CN1094945C - Process for preparing composite catalyst of rare-earth complex - Google Patents
Process for preparing composite catalyst of rare-earth complex Download PDFInfo
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- CN1094945C CN1094945C CN98125654A CN98125654A CN1094945C CN 1094945 C CN1094945 C CN 1094945C CN 98125654 A CN98125654 A CN 98125654A CN 98125654 A CN98125654 A CN 98125654A CN 1094945 C CN1094945 C CN 1094945C
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Abstract
The present invention belongs to a method for preparing a combined rare earth complex catalyst, which provides a method for preparing and combining a catalyst by compounding a rare earth complex prepared by rare earth oxide or a mixture thereof and carboxylic acid with K<a> greater than 1*10<-3> or volatile mineral acid with zinc alkyl. When the catalyst is used for synthesizing an epoxide / carbon dioxide alternate copolymer with high molecular weight, the efficiency of the catalyst exceeds a polymer /mol catalyst of 2.5*10<4>g, the molecular weight of the copolymer exceeds 20000, the carbon dioxide fixation ratio is as high as 40 wt%, and the alternation structure content in the copolymer exceeds 95%.
Description
Technical field: the invention belongs to a kind of method for preparing combination catalyst by rare earth compounding.
Background technology: the carbonic acid gas reserves are very huge in ocean, the earth and the atmospheric environment, and the Greenhouse effect that produced by it have constituted serious environmental pollution day by day.An important directions utilizing the carbonic acid gas resource is, and to be that raw material is synthetic with it have the organism of some properties or directly by its synthesized polymer material.But carbonic acid gas is a least active compound in the C1-chemistry, selects appropriate catalyst to make its activation fixedly have crucial meaning efficiently.U.S.Pat.No.3,585, the catalyzer of 168 employing zinc alkyl(s)/active hydrogen compoundses has obtained the alternating copolymer of carbonic acid gas and epoxy compounds, the activation of carbonic acid gas and fixing .U.S.Pat.No.3 have been realized, 900,424 and U.S.Pat.No.3,953,383 to adopt similar catalyzer be that raw material has directly synthesized various urethane and polyethers with the carbonic acid gas.
U.S.Pat.No.3, the catalytic efficiency of 585, the 168 zinc ethyl catalyst systems that adopt is generally 1 kilogram of polymkeric substance/0.3 kilogram catalyzer.Japanese Patent JP2575199 and JP02142824 adopt its catalytic efficiency of porphyrin metal complex catalyst system can reach 10
3-10
4G polymkeric substance/mol catalyzer, but catalyzer is relatively more expensive, and the molecular weight of products therefrom is on the low side.Chinese patent application numbers 89100701.6 and 91109459.8 discloses polymkeric substance load anion binding bimetallic catalyst system, also can obtain 10
4The catalytic efficiency of g polymkeric substance/mol catalyzer separates with the polycarbonate that generates but carrier is very difficult, and polymer treatment becomes white difficulty bigger.Macromolecules, 24,5305,1991 report phosphonic acid ester/triisobutyl aluminium catalyst system can obtain very high-molecular weight polycarbonate, but catalytic efficiency is lower, and the carbon dioxide fixation rate is lower than 30%.Macromolecules, 30,3147,1997 reports use trifluoracetic acid yttrium catalyst system can obtain catalytic effect preferably, and catalytic efficiency can reach 2 * 10
4G polymkeric substance/mol catalyzer, alternating copolymer content is higher than 95%, but part is more expensive, and catalytic efficiency must further improve.
Summary of the invention:
The purpose of this invention is to provide a kind of method for preparing combination catalyst by rare earth compounding.This method is selected rare earth oxide and composition thereof and K
a＞1 * 10
-3Carboxylic acid or volatility mineral acid prepare rare earth compounding, and with rare earth compounding and the compound preparation combination catalyst of metallorganics.
Because the metallorganics catalyzer plays an important role to obtaining high alternating structure polymkeric substance, but catalyst activity is lower, and the catalyzed by rare-earth complex agent has special effect to improving polymericular weight, but is difficult for obtaining the alternating structure polymkeric substance.We have prepared novel rare-earth title complex combination catalyst by the method for this patent.This catalyzer is when being used for the epoxide of synthetic macromolecule amount/carbon dioxide copolymer, and catalyst efficiency surpasses 2.5 * 10
4G polymkeric substance/mol catalyzer, and the molecular weight of polymkeric substance surpasses 20,000, and the carbon dioxide fixation rate is up to 40wt%, and alternating structure content surpasses 95% in the multipolymer.
Preparation method by the synthetic combination catalyst of rare earth compounding of the present invention is as follows:
1) rare earth compounding has following structure:
MX
nY
m
Wherein M is Y, Ce, Pr, Nd, Sm, Eu, Ho, Er, the mixture of one or more of Yb;
X is K
aValue is 10
-3Above carboxylic acid or sulfonic acid, i.e. trifluoroacetic acid, trichoroacetic acid(TCA), α-tartrate, 0-chloro-benzoic acid, the mixture of one or more of Phenylsulfonic acid;
Y is Cl
-
N is the positive integer of 0-3, and m is the positive integer of 3-n;
2) preparation method of rare earth compounding is as follows:
Adopt chemical method to change into oxyhydroxide rare earth oxide or its mixture, making itself and water form granularity with ball milling or sand milling again is the soup compound of 5-20 micron, it is added in carboxylic acid solution or the volatility inorganic acid solution, after solution becomes neutrality, add carboxylic acid or the volatility inorganic acid solution that is lower than 5% soup compound again, solution is heated to and boils subsequently, is cooled to room temperature again and removes by filter residue, and filtrate obtains rare earth compounding after underpressure distillation dewaters;
3) combination catalyst is composed as follows:
MX
nY
m+Z+G+C
MX wherein
nY
mBe 1) middle synthetic rare earth compounding;
Z is MgR
2, ZnR
2, AlR
3, R is CH
3-, CH
3CH
2-, CH
3CH
2CH
2-, (CH
3)
2CH-, CH
3CH
2CH
2CH
2-, (CH
3)
2CHCH
2-;
G is an ethylene glycol, tirethylene glycol, triethylene Glycol, 1, ammediol, one or more mixtures in the glycerol;
C is 1,3-dioxolane, 2-methyl isophthalic acid, 3-dioxolane, 2,4,5-trimethylammonium-1,3-dioxolane, 1,4-dioxane, 4,5-dimethyl-1,3-dioxolane; 4) preparation method of combination catalyst is as follows:
At CO
2Or N
2Or Ar protection adds C with Z down, and slowly adds G down at 0-40 ℃, and mixture adds rare earth compounding then 40-70 ℃ of following induction stirring or ball milling 1-10 hour, continues reaction 0.5-5 hour under the same conditions, obtains composite catalyst of rare-earth complex.
Embodiment:
Embodiment 1
With 10.0 gram Y (OH)
3Made soup compound in 3.5 hours, Y (OH) with 50 gram water for ball milling
3Granularity be the 8-10 micron.This soup compound is splashed in the solution that contains 25 gram trichoroacetic acid(TCA)s/25 gram water, and be heated to and boil, be cooled to the room temperature after-filtration.After dewatering, the filtrate decompression distillation obtains 30 gram trichoroacetic acid(TCA) yttrium rare earth compoundings.With 0.015molZnEt
2Under carbon-dioxide protecting, add in the 0.326mol dioxane; under 25 ℃, the 0.010mol glycerol is dripped wherein again; mixture joins under carbon-dioxide protecting after 3 hours in the 0.010mol trichoroacetic acid(TCA) yttrium rare earth compounding at 60 ℃ of following ball millings; continuation was reacted 1.2 hours down at 60 ℃, formed combination catalyst.This catalyzer is used for the copolymerization of propylene oxide and carbonic acid gas, obtains white polycarbonate.Catalytic efficiency reaches 3.5 * 10
4Gram polymkeric substance/mol catalyzer.
Embodiment 2
With 20 gram Neodymium trioxide/yttrium oxide mixture 10% dissolving with hydrochloric acid,, filter to neutral with the 5%NaOH drips of solution, throw out formed soup compound in 4 hours with 180 gram water for ball milling after being washed till no chlorion with deionized water again, and the granularity of oxyhydroxide is the 8--12 micron.Under agitation it is splashed in the solution that contains 120 gram Phenylsulfonic acids/120 gram water, be heated to the postcooling that boils to the room temperature after-filtration.After dewatering, the filtrate decompression distillation obtains the rare earth compounding of 42 gram Phenylsulfonic acid yttrium/Phenylsulfonic acid neodymiums.0.015mol sec.-propyl zinc/0.005mol magnesium ethide is added 1 of 0.326mol under carbon-dioxide protecting; in the 3-dioxolane; again under 25 ℃ with 0.010mol 1; ammediol splashes into wherein; mixture joins in 0.01mol Phenylsulfonic acid yttrium/Phenylsulfonic acid neodymium under carbon-dioxide protecting at 70 ℃ of following ball millings after 2 hours; continuation was reacted 1 hour down at 70 ℃, formed combination catalyst, also obtained white polycarbonate.Catalytic efficiency reaches 1.2 * 10
4Gram polymkeric substance/mol catalyzer.
Embodiment 3
With 20 gram cerium oxide/Samarium trioxide mixture 10% dissolving with hydrochloric acid,, filter to neutral with the 5%NaOH drips of solution, throw out formed soup compound in 4 hours with 180 gram water for ball milling after being washed till no chlorion with deionized water again, and the granularity of oxyhydroxide is the 8-10 micron.Under agitation it is splashed in the solution that contains 160 gram 0-chloro-benzoic acids/160 gram water, be heated to and boil, be cooled to the room temperature after-filtration.After dewatering, the filtrate decompression distillation obtains the rare earth compounding of 53 gram 0-chloro-benzoic acid cerium/samariums.The 2-methyl isophthalic acid that 0.015mol butyl zinc is added 0.326mol under carbon-dioxide protecting; in the 3-dioxolane; under 25 ℃, the 0.010mol tirethylene glycol is splashed into wherein again; mixture joins in 0.01mol 0-chloro-benzoic acid cerium/samarium under carbon-dioxide protecting at 70 ℃ of following ball millings after 2 hours; continuation was reacted 1 hour down at 70 ℃, formed combination catalyst.This catalyzer is used for Styrene oxide 98min. and carbon dioxide copolymerization closes, and also obtains white polycarbonate.Catalytic efficiency reaches 1.2 * 10
2Gram polymkeric substance/mol catalyzer.
Embodiment 4
With 20 gram europium sesquioxide/Erbium trioxide mixture 10% dissolving with hydrochloric acid,, filter to neutral with the 5%NaOH drips of solution, throw out formed soup compound in 4 hours with 180 gram water for ball milling after being washed till no chlorion with deionized water again, and the granularity of oxyhydroxide is the 8-13 micron.Under agitation it is splashed in the solution that contains 120 gram trifluoroacetic acids/120 gram water, be heated to and boil, be cooled to the room temperature after-filtration.After dewatering, the filtrate decompression distillation obtains the rare earth compounding of 44 gram trifluoroacetic acid europium/erbiums.0.015mol propyl group zinc is added 2 of 0.326mol under carbon-dioxide protecting; 4; 5-trimethylammonium-1; in the 3-dioxolane; under 25 ℃, 0.010mol ethylene glycol is splashed into wherein again; mixture joins under nitrogen protection after 2 hours in the rare earth compounding of 0.01mol trifluoroacetic acid europium/erbium at 55 ℃ of following ball millings, continues to react 1 hour down at 55 ℃, forms combination catalyst.This catalyzer is used for propylene oxide and carbon dioxide copolymerization closes, and obtains white polycarbonate.Catalytic efficiency reaches 1.2 * 10
4Gram polymkeric substance/mol catalyzer
Embodiment 5
With 20 gram protactinium oxide/Holmium trioxide mixture 10% dissolving with hydrochloric acid,, filter to neutral with the 5%NaOH drips of solution, throw out formed soup compound in 4 hours with 180 gram water for ball milling after being washed till no chlorion with deionized water again, and the granularity of oxyhydroxide is the 8-10 micron.Under agitation it is splashed in the solution that contains 160 gram tartrate/160 gram water, be heated to and boil, be cooled to the room temperature after-filtration.After dewatering, the filtrate decompression distillation obtains the rare earth compounding of the adjacent tartrate protactinium/holmium of 46 grams.The 0.015mol zinc ethyl is added 4 of 0.326mol under carbon-dioxide protecting; 5-dimethyl-1; in the 3-dioxolane; under 25 ℃, the 0.010mol triethylene Glycol is splashed into wherein again; mixture joins in the rare earth compounding of 0.01mol tartrate protactinium/holmium under carbon-dioxide protecting at 60 ℃ of following ball millings after 2 hours; continuation was reacted 1 hour down at 60 ℃, formed combination catalyst.This catalyzer is used for Styrene oxide 98min. and carbon dioxide copolymerization closes, and also obtains white polycarbonate.Catalytic efficiency reaches 1.2 * 10
3Gram polymkeric substance/mol catalyzer.
Claims (6)
1. one kind prepares the method for combination catalyst by rare earth compounding, it is characterized in that rare earth compounding has following structure:
MX
nY
m
Wherein M is Y, Ce, Pr, Nd, Sm, Eu, Ho, Er, the mixture of one or more of Yb;
X is K
aValue is 10
-3Above carboxylic acid or sulfonic acid, i.e. trifluoroacetic acid, trichoroacetic acid(TCA), α-tartrate, 0-chloro-benzoic acid, the mixture of one or more of Phenylsulfonic acid;
Y is Cl
-
N is the positive integer of 0-3, and m is the positive integer of 3-n;
2) preparation method of rare earth compounding is as follows:
Adopt chemical method to change into oxyhydroxide rare earth oxide or its mixture, making itself and water form granularity with ball milling or sand milling again is the soup compound of 5-20 micron, it is added in carboxylic acid solution or the volatility inorganic acid solution, after solution becomes neutrality, add carboxylic acid or the volatility inorganic acid solution that is lower than 5% soup compound again, solution is heated to and boils subsequently, is cooled to room temperature again and removes by filter residue, and filtrate obtains rare earth compounding after underpressure distillation dewaters;
3) combination catalyst is composed as follows:
MX
nY
m+Z+G+C
MX wherein
nY
mBe 1) middle synthetic rare earth compounding;
Z is MgR
2, ZnR
2, AlR
3, R is CH
3-, CH
3CH
2-, CH
3CH
2CH
2-, (CH
3)
2CH-, CH
3CH
2CH
2CH
2-, (CH
3)
2CHCH
2-;
G is an ethylene glycol, tirethylene glycol, triethylene Glycol, 1, ammediol, one or more mixtures in the glycerol;
C is 1,3-dioxolane, 2-methyl isophthalic acid, 3-dioxolane, 2,4,5-trimethylammonium-1,3-dioxolane, 1,4-dioxane, 4,5-dimethyl-1,3-dioxolane; 4) preparation method of combination catalyst is as follows:
At CO
2Or N
2Or Ar protection adds C with Z down, and slowly adds G down at 0-40 ℃, and mixture adds rare earth compounding then 40-70 ℃ of following induction stirring or ball milling 1-10 hour, continues reaction 0.5-5 hour under the same conditions, obtains composite catalyst of rare-earth complex.
2. preparation method as claimed in claim 1 is characterized in that adopting the preparation method of sec.-propyl zinc as the composite catalyst of rare-earth complex of Primary Catalysts.
3. preparation method as claimed in claim 1 is characterized in that adopting the preparation method of isobutyl-zinc as the composite catalyst of rare-earth complex of Primary Catalysts.
4.. preparation method as claimed in claim 1 is characterized in that adopting the 2-methyl isophthalic acid, the 3-dioxolane is as the preparation method of the composite catalyst of rare-earth complex of promotor.
5. preparation method as claimed in claim 1 is characterized in that adopting 2,4,5-trimethylammonium-1, and the 3-dioxolane is as the preparation method of the composite catalyst of rare-earth complex of promotor.
6. preparation method as claimed in claim 1 is characterized in that adopting 4,5-dimethyl-1, and the 3-dioxolane is as the preparation method of the composite catalyst of rare-earth complex of promotor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98125654A CN1094945C (en) | 1998-12-24 | 1998-12-24 | Process for preparing composite catalyst of rare-earth complex |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98125654A CN1094945C (en) | 1998-12-24 | 1998-12-24 | Process for preparing composite catalyst of rare-earth complex |
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|---|---|
| CN1257753A CN1257753A (en) | 2000-06-28 |
| CN1094945C true CN1094945C (en) | 2002-11-27 |
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| CN98125654A Expired - Fee Related CN1094945C (en) | 1998-12-24 | 1998-12-24 | Process for preparing composite catalyst of rare-earth complex |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1226348C (en) | 2002-03-04 | 2005-11-09 | 中国科学院长春应用化学研究所 | Process for preparing carbon dioxide, epoxy propene copolymer and polytri-hydroxy alkanoic ester comixer |
| CN100420705C (en) * | 2005-11-21 | 2008-09-24 | 中国科学院长春应用化学研究所 | Method for preparing crosslinked aliphatic series polycarbonate |
| CN100402151C (en) * | 2006-06-23 | 2008-07-16 | 内蒙古蒙西高新技术集团有限公司 | Industrial preparation of rare-earth ternary catalyst |
| CN101172168B (en) | 2007-10-10 | 2010-06-02 | 大连理工大学 | Metallic blood vessel bracket coating for osamine glycan load CD133 antibody and method for preparing the same |
| CN101402725B (en) * | 2008-11-12 | 2011-03-30 | 中国科学院长春应用化学研究所 | Supported rare earth ternary catalyst for combined polymerization of carbonic anhydride and epoxide and preparing method therefor |
| CN102391506B (en) * | 2011-08-29 | 2013-06-12 | 中国科学院长春应用化学研究所 | Method for preparing aliphatic polyester (urethane urea-amine) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85104956A (en) * | 1985-06-26 | 1986-07-02 | 浙江大学 | The method for preparing high molecular weight epoxyalkane with rare-earth complexation catalyst |
| US4665136A (en) * | 1986-04-07 | 1987-05-12 | Air Products And Chemicals, Inc. | Process for producing novel block alkylene polycarbonate copolymers |
| US4943677A (en) * | 1989-06-08 | 1990-07-24 | Air Products And Chemicals, Inc. | Making poly(alkylene carbonates) of controlled molecular weight |
| CN1044663A (en) * | 1989-02-02 | 1990-08-15 | 中国科学院广州化学研究所 | The catalyzer of polycarbonate synthesis, polyester and polyethers |
-
1998
- 1998-12-24 CN CN98125654A patent/CN1094945C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85104956A (en) * | 1985-06-26 | 1986-07-02 | 浙江大学 | The method for preparing high molecular weight epoxyalkane with rare-earth complexation catalyst |
| US4665136A (en) * | 1986-04-07 | 1987-05-12 | Air Products And Chemicals, Inc. | Process for producing novel block alkylene polycarbonate copolymers |
| CN1044663A (en) * | 1989-02-02 | 1990-08-15 | 中国科学院广州化学研究所 | The catalyzer of polycarbonate synthesis, polyester and polyethers |
| US4943677A (en) * | 1989-06-08 | 1990-07-24 | Air Products And Chemicals, Inc. | Making poly(alkylene carbonates) of controlled molecular weight |
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