CN101045783A - Synthetic process and catalyst preparation of fatty polycarbonate - Google Patents
Synthetic process and catalyst preparation of fatty polycarbonate Download PDFInfo
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- CN101045783A CN101045783A CN 200610066290 CN200610066290A CN101045783A CN 101045783 A CN101045783 A CN 101045783A CN 200610066290 CN200610066290 CN 200610066290 CN 200610066290 A CN200610066290 A CN 200610066290A CN 101045783 A CN101045783 A CN 101045783A
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Abstract
This invention relates to synthetic method of fatty series polycarbonate and preparation of catalyzer. Using bimetal complex compound catalyst acquired by special preparation and under medium pressure epoxide and carbon dioxide carry out copolymerisation, the catalytic efficiency exceed 70g polymer / g catalyzer, the polymeric number average molecular weight higher than twenty thousand , carbonate unitary content of polymer exceed 40 percent, alternating copolymerization structure exceed 95 percent, furthermore add different precipitant at treating process, could obtain series polycarbonate of different molecular weight. Product of different molecular weight possess different physical property and application. Product of low-molecular weight could used as binder; product of higher molecular weight could produce disposable plastic wrapping, such as meal box; Product of middle molecular weight could used as matrices raw material of chewing gum.
Description
Technical field
The present invention is synthetic method, molecular-weight gradation method, the method for preparing catalyst of relevant aliphatic polycarbonate, belongs to the chemical industry synthetical resin products that a kind of new technology is produced.
Background technology
The poly-alkylene carbonic ester that epoxide and carbon dioxide reaction generate can be used as engineering plastics, elastomerics, coating, tackiness agent, oxygen barrier film, biodegradable material.This base polymer is synthetic utilize extremely rich and come synthetic at nature content from the greenhouse gases carbonic acid gas that environment is worked the mischief of industrial a large amount of generations, product has biodegradability simultaneously, have dicyclo and protect function, having good economy and society benefit, is the industry that national policy is encouraged.The classical catalyst system of this reaction has following several: and the water of (one) zinc ethyl and equivalent (referring to Inoue, S; Koinuna, H; Tsuruta, T, Makromol.Chem.1969,130,210).This catalyst system is extremely responsive to steam and oxygen, is difficult to operation, and the zinc ethyl price is higher, causes product cost very high.(2) porphyrin metal complex (referring to Inoue, 5.:Aida.T.ACS Symp.Ser., 1985.286,137.) is though this catalyzer has more gratifying activity, and preparation process is very complicated, price is rather stiff.(3) composite catalyst of rare-earth complex Chinese patent 98125654.6,98125655.4,0013189.9 adopts composite catalyst of rare-earth complex to prepare polycarbonate, obtain catalyst efficiency and higher polymericular weight preferably, but Preparation of Catalyst is loaded down with trivial details, the operational requirement height.(4) pentanedioic acid zinc catalyst Chinese patent 0113009.x, 00130811.4 adopts pentanedioic acid zinc or hexanodioic acid zinc system to prepare polycarbonate, catalyst efficiency and polymericular weight all are greatly improved, but polymerization time is longer, and polymerization process requires very strict.(5) polymer anion coordination bimetallic catalyst system, though active higher, molecular weight product is lower, the catalyst efficiency ratio is lower.
Summary of the invention
Purpose of the present invention provides the method for the copolymerization aliphatic polycarbonate of a kind of lower-cost bimetal complex catalyst preparation method, epoxide and carbonic acid gas, and the method that obtains the polycarbonate of different molecular weights in the exquisite process of polymkeric substance by the different precipitation agents of adding.By sequestrant is handled, and adopt dewatering agent catalyzer to be carried out drying, the catalyst activity height of acquisition, good stability, processing ease; Be used for catalysis epoxidation thing and carbonic acid gas polymerization, less demanding to polymerizing condition, realize easily, be more suitable for industrial applications.Polymkeric substance adopts different precipitation agents and consumption thereof in treating process, can obtain the different polymeric articles of molecular weight.
1. the catalyzer composition of the present invention's employing is represented in order to following general expression:
PaM
IIX
b[ML
cX
d]
e(H
2O)
f(M
IX)
g
In the formula, M
IIBe the divalent metal, as zinc, cadmium, cobalt, nickel, iron, copper, M are 3 valencys or variable valency metal, as iron, cobalt, chromium, aluminium, tin, cerium, manganese, vanadium, M
IBe 1 valency metal such as potassium, sodium, lithium, X is the halogen rope, and P is that average per molecule contains k ligating atom such as oxygen, sulphur, nitrogen, and the organic sequestering agent of phosphorus (k＞2) is through termination process; It is oligopolymer or polymkeric substance preferably, as polyoxyethylene glycol, polyethers, polyvinyl alkyl oxide, polyoxymethylene, polyester, polymeric amide, polyvinyl alcohol, and their etherificate, acetalation or esterified derivative also can be micromolecular polynary ether, acetal, ketone, ester, amine, phosphine, thioether, acid amides; L be easily with the ligand of metal M formation complex anion such as alkoxyl group, halogen, cyano group, thiocyanogen, oxalate etc.
2. method for preparing catalyst of the present invention
Different with disclosed patent family is, earlier sequestrant is carried out termination process, and this closed-end technology makes the active group inactivation of sequestrant, the link after making it can not termination reaction to start; Preparing metal halogenide and processing back sequestrant mixed aqueous solution then to the aqueous solution that wherein adds people's metal complex anion, carry out drying with adding dewatering agent after the washing of precipitate again.
3. the preparation method of aliphatic polycarbonate
Dried catalyzer and epoxide are added under oxygen free condition in the autoclave, add (or not adding) solvent, charge into CO2 to 3～8MPa, 30～80 ℃ of copolyreaction temperature, reaction times 20～40h.
4. the processing of polymkeric substance and classification
Reaction product is dissolved in the solvent, adds complexing agent, remove catalyzer, in solution, add precipitation agent, isolate the polymkeric substance of different molecular weight, obtain serial polycarbonate after making with extra care.
The catalyst propylene oxide and the carbonic acid gas polymerization of the present invention's preparation, catalyst efficiency surpasses 70g polymkeric substance/g catalyzer, the molecular-weight average of polycarbonate is greater than 20,000, and wherein the content of carbonate unit surpasses 40%, approaches ideal alternating copolymerization structure.Polymkeric substance can obtain the polycarbonate of different molecular weight after precipitation process.
Embodiment, general operation:
Preparation of Catalyst: the sequestrant substance reacts with end-capping reagent in special catalyzer solvent, and products therefrom adds ZnCl
2To ZnCl
2In the mixing solutions (the former concentration is 10～20%) of sequestrant, under agitation add K
3M (CN)
65～10% aqueous solution of (M=Fe, Co).Centrifugal collection generates yellow (working as M=Fe) or white (working as M=Co) precipitation.To precipitate water, sequestrant or the washing of their mixture 1～4 time, the centrifuging collecting precipitation is used in each washing back, adds the dewatering agent drying in the precipitation.
Epoxide and carbon dioxide copolymerization: in autoclave pressure, add people's catalyzer, add propylene oxide (PO) in nitrogen, catalyst levels is 3.2% of a PO weight, and charging into carbonic acid gas to pressure is about 50atm, be heated to 40 ℃ of reaction regular hours, residual air is discharged in cooling.
The polymkeric substance crude product adds an amount of complexing agent through dissolution with solvents, and centrifugation goes out throw out, adds precipitation agent 1 in the solution, and centrifugation goes out precipitation 1; Add precipitation agent 2 again, centrifugation goes out precipitation 2, isolates the precipitation of different molecular weight successively.After the precipitation drying, obtain the polycarbonate of different molecular-weight average.
Embodiment 1
PEG is carried out the end group shutoff with diacetyl oxide, prepare mixed aqueous solution (latter's concentration 8%) with zinc chloride behind the end-blocking, the potassium ferricyanide aqueous solution of configuration 10% splashes in the mixed aqueous solution, collects the precipitation that generates.After precipitation washes with water, add dewatering of ethanol, vacuum-drying 8h.
Dried catalyzer and 100mL propylene oxide are introduced reactor under nitrogen protection, charge into carbonic acid gas to 5.0MPa, and polyreaction is reacted 24h down at 40 ℃.The refining back of polymkeric substance obtains polypropylene carbonic ether 112g, and color is near white, C13 nuclear magnetic resonance spectroscopy result, and alternating structure is greater than 96%, number-average molecular weight 50000.
Embodiment 2
Catalyzer and 100mL propylene oxide are introduced reactor under nitrogen protection, charge into carbonic acid gas to 6.0MPa, polyreaction is reacted 20h down at 50 ℃.The refining back of polymkeric substance obtains molecular weight less than 4000 polypropylene carbonic ether 6g, the polypropylene carbonic ether 10g of molecular weight 4000～9000, the polypropylene carbonic ether 18g of molecular weight 9000～20000, molecular weight 20000～40000 product 61g, molecular weight is greater than 40000 product 23g.
Embodiment 3
Catalyzer and 100mL propylene oxide and 85mL trichloromethane are introduced reactor under nitrogen protection, charge into carbonic acid gas to 6.0MPa, polyreaction is at 40 ℃ of reaction 40h down.The refining back of polymkeric substance obtains polypropylene carbonic ether 121g, C13 nuclear magnetic resonance spectroscopy result, and alternating structure is greater than 96%, and number-average molecular weight is greater than 35000.
Claims (8)
1. the preparation method of a controllable molecular weight aliphatic polycarbonate is characterized in that catalyzer is composed as follows:
PaM
IIX
b[ML
cX
d]
e(H
2O)
f(M
1X)
g
In the formula: M
IIBe the divalent metal,
M is 3 valencys or variable valency metal,
M
1Be 1 valency metal,
X is a halogen,
P is the sequestrant that treated average per molecule contains k ligating atom, k 〉=2,
L is the ligand that can form complex anion with M,
A, b, c, d, c, f are positive number or zero, and the value of a～g and k satisfies ak=1～3, ak+b+e=3～7, (c+d=6 when L is-1 valency; When L is-1 valency, when M is 3 valencys, b+3c=2);
The Preparation of Catalyst mode is as follows:
Earlier sequestrant is carried out termination process, the superfluous mixture mixed aqueous solution of preparing metal halogenide and processing back then to the aqueous solution that wherein adds people's metal complex anion, carries out drying with adding dewatering agent after the washing of precipitate again.
Dried catalyzer and epoxide are added under oxygen free condition in the autoclave, add (or not adding) solvent, charge into CO
2To 3～8MPa, 30～80 ℃ of copolyreaction temperature, reaction times 20～40h, epoxide are propylene oxide, oxyethane, Styrene oxide 98min. and epoxy cyclohexane.
Polymkeric substance is dissolved in solvent, add metal chelating agent and deviate from metal, add different precipitation agents, obtain the polycarbonate of different molecular weight.
2, according to the method described in the claim 1, the sequestrant that adopts when it is characterized in that preparing catalyzer is oligopolymer or the polymkeric substance that average each molecule contains K oxygen, sulphur, nitrogen or phosphorus ligating atom.Preferred polyoxyethylene glycol, polyethers, polyvinyl alkyl oxide, polyoxymethylene, polyester, polymeric amide, polyvinyl alcohol and etherificate thereof, formalizing or esterified derivative, or micromolecular polynary ether, acetal, ketone, ester, amine, phosphine, thioether, acid amide, one or more of these materials.
3. according to the method described in the claim 1,2, the sequestrant of preparation catalyzer is through special processings such as end-blockings.Capping reagent is acetate, propionic acid, butyric acid, maleic acid, oxalic acid and acid anhydride thereof.
4, according to the method described in the claim 1, the divalent metal that it is characterized in that preparing catalyzer is zinc, chromium, cobalt, nickel, iron, copper, manganese, etc.The trivalent or the variable valency metal of preparation catalyzer are iron, cobalt, chromium, aluminium, tin, molybdenum, vanadium, zirconium, manganese, cerium.
5,, it is characterized in that the sequestrant ligating atom that feeds intake is 1.5～10 to the mol ratio of divalent metal according to the method described in the claim 1.The ligand of preparation catalyzer is an alkoxyl group, halogen, cyano group, thiocyanogen, oxalate.
6, according in the claim 1 fixed method, it is characterized in that the catalyzer drying means handles for adding dewatering agent.Dewatering agent is ethanol, methyl alcohol, toluene, hexane, dimethylbenzene, isopropyl benzene, benzene, molecular sieve, Vanadium Pentoxide in FLAKES and Phosphorates phosphorus Halides.
7,, it is characterized in that entire reaction all can carry out having under the condition of no solvent according to the synthetic method of the aliphatic polycarbonate described in the claim 1.
8, according to the process for purification of the aliphatic polycarbonate described in the claim 1, it is characterized in that used precipitation agent is tetrahydrofuran (THF), water, acetone, ethanol, Virahol, methyl alcohol, toluene, dimethylbenzene, trichloromethane, methyl chloride, monochlorethane, 1,1-ethylene dichloride, 1,1,1-trichloroethane, 1,1,2-trichloroethane, tetracol phenixin, one or more of these materials.Precipitation agent is that difference, classification, segmentation add in treating process, and batch precipitation obtains different molecular weight, satisfies the polymerisate of different demands.
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| CN 200610066290 CN101045783A (en) | 2006-03-31 | 2006-03-31 | Synthetic process and catalyst preparation of fatty polycarbonate |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102585192A (en) * | 2011-12-31 | 2012-07-18 | 中国林业科学研究院林产化学工业研究所 | Biologic polycarbonate and preparation method thereof |
| CN102617844A (en) * | 2012-03-28 | 2012-08-01 | 中国科学院长春应用化学研究所 | Preparing method of poly (carbonic ester-ether) polyalcohol |
| CN107207738A (en) * | 2015-02-17 | 2017-09-26 | 株式会社Lg化学 | Metal complex, metal Nano structure and the carbon monoxide-olefin polymeric comprising the metal Nano structure |
-
2006
- 2006-03-31 CN CN 200610066290 patent/CN101045783A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102585192A (en) * | 2011-12-31 | 2012-07-18 | 中国林业科学研究院林产化学工业研究所 | Biologic polycarbonate and preparation method thereof |
| CN102585192B (en) * | 2011-12-31 | 2013-12-11 | 中国林业科学研究院林产化学工业研究所 | Biologic polycarbonate and preparation method thereof |
| CN102617844A (en) * | 2012-03-28 | 2012-08-01 | 中国科学院长春应用化学研究所 | Preparing method of poly (carbonic ester-ether) polyalcohol |
| CN107207738A (en) * | 2015-02-17 | 2017-09-26 | 株式会社Lg化学 | Metal complex, metal Nano structure and the carbon monoxide-olefin polymeric comprising the metal Nano structure |
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Open date: 20071003 |