under low catalyst concentration, still has higher catalytic activity;
(2) reaction conditions is gentle relatively, and process is easy;
(3) catalyst activity height, polymerisate selectivity height;
(4) alternating structure is higher than 97% in the polycarbonate product, and molecular weight distribution is narrower;
(5) need not to add any organic solvent.
Embodiment
Be described in detail specific embodiments of the invention below in conjunction with technical scheme.
Embodiment 1
In effective volume is to add in the following order under envrionment temperature in the stainless steel autoclave of 200ml: (X, Y are 2 to 0.1 mmole tetradentate schiff base cobalt complex, the 2, 4-dinitrophenol negative oxygen ion; R
1=R
2=H; R
3Be the tertiary butyl; R
4, R
5Be methyl; R
6Be normal-butyl; N is 2; Z is the nitrogen element; Contain quaternary ammonium salt group and be in 5 places of phenyl ring) and 1 mole of propylene oxide, feed carbon dioxide then and keep the 2.0MPa constant voltage.Temperature is controlled at 50 ℃, reaction slowly bled off unreacted carbonic acid gas in the autoclave after 6 hours under magnetic stirs, and collected 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 37 grams to constant weight.Molecular-weight average by this polymkeric substance of gel permeation chromatography is 53800, and molecular weight distribution is 1.27; With Varian INOVA-400MHz nmr determination its
1H-NMR finds that its alternating structure surpasses 99%.
Embodiment 2
With embodiment 1 in the same equipment that uses, under the same terms, be 3 by 5 changes just with containing quaternary ammonium salt group on the title complex phenyl ring in the tetradentate schiff base cobalt complex, the tertiary butyl is 5 by 3 changes.After 6 hours, obtain the poly-propylene carbonate of 31 grams 50 ℃ of reactions, its molecular weight is 52300, and molecular weight distribution is 1.17, and carbonate unit surpasses 99% in the polymkeric substance.
Embodiment 3
With embodiment 1 in the same equipment that uses, under the same terms, just be on the title complex phenyl ring in the tetradentate schiff base cobalt complex the tertiary butyl on 3 also change into be in 5 on the identical quaternary ammonium salt group that contains.After 6 hours, obtain the poly-propylene carbonate of 48 grams 50 ℃ of reactions, its molecular weight is 46200, and molecular weight distribution is 1.41, and carbonate unit surpasses 99% in the polymkeric substance.
Embodiment 4
With embodiment 1 under the same equipment and same catalyst condition that use, just with temperature of reaction by changing 25 ℃ at 50 ℃.After 24 hours, obtain the poly-propylene carbonate of 51 grams in reaction under this temperature, its molecular weight is 75100, and molecular weight distribution is 1.21, and carbonate unit surpasses 99% in the polymkeric substance.
Embodiment 5
With embodiment 1 under the same equipment and same catalyst condition that use, just with temperature of reaction by changing 75 ℃ at 50 ℃.After 2 hours, obtain the poly-propylene carbonate of 41 grams in reaction under this temperature, its molecular weight is 43800, and molecular weight distribution is 1.28, and carbonate unit surpasses 99% in the polymkeric substance.
Embodiment 6
With embodiment 1 under the same equipment and same catalyst condition that use, just the mol ratio with catalyzer and propylene oxide changes 1:20000 into by 1:10000.Reaction is after 12 hours down at 50 ℃, and acquisition 35 grams gather propylene carbonate, and its molecular weight is 91800, and molecular weight distribution is 1.24, and carbonate unit surpasses 99% in the polymkeric substance.
Embodiment 7
With embodiment 1 under the same equipment and same catalyst condition that use, just reaction pressure is brought up to 5.0MPa by 2.0MPa.Reaction is after 6 hours down at 50 ℃, and acquisition 31 grams gather propylene carbonate, and its molecular weight is 40800, and molecular weight distribution is 1.19, and carbonate unit surpasses 99% in the polymkeric substance.
Embodiment 8
With embodiment 1 under the same equipment and same catalyst condition that use, just with 1,2-butylene oxide ring replacement propylene oxide.After 10 hours, obtain 35 gram polycarbonate 50 ℃ of reactions, its molecular weight is 61400, and molecular weight distribution is 1.38, and carbonate unit surpasses 99% in the polymkeric substance.
Embodiment 9
With embodiment 1 under the same equipment and same catalyst condition that use, just replace propylene oxide with oxyethane.After 6 hours, obtain 32 gram polycarbonate 50 ℃ of reactions, its molecular weight is 44400, and molecular weight distribution is 1.41, and carbonate unit surpasses 99% in the polymkeric substance.
Embodiment 10
With embodiment 1 in the same equipment that uses, under the same terms, just change metal ion in the tetradentate schiff base metal complexes into chromium by cobalt, X, Y are by 2 in the title complex, the 2, 4-dinitrophenol negative oxygen ion changes NO into
3 -Negative ion.After 24 hours, obtain the poly-propylene carbonate of 29 grams 50 ℃ of reactions, its molecular weight is 102000, and molecular weight distribution is 1.37, and carbonate unit is 99% in the polymkeric substance.
Embodiment 11
With embodiment 1 in the same equipment that uses, under the same terms, just change metal ion in the tetradentate schiff base metal complexes into aluminium by cobalt, X, Y are by 2 in the title complex, the 2, 4-dinitrophenol negative oxygen ion changes Cl into
-Negative ion.After 24 hours, obtain the poly-propylene carbonate of 17 grams 50 ℃ of reactions, its molecular weight is 32000, and molecular weight distribution is 1.59, and carbonate unit is 97% in the polymkeric substance.
Embodiment 12
With embodiment 1 in the same equipment that uses, under the same terms, just with R in the tetradentate schiff base cobalt complex
5Change phenyl into by normal-butyl, Z changes phosphoric into by the nitrogen element.After 6 hours, obtain the poly-propylene carbonate of 34 grams 50 ℃ of reactions, its molecular weight is 63700, and molecular weight distribution is 1.21, and carbonate unit is 99% in the polymkeric substance.
Embodiment 13
With embodiment 11 in the same equipment that uses, under the same terms, just with X, Y in the tetradentate schiff base cobalt complex by 2, the 2, 4-dinitrophenol negative oxygen ion changes Cl into
-Negative ion.After 6 hours, obtain the poly-propylene carbonate of 29 grams 50 ℃ of reactions, its molecular weight is 51000, and molecular weight distribution is 1.38, and carbonate unit is 99% in the polymkeric substance.
Claims (4)
1. the dual-function catalyst that is used for polycarbonate synthesis is characterized in that this catalyzer is that the tetradentate schiff base metal is joined
Or
Or
In the formula: M is Fe
3+, Co
3+, Ni
3+, Cr
3+, Mn
3+, Al
3+Or Ru
3+R
1, R
2Be H, CH
3, CH
2CH
3Or Ph; R
3Be H, C
1～C
6Alkyl, C
1～C
6Alkoxyl group, Cl, Br or NO
2Group; R
4, R
5Be H, C
1～C
6Alkyl; R
6Be C
1～C
6Alkyl or Ph; N is 0～10; Z is elemental nitrogen or phosphorus; X, Y are F
-1, Cl
-1, Br
-1, I
-1, NO
3 -1, CH
3COO
-1, CCl
3COO
-1, CF
3COO
-1, ClO
4 -1, BF
4 -1, BPh
4 -1, N
3 -1, p-methylbenzoic acid root, p-methyl benzenesulfonic acid root, ONP oxygen, right-nitrophenols oxygen ,-nitrophenols oxygen, 2,2, 4-dinitrophenol oxygen, 3,5-dinitrophenol(DNP) oxygen, 2,4,6-trinitrophenol oxygen, 3,5-chlorophenesic acid oxygen, 3,5-difluorophenol oxygen, 3,5-di-trifluoromethyl phenol oxygen or pentafluranol negative oxygen ion.
2. according to the described dual-function catalyst that is used for polycarbonate synthesis of claim 1, it is characterized in that the part in the tetradentate schiff base metal complexes is to be made by salicylic aldehyde that contains quaternary ammonium salt Huo quaternary alkylphosphonium salt group and diamine compounds reaction; Diamine compounds is a quadrol, 1,2-propylene diamine, 1,3-propylene diamine, 1,2-butanediamine, 2,3-butanediamine or diphenyl ethylene diamine.
3. a method of using the described dual-function catalyst polycarbonate synthesis of claim 1 is characterized in that being used for catalysis carbonic acid gas and epoxy alkane prepared in reaction polycarbonate, and application rights requires 1 described dual-function catalyst, and temperature of reaction is 10～100 ℃, CO
2Pressure is 0.1～6.0MPa, and the mol ratio of catalyzer and epoxy alkane is 1:2000 to 1:200000, reacts 1～48 hour.
4. a kind of method of using the described dual-function catalyst polycarbonate synthesis of claim 1 according to claim 3 is characterized in that as the general structure of reactant epoxy alkane being:
R wherein
1, R
2Be H, CH
3, CH
2Cl, CH
2CH
3Or CH
2(CH
2)
nCH
3, wherein n is 1～12.
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| CNB2007100107066A CN100494248C (en) | 2007-03-21 | 2007-03-21 | Double function catalyst for synthesizing polycarbonate |
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| CN100494248C true CN100494248C (en) | 2009-06-03 |
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| GB0904654D0 (en) * | 2009-03-18 | 2009-04-29 | Univ Newcastle | Synthesis of cyclic carbonates |
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