CN1887934A - Polycarbonate material in alternating structure - Google Patents

Polycarbonate material in alternating structure Download PDF

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CN1887934A
CN1887934A CN 200610200053 CN200610200053A CN1887934A CN 1887934 A CN1887934 A CN 1887934A CN 200610200053 CN200610200053 CN 200610200053 CN 200610200053 A CN200610200053 A CN 200610200053A CN 1887934 A CN1887934 A CN 1887934A
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epoxy
epoxy alkane
alkane
ammonium
tetrahydrobenzene
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CN100384909C (en
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吕小兵
时磊
张英菊
王辉
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Dalian University of Technology
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Dalian University of Technology
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Abstract

The present invention belongs to the field of high molecular material, and is especially one kind of polycarbonate material in alternating structure. The present invention features that the polycarbonate material in alternating structure is prepared with two or more kinds of epoxy alkane and CO2 and through copolymerization under the action of catalyst. The polycarbonate material features carbonate unit content in the polymer chain of 90-100 %, alternate unit content of 5-95 %, and only one glass transition temperature depending on the kinds and ratio of the epoxy alkanes. The polycarbonate material has glass transition temperature and mechanical strength higher than that of aliphatic polycarbonate, and flexibility and tensile strength higher than that of polycyclocarbonate.

Description

A kind of alternately polycarbonate material of structure that is
Technical field
The invention belongs to polymeric material field, relate to a kind of alternately polycarbonate material of structure that is.
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.But, problem such as Kai Fa aliphatic polycarbonate material ubiquity second-order transition temperature and intensity is on the low side now, that poly-cyclic carbonate then exists is easily crisp, be difficult to shortcoming such as processing.Chinese patent application number: 03146996.5,02149612.9 and 200510034174.0 successively report prepare matrix material with natural mineral filler, starch or polyvinyl alcohol and aliphatic polycarbonate blending and modifying.People such as Tan change the performance of poly-carbon dioxide plastic in the mode of synthetic fat adoption carbonic ether and poly-cyclic carbonate ester block copolymer (Polymer, 2002,43,4535).Also have scientist's report will be used for carbonic acid gas/propylene oxide/epoxy cyclohexane copolymerization, but what obtain is the polycarbonate material (Macromol.Symp., 2003,195,281) that two second-order transition temperatures are arranged based on the three-element catalytic system of rare earth compounding.And degradability described in the invention is alternately structure polycarbonate material, only have only a second-order transition temperature and one section very narrow heat decomposition temperature, and second-order transition temperature changes with the difference of material 50% heat decomposition temperature with two or more epoxy alkane ratio of using the different of epoxy alkane and participation copolymerization.
At present, the patent report for preparing polycarbonate about carbonic acid gas and epoxy alkane copolymerization is arranged much both at home and abroad.Adopt 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 JP 02142824 and JP 02575199 adopt expensive 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 CN89100701.6 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, CN 00136189.9 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, a kind of highly active single-activity point organic zinc catalyzer has been described, obtain molecular weight between 20000 ~ 40000 and be the poly-propylene carbonate of narrow distribution, but also produce 13 ~ 25% cyclic carbonate propylene ester by product synchronously.
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; Problems such as product and catalyst separating difficulty.Recently, the inventor report a kind of under low pressure or middle pressure selectivity catalysis epoxy alkane and carbon dioxide reaction prepare method (Chinese patent application numbers 200410021316.5 and the Angew.Chem.Int.Ed. of the polycarbonate of high molecular, high alternating structure, 2004,43,3574).The present invention is the system that the employed catalyst system of structure polycarbonate material alternately once applied for protecting the same as or similar to us (Chinese patent application number 200410021316.5 and 200510046091.3) at the preparation degradability.
Summary of the invention
The present invention seeks to propose a kind of polycarbonate material of being convenient to second-order transition temperature and heat decomposition temperature within the specific limits, overcome that the on the low side and poly-cyclic carbonate of ubiquitous second-order transition temperature of aliphatic polycarbonate and intensity exists easily crisp, be difficult to shortcoming such as processing.
Technical scheme of the present invention is that the polycarbonate material that is proposed has following feature: carbonate unit content is 90%-100% in the polymeric chain; Different epoxy alkane and carbonic acid gas form different carbonate units and are the content that replaces character mutually account for 5~95% in the polymkeric substance carbonate unit, contain one or both of two kinds of structural units of following formula in the polycarbonate material structure:
R is H, CH3, C2H5, CH2Cl or CH2-(CH2) n-CH=CH2 in the formula, molecular formula n=0~8 wherein, and Ph is a phenyl.The number-average molecular weight of polycarbonate material is between 3000~250000, and molecular weight distribution is 1.01~15.00.This polycarbonate material has only a second-order transition temperature and one section very narrow heat decomposition temperature, and second-order transition temperature changes with the difference of using the different of epoxy alkane and the various epoxy alkane ratios of participation copolymerization with material 50% heat decomposition temperature.Wherein, variable glass transition temperature range is 45~120 ℃, and variable material 50% pyrolysis temperature range is 175~325 ℃.
The polycarbonate material that is proposed comprises oxyethane/tetrahydrobenzene epoxy alkane/carbonic acid gas terpolymer, propylene oxide/tetrahydrobenzene epoxy alkane/carbonic acid gas terpolymer, 1,2-butylene oxide ring/tetrahydrobenzene epoxy alkane/carbonic acid gas terpolymer, 1,2-epoxy-7-octene/tetrahydrobenzene epoxy alkane/carbonic acid gas terpolymer, 1,2-epoxy-5,6-epoxy hexane/tetrahydrobenzene epoxy alkane/carbonic acid gas terpolymer, oxyethane/phenyl ethylene oxide/carbonic acid gas terpolymer, propylene oxide/phenyl ethylene oxide/carbonic acid gas terpolymer, oxyethane/1,2-propylene oxide/tetrahydrobenzene epoxy alkane/carbon dioxide copolymer, oxyethane/1,2 epoxy prapane/phenyl ethylene oxide/carbon dioxide copolymer, oxyethane/tetrahydrobenzene epoxy alkane/phenyl ethylene oxide/carbon dioxide copolymer or propylene oxide/tetrahydrobenzene epoxy alkane/phenyl ethylene oxide/carbon dioxide copolymer.
Concrete preparation process is as follows:
With 1~5 kind of aliphatic epoxy alkane and at least a ring-type epoxy alkane and carbon dioxide copolymerization, adopt with tetradentate schiff base metal complexes (R 1) (R 2) SalenMX is Primary Catalysts and is R with the chemical formula 1R 2 3YX 1Salt or high hindered organic alkali be promotor; The mol ratio that participates in polymeric aliphatic epoxy alkane and ring-type epoxy alkane is 1: 0.05~20; When carrying out copolyreaction, help, the mol ratio of Primary Catalysts is 1: 0.2~5; Primary Catalysts and epoxy alkane mol ratio are 1: 100~10000; CO 2Pressure is 0.1~6.0MPa; Temperature of reaction is 0~80 ℃; Reaction times is 1~48 hour.
Employed aliphatic epoxy alkane is oxyethane, 1,2 epoxy prapane, 1,2-butylene oxide ring, 1,2-epoxy pentane, 1,2-epoxy hexane, 1,2-octylene oxide, 1,2-epoxy-5-hexene, 1,2-epoxy-7-octene, 1,2-epoxy-5,6-epoxy hexane, 1,2-epoxy-7,8-octylene oxide, 1,2-epoxy-9,10-epoxy certain herbaceous plants with big flowers alkane, epoxy chloropropane or epoxy fluoro-propane; Employed ring-type epoxy alkane is tetrahydrobenzene epoxy alkane (also being referred to as epoxy cyclohexane), phenyl ethylene oxide or cyclopentenes epoxy alkane.
Used Primary Catalysts tetradentate schiff base metal complexes (R 1) (R 2) general structure of SalenMX is:
Figure A20061020005300071
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 2For-H, C 1~C 6Alkyl, C 1~C 6Alkoxyl group ,-Cl ,-Br or-NO 2Group; R 3, R 4For-(CH 2) 4-, CH 3, H, Ph ,-(CH) 4-or-CH 2NHCH 2-; X is I -1, Br -1, Cl -1, NO 3 -1, CH 3COO -1, CCl 3COO -1, CF 3COO -1, ClO 4 -1, BF 4 -1, BPh 4 -1, N 3 -1Monovalence negative ion or 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 or 3,5-two-(trifluoromethyl) phenol negative oxygen ion.In the Primary Catalysts, with metal ions M coordinate 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 diamines or the reaction of three aminated compoundss make.Diamine compounds is a quadrol, 1,2-propylene diamine, 2,3-butanediamine, cyclohexanediamine, 1,2-O-Phenylene Diamine or diphenyl ethylene diamine.Three aminated compoundss are diethylenetriamine or Domistan.
Used promotor is an etamon chloride, tetraethylammonium bromide, tetraethyl ammonium iodide, Tetrabutyl amonium bromide, the tetraethyl-ammonium acetate, tetrabutylammonium chloride, tetrabutylammonium iodide, the tetrapropyl ammonium iodide, 4-propyl bromide, 4-propyl ammonium chloride, the tetrapropyl ammonium acetate, the benzyl triethyl ammonium ammonium iodide, benzyl triethyl ammonium bromide, benzyltriethylammoinium chloride, benzyl tripropyl ammonium chloride, benzyl tributyl ammonium chloride, benzyl tributyl brometo de amonio, 4-propyl ammonium chloride, two-(triphenyl phosphorus) brometo de amonios, two-(triphenyl phosphorus) ammonium chlorides, two-(triphenyl phosphorus) ammonium iodides, two-(triphenyl phosphorus) ammonium azide, two-(triphenyl phosphorus) ammonium acetates, four butyl phosphonium iodides, four butyl phosphonium bromides, 4-butyl phosphonium chloride, the butyl triphenyl phosphonium bromide, benzyl three phenyl phosphonium bromides, the butyl triphenyl phosphonium iodide, the butyl triphenyl phosphonium chloride, propyl group three phenyl phosphonium bromides, 1,8-diazabicyclo [5.4.0] 11-7-alkene (DBU), 3,3,6,9,9-pentamethyl--2,10-diazabicyclo [4.4.0] ten-1-alkene (PMDBD), the 7-methyl isophthalic acid, 5,7-three azabicyclos [4.4.0] ten-5-alkene (MTBD), 7-ethyl-1,5,7-three azabicyclos [4.4.0] ten-5-alkene (ETBD), 7-normal-butyl-1,5,7-three azabicyclos [4.4.0] ten-5-alkene (BTBD), 7-benzyl-1,5,7-three azabicyclos [4.4.0] ten-5-alkene (BnTBD), 1,5-diazabicyclo [4.3.0] nine-5-alkene (DBN) or 1,5,7-three azabicyclos [4.4.0] ten-5-alkene (TBD).
Figure A20061020005300081
Effect of the present invention and benefit are: polycarbonate material of the present invention has second-order transition temperature and the physical strength that is higher than aliphatic polycarbonate, and poly-better flexibility of cyclic carbonate and tensile strength.Can require to obtain different polymer materialss to the difference of degradability polymer materials performance at environment for use.
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: 0.5 * 10-3 mole (R1) (R2) SalenCoX (R1 and R2 are t-Bu, X is 2, the 2, 4-dinitrophenol negative oxygen ion), 0.5 * 10-3 mole tetrabutylammonium chloride, 0.25 mole of propylene oxide and 0.25 mole of tetrahydrobenzene epoxy paraffins mixture, feed carbon dioxide then and keep the 2.0MPa constant voltage.Temperature is controlled at 25 ℃, stir reaction down after 6 hours in magnetic, slowly bleed off unreacted carbonic acid gas in the autoclave, collect unreacted propylene oxide and tetrahydrobenzene epoxy alkane in-20 ℃ under the low pressure, 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 24.6 gram polycarbonate white solids to constant weight.Number-average molecular weight by this polymkeric substance of gel permeation chromatography is 29400, and molecular weight distribution is 1.24; With its 1H-NMR of Varian INOVA-400MHz nmr determination, find that carbonate unit content reaches 99% in the polymkeric substance, linear propylene carbonate ester units is about 6: 4 with the ratio that contains the hexanaphthene carbonate unit, by 13C-NMR analyze to find these two kinds of epoxy alkane and carbonic acid gas form content that different carbonate units are character alternately mutually in all carbonate units of polymkeric substance above 75%.Having only one with its second-order transition temperature of dsc analysis (Tg), is 70.2 ℃; Thermogravimetric analysis shows that its 50% material breakdown temperature is 275 ℃.
Embodiment 2
Operation is with embodiment 1, and the amount that just will participate in reacting epoxy alkane changes 0.35 mole of propylene oxide and 0.15 mole of tetrahydrobenzene epoxy paraffins mixture into, and 25 ℃ and 2.0MPa reaction 6 hours down obtains 28.1 gram polycarbonate white solids.Its number-average molecular weight is 31600, and molecular weight distribution is 1.21; Carbonate unit content reaches 99% in the polymkeric substance, and linear propylene carbonate ester units is about 7.5: 2.5 with the ratio that contains the hexanaphthene carbonate unit; Two kinds of epoxy alkane and carbonic acid gas form different carbonate units and are mutually alternately that the content of character surpasses 45% in all carbonate units of polymkeric substance; Second-order transition temperature (Tg) is 54.5 ℃; Thermogravimetric analysis shows that its 50% material breakdown temperature is 268 ℃.
Embodiment 3
Operation is with embodiment 1, and the amount that just will participate in reacting epoxy alkane changes 0.15 mole of propylene oxide and 0.35 mole of tetrahydrobenzene epoxy paraffins mixture into, and 25 Fei and 2.0MPa reacted 6 hours down, obtains 22.4 gram polycarbonate white solids.Its number-average molecular weight is 28500, and molecular weight distribution is 1.29; Carbonate unit content reaches 99% in the polymkeric substance, and linear propylene carbonate ester units is about 6.1: 3.9 with the ratio that contains the hexanaphthene carbonate unit; Two kinds of epoxy alkane and carbonic acid gas form different carbonate units and are mutually alternately that the content of character surpasses 75% in all carbonate units of polymkeric substance; Second-order transition temperature (Tg) is 85.5 ℃; Thermogravimetric analysis shows that its 50% material breakdown temperature is 292 ℃.
Embodiment 4
Operation is with embodiment 1, the aliphatic epoxy alkane that just will participate in reaction changes oxyethane into by propylene oxide, promptly use 0.25 moles of ethylene oxide and 0.25 mole of tetrahydrobenzene epoxy paraffins mixture, 25 Fei and 2.0MPa reacted 6 hours down, obtained 30.1 gram polycarbonate white solids.Its number-average molecular weight is 27900, and molecular weight distribution is 1.33; Carbonate unit content reaches 99% in the polymkeric substance, and linear ethylene carbonate ester units is about 6.4: 3.6 with the ratio that contains the hexanaphthene carbonate unit; Two kinds of epoxy alkane and carbonic acid gas form different carbonate units and are mutually alternately that the content of character surpasses 60% in all carbonate units of polymkeric substance; Second-order transition temperature (Tg) is 51.5 ℃; Thermogravimetric analysis shows that its 50% material breakdown temperature is 257 ℃.
Embodiment 5
Operation is with embodiment 1, the aliphatic epoxy alkane that just will participate in reaction changes butylene oxide ring into by propylene oxide, promptly use 0.25 mole of butylene oxide ring and 0.25 mole of tetrahydrobenzene epoxy paraffins mixture, 25 Fei and 2.0MPa reacted 6 hours down, obtained 22.3 gram polycarbonate white solids.Its number-average molecular weight is 24900, and molecular weight distribution is 1.26; Carbonate unit content reaches 99% in the polymkeric substance, and linear ethylene carbonate ester units is about 5.7: 4.3 with the ratio that contains the hexanaphthene carbonate unit; Two kinds of epoxy alkane and carbonic acid gas form different carbonate units and are mutually alternately that the content of character surpasses 80% in all carbonate units of polymkeric substance; Second-order transition temperature (Tg) is 71.9 ℃; Thermogravimetric analysis shows that its 50% material breakdown temperature is 291 ℃.
Embodiment 6
Operation is with embodiment 1, the catalyzer that just will be used for catalytic polymerization by (R1) (R2) SalenCoX (R1 and R2 are t-Bu, and X is 2, the 2, 4-dinitrophenol negative oxygen ion)/tetrabutylammonium chloride change (R1) (R2) SalenCoNO into 3(R1 and R2 are t-Bu)/7-methyl isophthalic acid, 5,7-three azabicyclos [4.4.0] ten-5-alkene (MTBD).25 ℃ and 2.0MPa reaction 10 hours down obtains 25.1 gram polycarbonate white solids.Its number-average molecular weight is 41300, and molecular weight distribution is 1.19; Carbonate unit content reaches 99% in the polymkeric substance, and linear propylene carbonate ester units is about 6.1: 3.9 with the ratio that contains the hexanaphthene carbonate unit; Two kinds of epoxy alkane and carbonic acid gas form different carbonate units and are mutually alternately that the content of character surpasses 75% in all carbonate units of polymkeric substance; Second-order transition temperature (Tg) is 71.1 ℃; Thermogravimetric analysis shows that its 50% material breakdown temperature is 277 ℃.
Embodiment 7
Operation is with embodiment 1, the aliphatic epoxy alkane that just will participate in reaction changes oxyethane and propylene oxide mixture (1/1 mol ratio) into by propylene oxide, promptly use 0.125 moles of ethylene oxide, 0.125 moles of ethylene oxide and 0.25 mole of tetrahydrobenzene epoxy paraffins mixture, 25 Fei and 2.0MPa reacted 6 hours down, obtained 25.3 gram polycarbonate white solids.Its number-average molecular weight is 29500, and molecular weight distribution is 1.19; Carbonate unit content reaches 99% in the polymkeric substance, and linear propylene carbonate ester units is about 6.3: 3.7 with the ratio that contains the hexanaphthene carbonate unit; Two kinds of epoxy alkane and carbonic acid gas form different carbonate units and are mutually alternately that the content of character surpasses 70% in all carbonate units of polymkeric substance; Second-order transition temperature (Tg) is 63.5 ℃; Thermogravimetric analysis shows that its 50% material breakdown temperature is 266 ℃.
Embodiment 8
Operation is with embodiment 1, the ring-type epoxy alkane that just will participate in reaction changes tetrahydrobenzene epoxy alkane and phenyl ethylene oxide mixture (1/1 mol ratio) into by tetrahydrobenzene epoxy alkane, promptly use 0.25 mole of propylene oxide, 0.125 mole of tetrahydrobenzene epoxy alkane and 0.125 mole of phenyl ethylene oxide mixture, 25 ℃ and 2.0MPa reaction 6 hours down obtains 27.8 gram polycarbonate white solids.Its number-average molecular weight is 35500, and molecular weight distribution is 1.22; Carbonate unit content reaches 99% in the polymkeric substance, and linear propylene carbonate ester units is about 6.5: 3.5 with the ratio that contains hexanaphthene carbonic ether and phenyl-carbonic acid ester units; Two kinds of epoxy alkane and carbonic acid gas form different carbonate units and are mutually alternately that the content of character surpasses 60% in all carbonate units of polymkeric substance; Second-order transition temperature (Tg) is 68.5 ℃; Thermogravimetric analysis shows that its 50% material breakdown temperature is 288 ℃.
Embodiment 9
Operation is with embodiment 1, the catalyzer that just will be used for catalytic polymerization by (R1) (R2) SalenCoX (R1 and R2 are t-Bu, X is 2, the 2, 4-dinitrophenol negative oxygen ion)/tetrabutylammonium chloride changes (R1) (R2) SalenCr Seed 03 (R1 and R2 are t-Bu)/7-methyl isophthalic acid into, 5,7-three azabicyclos [4.4.0] ten-5-alkene (MTBD), temperature of reaction changes 50 ℃ and 2.0MPa reaction 10 hours down into by 25 ℃, obtains 29.4 gram polycarbonate white solids.Its number-average molecular weight is 26300, and molecular weight distribution is 1.35; Carbonate unit content reaches 98% in the polymkeric substance, and linear propylene carbonate ester units is about 5.8: 4.2 with the ratio that contains the hexanaphthene carbonate unit; Two kinds of epoxy alkane and carbonic acid gas form different carbonate units and are mutually alternately that the content of character surpasses 60% in all carbonate units of polymkeric substance; Second-order transition temperature (Tg) is 76.1 ℃; Thermogravimetric analysis shows that its 50% material breakdown temperature is 283 ℃.

Claims (6)

1. one kind is the alternately polycarbonate material of structure, it is characterized in that carbonate unit content is 90%-100% in the polymeric chain; Different epoxy alkane and carbonic acid gas form different carbonate units and are the content that replaces character mutually account for 5~95% in the polymkeric substance carbonate unit, contain one or both of two kinds of structural units of following formula in the polycarbonate material structure:
R is H, CH in the formula 3, C 2H 5, CH 2Cl or CH 2-(CH 2) n-CH=CH 2, molecular formula n=0~8 wherein, Ph is a phenyl; The number-average molecular weight of polycarbonate material is between 3000~250000, and molecular weight distribution is 1.01~15.00.
2. a kind of alternately structure polycarbonate material that is according to claim 1, it is characterized in that this polymer materials has only a second-order transition temperature and one section very narrow heat decomposition temperature, and second-order transition temperature changes with the difference of material 50% heat decomposition temperature with the various epoxy alkane ratios of using the different of epoxy alkane and participation copolymerization; Wherein, variable glass transition temperature range is 45~120 ℃, and variable material 50% pyrolysis temperature range is 175~325 ℃.
3. a kind of alternately structure polycarbonate material that is according to claim 1, it is characterized in that this polymer materials comprises oxyethane/tetrahydrobenzene epoxy alkane/carbonic acid gas terpolymer, propylene oxide/tetrahydrobenzene epoxy alkane/carbonic acid gas terpolymer, 1,2-butylene oxide ring/tetrahydrobenzene epoxy alkane/carbonic acid gas terpolymer, 1,2-epoxy-7-octene/tetrahydrobenzene epoxy alkane/carbonic acid gas terpolymer, 1,2-epoxy-5,6-epoxy hexane/tetrahydrobenzene epoxy alkane/carbonic acid gas terpolymer, oxyethane/phenyl ethylene oxide/carbonic acid gas terpolymer, propylene oxide/phenyl ethylene oxide/carbonic acid gas terpolymer, oxyethane/1,2-propylene oxide/tetrahydrobenzene epoxy alkane/carbon dioxide copolymer, oxyethane/1,2 epoxy prapane/phenyl ethylene oxide/carbon dioxide copolymer, oxyethane/tetrahydrobenzene epoxy alkane/phenyl ethylene oxide/carbon dioxide copolymer or propylene oxide/tetrahydrobenzene epoxy alkane/phenyl ethylene oxide/carbon dioxide copolymer.
4. prepare the described a kind of alternately method of structure polycarbonate material that is of claim 1, it is characterized in that, adopt with tetradentate schiff base metal complexes (R with 1~5 kind of aliphatic epoxy alkane and at least a ring-type epoxy alkane and carbon dioxide copolymerization 1) (R 2) SalenMX is Primary Catalysts and is R with the chemical formula 1R 2 3YX 1Salt or high hindered organic alkali be promotor; The mol ratio that participates in polymeric aliphatic epoxy alkane and ring-type epoxy alkane is 1: 0.05~20; When carrying out copolyreaction, help, the mol ratio of Primary Catalysts is 1: 0.2~5; Primary Catalysts and epoxy alkane mol ratio are 1: 100~10000; CO 2Pressure is 0.1~6.0MPa; Temperature of reaction is 0~80 ℃; Reaction times is 1~48 hour.
5. a kind of alternately method of structure polycarbonate material that is of preparation according to claim 4, it is characterized in that participating in polymeric aliphatic epoxy alkane is oxyethane, 1,2-propylene oxide, 1,2-butylene oxide ring, 1,2-epoxy pentane, 1,2-epoxy hexane, 1,2-octylene oxide, 1,2-epoxy-5-hexene, 1,2-epoxy-7-octene, 1,2-epoxy-5,6-epoxy hexane, 1,2-epoxy-7,8-octylene oxide, 1,2-epoxy-9,10-epoxy certain herbaceous plants with big flowers alkane, epoxy chloropropane or epoxy fluoro-propane; Participating in polymeric ring-type epoxy alkane is tetrahydrobenzene epoxy alkane, phenyl ethylene oxide or cyclopentenes epoxy alkane.
6. a kind of alternately method of structure polycarbonate material that is of preparation according to claim 4 is characterized in that:
Used Primary Catalysts tetradentate schiff base metal complexes (R 1) (R 2) general structure of SalenMX is:
Figure A2006102000530003C1
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 2For-H, C 1~C 6Alkyl, C 1~C 6Alkoxyl group ,-Cl ,-Br or-NO 2Group; R 3, R 4For-(CH 2) 4-, CH 3, H, Ph ,-(CH) 4-or-CH 2NHCH 2-; X is I -1, Br -1, Cl -1, NO 3 -1, CH 3COO -1, CCl 3COO -1, CF 3COO -1, ClO 4 -1, BF 4 -1, BPh 4 -1, N 3 -1Monovalence negative ion or 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 or 3,5-two-(trifluoromethyl) phenol negative oxygen ion; In the Primary Catalysts, with metal ions M coordinate 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 diamines or the reaction of three aminated compoundss make; Diamine compounds is a quadrol, 1,2-propylene diamine, 2,3-butanediamine, cyclohexanediamine or 1,2-O-Phenylene Diamine or diphenyl ethylene diamine; Three aminated compoundss are diethylenetriamine or Domistan.
Used promotor is an etamon chloride, tetraethylammonium bromide, tetraethyl ammonium iodide, Tetrabutyl amonium bromide, the tetraethyl-ammonium acetate, tetrabutylammonium chloride, tetrabutylammonium iodide, the tetrapropyl ammonium iodide, 4-propyl bromide, 4-propyl ammonium chloride, the tetrapropyl ammonium acetate, the benzyl triethyl ammonium ammonium iodide, benzyl triethyl ammonium bromide, benzyltriethylammoinium chloride, benzyl tripropyl ammonium chloride, benzyl tributyl ammonium chloride, benzyl tributyl brometo de amonio, 4-propyl ammonium chloride, two-(triphenyl phosphorus) brometo de amonios, two-(triphenyl phosphorus) ammonium chlorides, two-(triphenyl phosphorus) ammonium iodides, two-(triphenyl phosphorus) ammonium azide, two-(triphenyl phosphorus) ammonium acetates, four butyl phosphonium iodides, four butyl phosphonium bromides, 4-butyl phosphonium chloride, the butyl triphenyl phosphonium bromide, benzyl three phenyl phosphonium bromides, the butyl triphenyl phosphonium iodide, the butyl triphenyl phosphonium chloride, propyl group three phenyl phosphonium bromides, 1,8-diazabicyclo [5.4.0] 11-7-alkene (DBU), 3,3,6,9,9-pentamethyl--2,10-diazabicyclo [4.4.0] ten-1-alkene (PMDBD), the 7-methyl isophthalic acid, 5,7-three azabicyclos [4.4.0] ten-5-alkene (MTBD), 7-ethyl-1,5,7-three azabicyclos [4.4.0] ten-5-alkene (ETBD), 7-normal-butyl-1,5,7-three azabicyclos [4.4.0] ten-5-alkene (BTBD), 7-benzyl-1,5,7-three azabicyclos [4.4.0] ten-5-alkene (BnTBD), 1,5-diazabicyclo [4.3.0] nine-5-alkene (DBN) or 1,5,7-three azabicyclos [4.4.0] ten-5-alkene (TBD).
Figure A2006102000530004C1
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