CN85104956A - The method for preparing high molecular weight epoxyalkane with rare-earth complexation catalyst - Google Patents
The method for preparing high molecular weight epoxyalkane with rare-earth complexation catalyst Download PDFInfo
- Publication number
- CN85104956A CN85104956A CN 85104956 CN85104956A CN85104956A CN 85104956 A CN85104956 A CN 85104956A CN 85104956 CN85104956 CN 85104956 CN 85104956 A CN85104956 A CN 85104956A CN 85104956 A CN85104956 A CN 85104956A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- molecular weight
- epoxyalkane
- high molecular
- polymerization
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Landscapes
- Polymerization Catalysts (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Polyethers (AREA)
Abstract
The method for preparing high molecular weight epoxyalkane with rare-earth complexation catalyst has been developed the brand-new complex catalyst of being made up of rare earth compound (naphthenate of 16 kinds of rare earth element, pentanedione salt and phosphonate ester salt) and aluminum alkyls and water (also claiming Ziegler type catalyzer) of a class and has been made epoxy alkane ring opening polymerizations such as oxirane, epoxypropane and epichlorokydrin prepare the method for high molecular weight epoxyalkane with this catalyzer.
The present invention comprises tens kinds of catalyst systems.The polymerizing condition variation range is quite wide.Can need selecting catalyst and selected polymerizing condition according to polymerization.The present invention has opened up the epoxy alkane ring opening polymerization new way.
Description
The invention belongs to high polymer chemistry.
The homopolymer of epoxyalkane such as oxirane, epoxypropane and epichlorokydrin and multipolymer are the macromolecules that class people early know and have extensive use.For example high molecular (molecular weight is 100,000 to 5,000,000) polyethylene oxide (also claiming polyoxyethylene) can be used as tackifier, water-soluble film, spinning sizing agent, thickening agent, lubricant, drag reducer, flocculating agent, spreading agent and medicated premix etc. flow.The homopolymer of epoxypropane and epichlorokydrin and multipolymer then are the specific rubbers with premium properties such as oil resistant, anti-solvent, cold-resistant, heat-resisting, ageing-resistant and anti-ozone.
The sixties begin so far, and research has been established: aluminum alkyls-water-pentanedione system; Zinc alkyl-aqueous systems; Aluminum alkyls-phosphoric acid-lewis base system; Aluminum alkyls-composite catalyst applied to alkylene oxide ring-expansion polymerization such as nitrogen-containing compound system.(be meant the catalyst system and catalyzing of forming to the metal alkyl compound or the hydride of III family to the transistion metal compound and the I of VIII family by IV in the periodic table of elements as for using Ziegler type catalyzer by definition Ziegler type catalyzer.) have only several work in the ring-opening polymerization of epoxyalkane, find that these catalyzer are not that polymerization activity is low, polymerization speed is slow, be exactly that polymer yield and molecular weight are low.Use TiCl as 1958 (Journal of Polymer Science 27,584(1958)) such as former weeks of god
4Or ZnCl
2Or FeCl
3With AlEt
3The polymerization-filling epoxypropane, through 50 hours, the highest yield was 68%, but polymer molecular weight is little, is half decorating film.(Journal of Polymer Science 51, S in 1961
7(1961)) they use pentanedione salt and the AlEt of Co, Cr, V and Ti again
2Be combined in 25 ℃ of polymeric rings Ethylene Oxides.Obtained the highest yield 70% through 38 hours, limiting viscosity ((η)) is less than 2 half shaped polymer admittedly.Refreshing former week in 1963 etc. is used the salicylide (CO(Sal) of Co, Ni again
2) and diformazan glyoxime (Ni(dmg)
2) wait system that chelate and aluminium triethyl form in 30 ℃ of polymeric rings Ethylene Oxides, (the chelate consumption is 6 * 10 under the high catalyst consumption
-3Grammol/gram monomer) polymerase 17 is 2 hours, can obtain the polypropyleneoxide of crystallinity and (η)=2-11.Ni(dmg)
2-AlEt
3Polymerization-filling oxirane 48 hours can get high yield (near 100%) but molecular weight is (η)=3.0(35 ℃, measures in the water) polymkeric substance (Makromolecular Chemie 63,89(1963)).Takahashi in 1966 etc. with the catalyzer of sad, the lauric acid of transition metal such as Ti, V, Cr, Zr, Mo, Co and Ni or naphthenate and aluminum alkyls or alkyl aluminum chloride composition in polymerized at room temperature epoxypropane 72 hours, except that indivedual systems such as zirconium caprylate system, the yield of gained polypropyleneoxide and molecular weight are not high.When epoxypropane was used the zirconium caprylate polymerization-filling, polymer yield was high but its molecular weight (η) also is about 4 (Journal of Polymer Science A-1 4(8), 2015(1966)).The catalyst system and catalyzing that Hsieh 1971 forms with the pentanedione salt of V, Cr, Mn, Fe, Co, Ni and Zn and triisobutyl aluminium and water makes the epoxypropane polymerization; obtained the polymkeric substance of higher yields and molecular weight; be best with pentanedione zinc system wherein, (η) of polypropyleneoxide is up to 5.5.The homopolymerization and the copolymerization (Journal of Applied Polymer Science 15,2425(1971)) of epichlorokydrin that he has also used this architectural study.It is generally acknowledged that Zn does not include transition metal.As fully visible, do not see the Ziegler type catalyzer of forming with transistion metal compound and aluminum alkyls so far as yet and prepare the high molecular weight epoxyalkane successful method with quite high polymerization activity and polymerization speed.
Main points of the present invention be to develop a class brand-new by rare earth compound as major catalyst, aluminum alkyls is as promotor, the Ziegler type catalyzer that water is formed as the 3rd component can be conveniently used for preparing the homopolymer of high molecular weight epoxy ethane, epoxypropane and epichlorokydrin of molecular weight from 200,000 to 3,000,000 and the method for multipolymer.
Rare earth element in the rare earth compound means in the periodic table III B Sc of family, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and 16 kinds of rare earth element of Lu any.And negative ion in the rare earth compound or part can be cycloalkanes acidic group, pentanedione base or 2-ethylhexyl phosphonate group (P partly
204) and 2-ethylhexyl phosphonic acid mono ester group (P
507) in choose any one kind of them.Aluminum alkyls can be aluminium triethyl, triisobutyl aluminium or aluminium diethyl monochloride.
The inventive method at first is to prepare catalyst for polymerization solution under certain condition.Generally be to add rare earth compound in the catalyst preparation pipe, add a certain amount of toluene then, the aluminum alkyls that reinjects was higher than under the room temperature more than ageing half an hour, and the cooling back slowly drips certain water gaging, and fully the reaction back is standby.Catalyst solution concentration in rare earth compound 3.2 * 10
-5Grammol/ml soln to 2.0 * 10
-4Be advisable in grammol/ml soln scope.Wherein aluminum alkyls is that 3-30 is than 1 with the mole ratio of rare earth compound; Water is that 0.3-0.9 is than 1 with the mole ratio of aluminum alkyls.
This method is to adopt solution polymerization process.Polyreaction can be carried out in aromatic hydrocarbons such as toluene or benzene, also can carry out in alkane such as hexane, sherwood oil or hydrogasoline.The polymerization temperature wide ranges can be from 10 ℃ to 95 ℃, and with 70 ℃-90 ℃ for well.Monomer concentration can for 8 grams to the per 100 milliliters of solvents of 30 grams, generally with contain in 100 milliliters of solvents 10 grams to 20 gram monomers for well.Catalyst amount is 3 * 10
-5The grammol rare earth compound/more than the gram monomer.Polymerization time 4 hours to 12 hours.
Implementation method of the present invention is shown in example one to four.
Example one, preparation high molecular weight polyethylene oxide
1. Preparation of Catalyst: in through 120 ℃ of bakings and find time repeatedly to fill in the glass catalyst preparation pipe of nitrogen and add 2.2 gram Nd(P
204)
3With 9.0 milliliters of toluene, inject 4 milliliters of triisobutyl aluminiums then, the above ageing of room temperature half an hour, slowly drip 0.17 ml deionized water after the cooling again, the back that reacts completely is standby.
2. polymerization: in baking in 50 milliliters of polymerization bottles that fill the nitrogen processing, add 20 milliliters of toluene of handling through molecular sieve drying, inject 1.2 milliliters of the above-mentioned catalyst solutions for preparing, add 3.0 gram oxirane again through taking out repeatedly.After sealing, puts into polymerization bottle 90 ℃ of water bath with thermostatic control polymerizations 12 hours.Catalyst amount is: 5.7 * 10
-5Grammol Nd(P
204)
3/ gram oxirane; Aluminum alkyls/neodymium compound (mole ratio) is 8; Water/aluminum alkyls (mole ratio) is 0.6.
3. aftertreatment: polymerization finishes, and opens polymerization bottle and adds the sherwood oil that contains 2.6-di-tert-butyl-4-methy phenol (antioxidant 264) 1.0%, obtains the white solid polymkeric substance, uses petroleum ether 3 times.To constant weight, polymer yield is 96% to polymkeric substance in 60 ℃ of vacuum drying.
4. molecular weight determination: the polyethylene oxide molecular weight ties up to 30 ℃ of limiting viscosities ((η)) of measuring its 0.1% aqueous solution, calculates according to following formula then: (η)=1.25 * 10
-4M
0.78(η) of this routine resulting polymers is 10.31, and molecular weight is 2,090,000.
Example two, the preparation of high-molecular-weight poly epoxy propane rubber
This example Nd(P
507)
3-Al(i-Bu)
3-H
2O is the catalyzer of preparation polypropyleneoxide, and its operation steps and example one are basic identical.Just polymerization finishes, and adds 5 milliliters of toluene that contain 1% antioxidant 264 and shakes up in polymerization bottle, then polymer solution is poured in 125 milliliters of separating funnels, to contain the deionized water wash secondary of 10% hydrochloric acid, with 10%NaHCO
3Solution washing 3 times, again with deionized water wash to neutral, boil off solvent, obtain solid polymer in 60 ℃ of vacuum drying to constant weight.Its molecular weight ties up to 25 ℃ of limiting viscosities of measuring 0.1% polymkeric substance toluene solution, is calculated as follows to obtain again: (η)=1.29 * 10
-4M
0.75
(3.32 gram) epoxypropane is worked as catalyst amount and is:
* 10
-3Grammol Nd(P
507)
3/ gram monomer; Aluminum alkyls/neodymium compound (mole ratio) is 10; H
2O/ aluminum alkyls (mole ratio) is 0.6, in 80 ℃ of polymerizations 6 hours, gets yield 96%, (η)=6.23, and molecular weight is 1,760,000 white polypropyleneoxide rubber.
Example three, preparation high molecular chlorohydrin rubber
Preparation process is identical with example one.0.43 gram Nd(acao)
33H
2O adds 8 milliliters of toluene and 2.1 milliliters of triisobutyl aluminiums more than the above temperature ageing of room temperature half an hour, adds 0.075 ml deionized water after the cooling lentamente, and it is standby promptly to get catalyst solution behind the sufficient reacting.During polymerization 3 milliliters of catalyst solutions are added in 20 milliliters of toluene, add 3 milliliters of epichlorokydrin again, in 80 ℃ of polymerizations 8 hours.After the petroleum ether precipitation washing, vacuum drying gets little yellow elastic body to constant weight.Its conversion ratio is 91%, and it is 5.89 that molecular weight gets limiting viscosity by 50 ℃ of its 0.1% cyclohexanone solution of mensuration, again by (η)=8.9 * 10
-3M
0.75Calculate to such an extent that be 2,670,000.
Example four, epichlorokydrin, oxirane and epoxypropane ternary polymerization.
1.53 gram Gd(P
204)
3Add 4ml toluene, add 7ml Al(i-Bu)
3Make catalyst solution with the 0.2ml deionized water by example one step.Add 1.6 milliliters of catalyst solutions during polymerization in the 20ml toluene.Add 2 gram epichlorokydrin then, 0.6 gram oxirane and 0.5 gram epoxypropane, in 70 ℃ of polymerizations 10 hours, its catalyst amount was 1.0 * 10
-4Grammol (Gd(P
204)
3/ gram monomer, aluminum alkyls/gadolinium thing (mole ratio)=20, H
2O/ aluminum alkyls (mole ratio)=0.5.Polymerization finishes, and the aftertreatment of multipolymer is with example two, and molecular weight determination is undertaken by the example three therapeutic methods of traditional Chinese medicine.This example can make 91% yield, and molecular weight is 200,000 terpolymer rubbers.
The present invention has opened up the new way of preparation high molecular weight epoxyalkane, has following characteristics:
1. the rare-earth complexation catalyst of the present invention's exploitation is that a up to now unique class can be high Yield, high polymerization speed prepare the Ziegler type catalyst of high molecular weight epoxyalkane. It is convenient to prepare high molecular weight epoxyalkane with catalyst of the present invention and polymerization.
2. rare-earth compound finds it is effective major catalyst of epoxy alkane ring opening polymerization at home and abroad first. Rare earth compound means naphthenate, pentanedione salt, the 2-ethylhexyl phosphonate ester (P of Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and 16 kinds of rare earth elements of Lu204) salt and 2-ethylhexyl phosphonic acid mono ester (P507) salt. This shows that rare-earth complexation catalyst is actual comprises tens kinds of catalyst systems, can select suitable catalyst system and catalyzing according to the polymerization needs. P204，P
507Also be in ring-opening polymerization, to show first its good catalytic performance Deng the phosphonate ester part.
The catalyst activity life-span of the present invention exploitation long, to polymer raw purity requirement harshness not too.
4. various polymerizing conditions such as catalyst component proportioning, polymerization temperature, monomer concentration etc. can change in quite wide scope and little to the yield of polymkeric substance and molecular weight influence.
5. polyethylene oxide, polypropyleneoxide and the Hydrin that catalyzer of the present invention and polymerization prepare is crystallinity, the resilient polymkeric substance of molecular weight from 200,000 to 3,000,000 high molecular white.
Claims (6)
1, a kind of method with Ziegler type Preparation of Catalyst high molecular weight epoxyalkane, it is to prepare catalyst for polymerization under certain condition by major catalyst (transistion metal compound) and promotor (aluminum alkyls) and the 3rd component (water etc.) to make epoxy alkane ring opening polymerization obtain heavy polymer, it is characterized in that said major catalyst means rare earth compound.
2, a kind of method with Ziegler type Preparation of Catalyst high molecular weight epoxyalkane according to claim 1 is characterized in that the rare earth element in the said rare earth compound means Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and 16 kinds of elements of Lu.
3,, it is characterized in that the negative ion part or the part of described rare earth compound means P according to claim 1,2 described a kind of methods with Ziegler type Preparation of Catalyst high molecular weight epoxyalkane
204Base (2-ethylhexyl phosphonate group), P
507Base (2-ethylhexyl phosphonic acid mono ester group), cycloalkanes acidic group and pentanedione base.
4, a kind of method with Ziegler type Preparation of Catalyst high molecular weight epoxyalkane according to claim 1, it is characterized in that must preparation catalyst for polymerization solution.Generally add rare earth compound during preparation earlier, add toluene again, inject aluminum alkyls then, more than ageing half an hour, the cooling back slowly drips minor amount of water under higher temperature, and fully the reaction back is standby.
5, a kind of method with Ziegler type Preparation of Catalyst high molecular weight epoxyalkane according to claim 1 is characterized in that polymerization temperature is 10 °-95 ℃, wherein with 70 °-90 ℃ for well.
6, a kind of method with Ziegler type Preparation of Catalyst high molecular weight epoxyalkane according to claim 1 is characterized in that monomer concentration is to contain 8 to 30 gram monomers in per 100 milliliters of solvents, wherein with 10 grams to 20 grams for well.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 85104956 CN85104956B (en) | 1985-06-26 | 1985-06-26 | New series of ziegler-type catalysts and high polymer manuf. process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 85104956 CN85104956B (en) | 1985-06-26 | 1985-06-26 | New series of ziegler-type catalysts and high polymer manuf. process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85104956A true CN85104956A (en) | 1986-07-02 |
| CN85104956B CN85104956B (en) | 1987-09-30 |
Family
ID=4794166
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 85104956 Expired CN85104956B (en) | 1985-06-26 | 1985-06-26 | New series of ziegler-type catalysts and high polymer manuf. process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN85104956B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1094945C (en) * | 1998-12-24 | 2002-11-27 | 中国科学院长春应用化学研究所 | Process for preparing composite catalyst of rare-earth complex |
| CN101701063B (en) * | 2009-11-18 | 2012-01-11 | 武汉工程大学 | Preparation method of polyepichlorohydrin |
| CN104910367A (en) * | 2015-06-19 | 2015-09-16 | 大连理工大学 | Binary star branched rare-earth epichlorohydrin rubber and preparation method thereof |
| CN105037705A (en) * | 2015-06-19 | 2015-11-11 | 大连理工大学 | Ternary rare earth epichloro-hydrin rubber and preparation method thereof |
-
1985
- 1985-06-26 CN CN 85104956 patent/CN85104956B/en not_active Expired
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1094945C (en) * | 1998-12-24 | 2002-11-27 | 中国科学院长春应用化学研究所 | Process for preparing composite catalyst of rare-earth complex |
| CN101701063B (en) * | 2009-11-18 | 2012-01-11 | 武汉工程大学 | Preparation method of polyepichlorohydrin |
| CN104910367A (en) * | 2015-06-19 | 2015-09-16 | 大连理工大学 | Binary star branched rare-earth epichlorohydrin rubber and preparation method thereof |
| CN105037705A (en) * | 2015-06-19 | 2015-11-11 | 大连理工大学 | Ternary rare earth epichloro-hydrin rubber and preparation method thereof |
| CN104910367B (en) * | 2015-06-19 | 2017-06-16 | 大连理工大学 | Star-branched rare earth epichlorohydrin rubber of binary and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN85104956B (en) | 1987-09-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1124289C (en) | Anionic polymerisation process | |
| Hsieh et al. | Polymerization of butadiene and isoprene with lanthanide catalysts; characterization and properties of homopolymers and copolymers | |
| US4265785A (en) | Polymerization catalyst | |
| US20020143115A1 (en) | Increased throughput in the manufacture of anionic polymers by reduction in polymer cement viscosity through the addition of metal alkyls | |
| CN101260164B (en) | Syn form 1,4-selectivity polymerization catalysis system for Isoprene or butadiene and preparation method and using method | |
| US6455651B1 (en) | Uniform initiation of anionic polymerization using organo-substituted alkali metal initiators | |
| EP2289949A1 (en) | Isoprene or butadiene cis 1,4-polymeric bi-component catalyst system and polymerization process | |
| CN101397348B (en) | Catalytic system for isoprene or butadiene high cis-1,4- selective polymerization, preparation method and use thereof | |
| CN101475652A (en) | Rare earth catalyst for isoprene high cis 1,4-polymerization and preparation | |
| US5300597A (en) | Olefin polymerization catalyst and process | |
| CN101693754A (en) | Application of rare-earth complexes chelated by tridentate carbazolyl in conjugated diene and polar monomer copolymerization catalyst system | |
| KR100386165B1 (en) | Olefin Polymerization | |
| JP2000026516A (en) | Organic zinc and alkaline earth catalyst system in polymerizing conjugated diene | |
| CN101704848B (en) | Rare earth allyl complex with constrained geometry configuration, preparation method thereof and applications thereof in conjugated diene high-cis-1, 4-selective polymerization | |
| CN85104956A (en) | The method for preparing high molecular weight epoxyalkane with rare-earth complexation catalyst | |
| CN101367825B (en) | Double-carbene clamp type rareearth complexes, preparation method and uses of the same in cis-1,4 selective polymerization of diolefin | |
| US3998996A (en) | Process for the manufacture of a mixed catalyst | |
| US5286694A (en) | Lanthanide halide catalyst, method of producing the catalyst, and polymerization process employing the catalyst | |
| CN110092855B (en) | Rare earth complex, catalyst and preparation method thereof, and preparation method of diolefin polymer | |
| JP6287442B2 (en) | Catalyst removal method | |
| EP0965600B1 (en) | Process for preparing polymer by using copper compound | |
| CA1338033C (en) | Process for polymerizing ethylene and copolymerizing ethylene with alpha-olefins and relevant catalyst | |
| CN110144025A (en) | A kind of preparation method of rare earth catalyst and its application in diolefin polymerization and combined polymerization | |
| WO2006057229A1 (en) | Process for production of low-molecular olefin polymer having a terminal double bond | |
| JP3937830B2 (en) | Catalyst for polymerization of oxirane compound, and method for producing oxirane compound polymer using the catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| PB01 | Publication | ||
| C06 | Publication | ||
| C13 | Decision | ||
| GR02 | Examined patent application | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |