CN85104956B - New series of ziegler-type catalysts and high polymer manuf. process - Google Patents
New series of ziegler-type catalysts and high polymer manuf. processInfo
- Publication number
- CN85104956B CN85104956B CN 85104956 CN85104956A CN85104956B CN 85104956 B CN85104956 B CN 85104956B CN 85104956 CN85104956 CN 85104956 CN 85104956 A CN85104956 A CN 85104956A CN 85104956 B CN85104956 B CN 85104956B
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- polymerization
- catalyzer
- ring opening
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Abstract
The present invention relates to a method for preparing high molecular weight poly-epoxyalkane from a rare-earth complex catalyst, which develops a brand-new complex catalyst (which is also called Ziegler type catalyst) prepared from rare-earth compounds (the naphthenate, the acetyl acetone salt and the phosphonic acid ester salt of sixteen rare-earth elements), aluminium alkyl and water and a method for carrying out the ring opening polymerization of epoxyalkane, such as epoxy ethane, propylene oxide, epoxy chloropropane, etc., for preparing high molecular weight poly-epoxyalkane from the complex catalyst. The present invention comprises scores of catalyst systems, the variation range of polymerizing conditions is wide, and catalysts and polymerizing conditions can be selected according to the requirements of polymerization. The present invention develops a new path for epoxyalkane ring opening polymerization.
Description
The invention relates to the method for preparing the polyalkylene oxide of polymer with rare-earth complexation catalyst.
The homopolymer of the epoxy alkane such as oxyethane, propylene oxide and epoxy chloropropane and multipolymer are the polymers that class people early know and have extensive use.Such as high molecular (molecular weight is 100,000 to 5,000,000) polyethylene oxide (also claiming polyoxyethylene) can be used as tackiness agent, water-soluble film, spinning sizing agent, thickening material, lubricant, flowing subtracts positive agent, flocculation agent, dispersion agent and medicated premix etc.The homopolymer of propylene oxide and epoxy chloropropane and multipolymer are the specialty elastomers with premium propertiess such as oil resistant, resistance to solvent, cold-resistant, heat-resisting, ageing-resistant and resistance to ozone.
The sixties start so far, and research has been established: aluminum alkyls-water-Acetyl Acetone system; Zinc alkyl(s)-aqueous systems; Aluminum alkyls-phosphoric acid-Lewis base system; The composite catalyst applied to alkylene oxide ring-expansion polymerization such as aluminum alkyls-nitrogenous compound system.(refer to by definition Ziegler type catalyzer the catalyst system being formed to metal alkyl compound or the hydride of III family by transistion metal compound and the I of IV to VIII family in the periodic table of elements as for application Ziegler type catalyzer.) only have several work in the ring-opening polymerization of epoxy alkane, find that these catalyzer are not that polymerization activity is low, polymerization velocity is slow, be exactly that polymer yield and molecular weight are low.Weeks as former in god etc. 1958 (Journal of Polymer Science 27,584 (1958)) are used TiCl
4or ZnCl
2or FeCl
3with AlEt
3polymerization-filling propylene oxide, through 50 hours. and the highest yield is 68%, but polymericular weight is little, is half decorating film.(Journal of Polymer Science 51, S in 1961
7(1961)) they use again Acetyl Acetone salt and the AlEt of Co, Cr, V and Ti
3be combined in 25 ℃ of polymeric rings Ethylene Oxides, obtained the highest yield 70% through 38 hours, half shaped polymer admittedly that limiting viscosity ((η)) is less than 2.Former week of god in 1963 is waited the salicylic aldehyde (CO (Sal) that uses again Co, Ni
2) and diformazan glyoxime (Ni (dmg)
2) etc. the system of inner complex and triethyl aluminum composition in 30 ℃ of polymeric rings Ethylene Oxides, under high catalyst consumption, (inner complex consumption is
/ gram monomer) polymerase 17 2 hours, can obtain the poly(propylene oxide) of crystallinity and (η)-2-11.Ni (dmg)
2-AlEL China is polymerization of ethylene oxide 48 hours, can obtain high yield (approaching 100%) but molecular weight is the polymkeric substance (Makromolecular Chemie 63,89 (1963)) of (η)=3.0 (35 ℃, measure in water).1966
for Takahashi etc., the catalyzer of sad, the lauric acid of the transition metal such as Ti, V, Cr, Zr, Mo, Co and Ni or naphthenate and aluminum alkyls or alkyl aluminum chloride composition is in polymerized at room temperature propylene oxide 72 hours,
complicated variant is that the yield of gained poly(propylene oxide) and molecular weight are not high as outside zirconium caprylate system.When propylene oxide is used zirconium caprylate polymerization-filling, polymer yield is high but its molecular weight (η) is also 4 left and right (Joumal of Polymer Science A-14 (8), 2015 (1966)).For Hsieh1971, in the ethanoyl of V, Cr, Mn, Fe, Co, Ni and Zn, ketone salt makes Polymerization of Propylene Oxide with the catalyst system that triisobutyl aluminium and water form; obtain the polymkeric substance of higher yields and molecular weight; wherein, take acyl group acetone zinc system as best, (η) of poly(propylene oxide) is up to 5.5.Homopolymerization and the copolymerization (Journal of Applied Polymer Science15,2425 (1971)) of epoxy chloropropane that he has also used this architectural study.It is generally acknowledged that Zn does not include transition metal.
upper visible, it is not yet seen and prepare the successful method of high molecular weight epoxyalkane with quite high polymerization activity and polymerization velocity with the Ziegler type catalyzer that transistion metal compound and aluminum alkyls form.
Main points of the present invention be to develop a class brand-new by rare earth compound as Primary Catalysts, aluminum alkyls is as promotor, water, as the Ziegler type catalyzer of the 3rd component composition, can be conveniently used for preparing the homopolymer of high molecular weight epoxy ethane, propylene oxide and epoxy chloropropane and the method for multipolymer of molecular weight from 200,000 to 3,000,000.
Rare earth element in rare earth compound means the cycle Table III B Sc of family, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, in Ho, Er, Tm, Yb and 16 kinds of rare earth elements of Lu any.And negatively charged ion or ligand moiety in rare earth compound can be cycloalkanes acidic group, Acetyl Acetone base or 2-ethylhexyl phosphonic acid ester group (P
204) and 2-ethylhexyl phosphonic acid monoesters base (P
507) in choose any one kind of them.Aluminum alkyls can be aluminium triethyl, triisobutyl aluminium or aluminium diethyl monochloride.
First the inventive method is to prepare catalyst for polymerization solution under certain condition.Be generally to add rare earth compound in catalyst preparation pipe, after combustion, add quantitative toluene, the aluminum alkyls that reinjects, more than higher than ageing half an hour under room temperature, the certain water gaging of cooling rear slow dropping, fully for subsequent use after reaction.Catalyst solution concentration in rare earth compound 3.2 × 10
-5mol/ml soln to 2.0 × 10
-4gram point/be advisable within the scope of ml soln.Wherein aluminum alkyls and the mole ratio of rare upper compound be 3-30 than 1, water is that 0.3-0.9 is than 1 with the mole ratio of aluminum alkyls.
Present method is to adopt solution polymerization process.Polyreaction can be carried out in as toluene or benzene at aromatic hydrocarbons, also can carry out in as hexane, sherwood oil or hydrogenated gasoline at alkane.Polymerization temperature wide ranges can be from 10 ℃ to 95 ℃, and take 70 ℃-90 ℃ as good monomer concentration can be as 6 grams to 30 grams every 100 milliliters of solvents, generally to have closed 10 grams to 20 grams monomers in 100 milliliters of solvents for well.Catalyst levels is 3 × 10
-5the rare upper compound of mol gram more than monomer, returns when polymerization 4 hours to 12 hours
Implementation method of the present invention is shown in example to four.
Example one, prepare high molecular weight polyethylene oxide
1. catalyzer preparation: add 2.2 grams of Nd (P in the glass catalyst preparation pipe of also repeatedly finding time to fill nitrogen through 120 ℃ of bakings
204)
3with 90 milliliters of toluene, then inject 4 milliliter three and differ from base aluminium, the above ageing of room temperature half an hour, slowly drip again 0.17 ml deionized water after cooling, for subsequent use after reacting completely.
2, polymerization: in through repeatedly taking out roasting filling in 50 milliliters of polymerization bottles of nitrogen processing, add 20 milliliters of toluene through molecular sieve drying processing, inject 1.2 milliliters of the above-mentioned catalyst solutions preparing, then add 3.0 grams of oxyethane.After polymerization bottle sealing, put into 90 ℃ of water bath with thermostatic control polymerizations 12 hours.Catalyst levels is: 5.7 × 10
-5mol Nd (P
204)
3/ gram oxyethane; Aluminum alkyls/neodymium compound (mole ratio) is 8; Water/aluminum alkyls (mole ratio) is 0.6.
3. aftertreatment: polymerization is complete, opens polymerization bottle and adds the sherwood oil containing 2.6-di-t-butyl-4 methylphenols (antioxidant 264) 1.0%, obtains white solid polymkeric substance, uses petroleum ether 3 times.Polymkeric substance is in 60 ℃ of vacuum-dryings to constant weight, and polymer yield is 96%.
4. molecular weight determination: polyethylene oxide molecular weight ties up to 30 ℃ of limiting viscosities ((η)) of measuring its 0.196 aqueous solution, then calculates according to the following formula: (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
(the P of Nd for this example
507)
3-Al (i-Bu)
3-H
2o is the catalyzer of preparing poly(propylene oxide), and its operation steps and example one are basic identical.Just polymerization is complete, adds 5 milliliters of toluene containing 1% antioxidant 264 and shakes up in polymerization bottle, then polymers soln is poured in 125 milliliters of separating funnels, with the deionized water wash secondary that contains 10% hydrochloric acid, with 10%NaHCO
3solution washing 3 times, more extremely neutral with deionized water wash, boil off solvent, obtain solid polymer in 60 ℃ of vacuum-dryings to constant weight.Its molecular weight ties up to 25 ℃ and measures 0.1% polymkeric substance
the limiting viscosity of solution, then be calculated as follows and obtain
4ml (3.32 grams) propylene oxide is worked as catalyst levels.
8.0 × 10
-5mol Nd (P
507)
3/ gram monomer: aluminum alkyls/
compound (mole ratio) is 10; H
2o/ aluminum alkyls (mole ratio) is 0.6, in 30 ℃ of polymerizations 6 hours, obtains yield 96%. (η)
2 molecular weight are 1,760,000 white poly(propylene oxide) rubber
Example
preparation high molecular chlorohydrin rubber
Preparation process 0.43 gram Nd (acacl identical with example
23H
2o adds 8 milliliters of toluene and 2.1 milliliters
aluminium isobutyl
above temperature ageing half an hour is above adds 0.075 ml deionized water after cooling lentamente, obtains catalyst solution for subsequent use after sufficient reacting, when polymerization, 3 milliliters of catalyst solutions is added to 20 millis
in, then add 3 milliliters of epoxy chloropropane in 80 ℃ of polymerizations 8 hours
after washing of precipitate, vacuum-drying is to constant weight, and obtaining micro-its transformation efficiency of yellow elastomerics is 91%, and it is 5.89 that molecular weight obtains limiting viscosity by 50 ℃ of mensuration tool 0.1 pimelinketone solution, then by (η) 8.9 × 10
-5m
0.25calculate to such an extent that be 2,670,000.
Example four, epoxy chloropropane, oxyethane and propylene oxide terpolymer
1 53 grams of Gd (P
204)
3add 4ml toluene, add 7mlAl (i-Bu), and 0.2ml deionized water is made catalyst solution by example one step.When polymerization, in 20ml toluene, add 1.6 milliliters of catalyst solutions, then add 2 grams of epoxy chloropropane, 0.6 gram of oxyethane and 0.5 gram of propylene oxide, in 70 ℃ of polymerizations 10 hours.Its catalyst levels is 1.0 × 10
-4mol (Gd (P
204)
3/ gram monomer, aluminum alkyls/gadolinium compound (mole ratio)=20, H
2o/ aluminum alkyls (mole ratio)=0.5.Polymerization is complete, and the aftertreatment of multipolymer is with example two, and molecular weight determination is undertaken by example three methods.This example can make 91% yield, molecular weight is 200,000 terpolymer rubbers.
The present invention has opened up the new way of preparing high molecular weight epoxyalkane.There is following feature:
1. the rare-earth complexation catalyst of the present invention exploitation is that a unique up to now class can high yield, and high polymerization velocity is prepared the Ziegler type catalyzer of high molecular weight epoxyalkane.Prepare high molecular weight epoxyalkane with catalyzer of the present invention and polymerization process convenient.
2. rare-earth compound finds it is effective Primary Catalysts of epoxy alkane ring opening polymerization at home and abroad first.Rare earth compound means Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, naphthenate, Acetyl Acetone salt, 2-ethylhexyl phosphonic acid ester (P204) salt and 2-ethylhexyl phosphine branch monoesters (D507) salt of the upper six kinds of rare earth elements of Er, Tm, Yb and Lu.As can be seen here rare-earth complexation catalyst actual comprise tens kinds of catalyst systems, can be according to polymerization needs
change system.
P
204, P
507deng phosphonic acid ester part be also first and cyclopolymerization reaction in show the catalytic performance that it is good.
3. the catalyst activity life-span that the present invention develops is long, not too harsh to polymer raw purity requirement.
4. various polymerizing conditions are as catalyst component proportioning, and polymerization temperature, monomer concentration etc. can change in quite wide scope and yield and molecular weight impact on polymkeric substance is little.
5. polyethylene oxide, poly(propylene oxide) and the Hydrin that catalyzer of the present invention and polymerization process prepare is crystallinity, the resilient polymkeric substance of molecular weight from 200,000 to 3,000,000 high molecular white.
Claims (6)
1. the catalyzer that epoxy alkane ring opening polymerization is used, is characterized in that by Primary Catalysts---Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, any and P in 16 kinds of rare earth elements of Yb and Lu
104(2-ethylhexyl phosphonic acid ester), P
507(2-ethylhexyl phosphonic acid monoesters); any rare earth compound forming in naphthenic acid and Acetyl Acetone; promotor---base aluminium (triethyl aluminum, triisobutyl aluminium or-chlorodiethyl aluminium) and the 3rd component (water) composition.
2. the catalyzer of using by epoxy alkane ring opening polymerization claimed in claim 1, is characterized in that promotor (aluminum alkyls) and the mole ratio of Primary Catalysts (rare earth compound) are 3～30 ratios! .
3. the catalyzer of using by epoxy alkane ring opening polymerization claimed in claim 1, is characterized in that the 3rd component (water) and the mole ratio of promotor (aluminum alkyls) are 0.3～0.9 to 1.
4. the preparation method of the catalyzer of using by epoxy alkane ring opening polymerization claimed in claim 1, is characterized in that preparing the catalyst solution that polymerization is used.Its preparation method is to add toluene in rare upper compound, injects aluminum alkyls, higher than more than room temperature ageing half an hour, adds water after cooling, for subsequent use after reaction.
5. prepare the method for polyalkylene oxide with catalyzer claimed in claim 1, it is characterized in that polymerization temperature is 10～95 ℃, wherein with 70～90 ℃ for well.
6. prepare the method for polyalkylene oxide with catalyzer claimed in claim 1, adopt toluene, benzene or hexane, sherwood oil, hydrogenated gasoline is the solution polymerization of solvent, it is characterized in that monomer concentration be in every 100 milliliters of solvents containing 8～30 grams of monomers, wherein with 10～20 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 CN85104956A (en) | 1986-07-02 |
| CN85104956B true 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 |
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|---|---|
| CN (1) | CN85104956B (en) |
Families Citing this family (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 |
| 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 |
-
1985
- 1985-06-26 CN CN 85104956 patent/CN85104956B/en not_active Expired
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