CN100436485C - Method for catalyzing water phase polymerization by metallocene catalyst - Google Patents
Method for catalyzing water phase polymerization by metallocene catalyst Download PDFInfo
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- CN100436485C CN100436485C CNB2006101555794A CN200610155579A CN100436485C CN 100436485 C CN100436485 C CN 100436485C CN B2006101555794 A CNB2006101555794 A CN B2006101555794A CN 200610155579 A CN200610155579 A CN 200610155579A CN 100436485 C CN100436485 C CN 100436485C
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Abstract
The invention discloses a catalyzing method of metallocene catalyst to do water-phase polymerize, which comprises the following steps: adding metallocene catalyst in the reactor; putting 1-2% polar monomer; stirring 0.5-3h; adding emulsifier; stirring continuously for 0.5-3h; supplementing 1-2% polar monomer; polymerizing under 30-85 deg. c in the water phase for 2. 5-25h; adding alcohol solution of alcaine to terminate the reaction; sedimenting the polymer; proceeding after-disposal to obtain the product.
Description
Technical field
The present invention relates to the method in a kind of catalyzing water phase polymerization by metallocene catalyst, particularly in the method for catalysis polar monomer esters of acrylic acid, cinnamic homopolymerization and copolymerization.
Background technology
Metallocene catalyst has high catalytic activity, and the active centre is single, and polymerization product has good homogeneity, the molecular weight distribution relative narrower.And has excellent copolymerized ability, advantage such as the microtexture of resulting polymers and molecular weight and distribution thereof are controlled.In recent years, synthetic double-core or multinuclear metallocene compound become a big research focus of metallocene catalysis field of olefin polymerisation, can form more than one active centre in polymerization process, thereby can obtain the polymkeric substance of wide molecular weight distribution or bimodal distribution.
Because metallocene catalysis system is to the susceptibility of empty G﹠W, the metallocene catalysis polymerization reaction system is to carry out in mutually at organic solvent usually, and must carry out under anhydrous and oxygen-free and protection of inert gas.Metallocene catalyst is very limited in the use, makes severe reaction conditions, wayward, also increased production cost.
Summary of the invention
The invention provides a kind of method of catalyzing water phase polymerization by metallocene catalyst, simplified reaction conditions, reduced cost and environmental protection more.
In reactor, add metallocene catalyst, drop into polar monomer 1～2 weight part earlier, stirred 0.5～3 hour, add the aqueous solution of emulsifying agent, continue to stir 0.5～3 hour, add polar monomer 1～2 weight part; 30～85 ℃ carry out aqueous polymerization reaction 2.5～25h after, add the ethanolic soln termination reaction of hydrochloric acid, obtain polymer precipitation, obtain polymerisate through aftertreatment.
Described metallocene catalyst structural formula is:
CpMCl
3
Or
Or
Or
Wherein Cp is cyclopentadienyl-C
5H
5, Cp
1, Cp
2, Cp
3Be separate not replacement or have Me or have Me
3Si is substituent to have cyclopentadiene, indenes or fluorene structured part;
X is (CH
3)
2C-or (CH
3)
2Si-;
X
1Be ether bridge-(CH
2)
2O (CH
2)
2-, second sulphur bridge-(CH
2)
2S (CH
2)
2-or-CH
2C
6H
4CH
2-bridge construction (two methylene radical on the phenyl ring can be adjacent, or contraposition);
M is Ti, Zr or Hf.
Described polar monomer is one or more in methyl methacrylate (MMA), butyl methacrylate (BMA), methyl acrylate (MA), butyl acrylate (BA) or the vinylbenzene (St).
Described emulsifying agent is sodium laurylsulfonate (SDS).The concentration of aqueous solution of described emulsifying agent is 0.2～2.0g/l, counts 1 gram with the polar monomer weight that drops into earlier, and the consumption of the aqueous solution of described emulsifying agent is 2.5～40ml.
The total mole number of described polar monomer that drops into earlier and the polar monomer added is 50～800: 1 with ratio with the mole number of metallocene catalyst.
The entire operation of described aqueous polymerization and reaction process are carried out under protection of inert gas.
The concentration of volume percent of the ethanolic soln of described hydrochloric acid is 10%.Described hydrochloric acid is concentrated hydrochloric acid, and the run-of-the-mill percentage concentration is greater than 30%.
Described aqueous polymerization, can be a kind of homopolymerization or the monomeric copolymerization of various polarity of polar monomer, during the monomeric copolymerization of various polarity between each comonomer weight ratio be 1: 1, when the monomeric copolymerization of various polarity fed intake, various polar monomers all were divided into elder generation according to identical ratio and drop into part and add part.
Described aftertreatment is with the resulting polymers precipitation after filtering, with ethanol and distilled water wash polymkeric substance, removes residual catalyzer, acid and emulsifying agent, and vacuum-drying is to constant weight then.When vinylbenzene and methyl methacrylate copolymer, aftertreatment is with the resulting polymers precipitation after filtering, with ethanol and distilled water wash polymkeric substance, removes the homopolymer polystyrene with the hexanaphthene extracting, remove the homopolymer polymethylmethacrylate with the acetonitrile extracting again, be dried to constant weight then.
CpMCl
3With Cp
1[MCl
2] Cp
2Compare CpMCl
3The resulting polymers productive rate is higher at a lower temperature, and the molecular weight of resulting polymers is bigger, so CpMCl
3Catalytic performance be better than Cp
1[MCl
2] Cp
2
Among the present invention, IV subgroup transition metal metallocene compound, only single component can be at the aqueous phase catalytic polymerization, resulting polymers such as polymethylmethacrylate (PMMA) viscosity-average molecular weight is up to 3,600,000, molecular weight distribution is 2.28～4.39, and a rule content is about 60%, and polystyrene (PS) viscosity-average molecular weight reaches 750,000, molecular weight distribution is up to 10.82, on gpc chromatogram even bimodal distribution occurs.The inventive method is that medium is used for catalytic polymerization, not only economy but also environmental protection with water.
Embodiment
Embodiment 1:
With metallocene CpTiCl
3Be catalyzer, catalysis MMA polymerization in aqueous phase system
Whole converging operation and reaction process are carried out under protection of inert gas, add metallocene catalyst CpTiCl in reactor successively
3, polymerization single polymerization monomer MMA 1g, stirred 1 hour, add the aqueous solution (5.77 * 10 of sodium laurylsulfonate
-3G SDS/10ml H
2O), continue to stir 1 hour, add MMA 1g.Put under the temperature of setting and react, behind the polymerization certain hour, the ethanol solution hydrochloride 20ml cancellation with 10% stops polymerization, add excess ethyl alcohol make polymkeric substance separate out immediately adularescent PMMA precipitation generates.Filter, PMMA removes residual catalyzer and acid with ethanol and distilled water wash repeatedly, 60 ℃ of following vacuum-dryings to constant weight.
Reaction conditions and result are as the total consumption 2g of table 1:(MMA monomer)
Table 1
| Embodiment | Temperature of reaction (℃) | Reaction times (h) | mol(MMA )/mol(CpTi Cl 3) | The SDS aqueous solution (ml) | Transformation efficiency Conv./% (PMMA) | Viscosity-average molecular weight M η/(10 4) |
| 1 | 30 | 15 | 100 | 10 | 45.8 | 360.29 |
Annotate: mol (MMA)/mol (CpTiCl
3) for the total mole number of MMA that drops into earlier and the MMA that adds with the ratio of the mole number of metallocene catalyst, be among all in the back embodiment monomer that drops into earlier and the monomeric total mole number of adding with the ratio of the mole number of metallocene catalyst.
Will be with CpTiCl
3The polymkeric substance that obtains for the reaction of catalyst MMA aqueous polymerization carries out molecular weight distribution and Micro-Structure Analysis.
Gpc analysis: PMMA molecular weight distribution (MWD) is bimodal distribution in the time of 30 ℃ between 2.28～4.39.
DSC surveys fusing point and the second-order transition temperature of PMMA, does not also detect during temperature programming to 300 ℃, and possible PMMA exists certain crosslinked under the effect of kish ionic.
1HNMR surveys the degree of isotacticity of polymer P MMA, and a rule content is 58%.
Embodiment 2:
With metallocene CpTiCl
3Be catalyzer, catalysis St polymerization in aqueous phase system
Whole converging operation and reaction process are carried out under protection of inert gas, add metallocene catalyst CpTiCl in reactor successively
3, polymerization single polymerization monomer St 1g, stirred 1 hour, add the aqueous solution (5.77 * 10 of sodium laurylsulfonate
-3G SDS/10ml H
2O), continue to stir 1 hour, add St 1g.Put under the temperature of setting and react, behind the polymerization certain hour, the ethanol solution hydrochloride 20ml cancellation with 10% stops polymerization, add excess ethyl alcohol make polymkeric substance separate out immediately adularescent PS precipitation generates.Filter, PS removes residual catalyzer and acid with ethanol and distilled water wash repeatedly, 60 ℃ of following vacuum-dryings to constant weight.
Reaction conditions and result are as the total consumption 2g of table 2:(St monomer)
Table 2
| Embodiment | Temperature of reaction (℃) | Reaction times (h) | mol(St)/ mol(CpTi Cl 3) | The SDS aqueous solution (ml) | Conv./％( PS) | M η/(10 4) |
| 2 | 55 | 15 | 100 | 10 | 26.82 | 58.55 |
Will be with CpTiCl
3The polymkeric substance that obtains for the reaction of catalyst St aqueous polymerization carries out the molecular weight distribution analysis.
Gpc analysis: PS molecular weight distribution (MWD) reaches 10.82 in the time of 30 ℃, and is bimodal distribution, and the PS molecular weight distribution is between 2.15～3.93 under all the other conditions.
Embodiment 3:
With metallocene CpTiCl
3Be catalyzer, catalysis MMA and St copolymerization in aqueous phase system
Whole converging operation and reaction process are carried out under protection of inert gas, add metallocene catalyst CpTiCl in reactor successively
3, polymerization single polymerization monomer MMA 0.5g, St 0.5g, stirred 1 hour, add the aqueous solution (5.77 * 10 of sodium laurylsulfonate
-3G SDS/10ml H
2O), continue to stir 1 hour, add MMA 0.5g, St 0.5g.Put under the temperature of setting and react, behind the polymerization certain hour, the ethanol solution hydrochloride 20ml cancellation with 10% stops polymerization, adds excess ethyl alcohol polymkeric substance is separated out, and the adularescent precipitation generates immediately.Filter, multipolymer is removed residual catalyzer and acid with ethanol and distilled water wash repeatedly, removes homopolymer PS with the hexanaphthene extracting, removes homopolymer PMMA with the acetonitrile extracting again, 60 ℃ of following vacuum-dryings to constant weight.
Reaction conditions and result are 1g as table 3:(MMA, the total consumption of St monomer)
Table 3
| Embodiment | Temperature of reaction (℃) | Reaction times (h) | mol(St+MMA) /mol(CpTiCl 3) | The SDS aqueous solution (ml) | Conv./% (multipolymer of MMA and St) | M w/(10 4) |
| 3 | 55 | 15 | 100 | 20 | 24.79 | 149.96 |
Annotate: molecular weight is measured by GPC
Will be with CpTiCl
3The polymkeric substance that obtains for catalyst MMA, St water copolymerization carries out the molecular weight distribution analysis.
Gpc analysis: under the above-mentioned condition, the molecular weight distribution of multipolymer (MWD) is 3.45.
Embodiment 4:
With metallocene CpZrCl
3Be catalyzer, catalysis MMA polymerization in aqueous phase system
Whole converging operation and reaction process are carried out under protection of inert gas, add metallocene catalyst CpZrCl in reactor successively
3, polymerization single polymerization monomer MMA 1g, stirred 1 hour, add the aqueous solution (5.77 * 10 of sodium laurylsulfonate
-3G SDS/10ml H
2O), continue to stir 1 hour, add MMA 1g.Put under the temperature of setting and react, behind the polymerization certain hour, the ethanol solution hydrochloride 20ml cancellation with 10% stops polymerization, add excess ethyl alcohol make polymkeric substance separate out immediately adularescent PMMA precipitation generates.Filter, PMMA removes catalyzer and the acid that participates in ethanol and distilled water wash repeatedly, 60 ℃ of following vacuum-dryings to constant weight.
Reaction conditions and result are as the total consumption 2g of table 4:(MMA monomer)
Table 4
| Embodiment | Temperature of reaction (℃) | Reaction times (h) | mol(MMA )/mol(CpZr Cl 3) | The SDS aqueous solution (ml) | Conv./％( PMMA) | M w/(10 4) |
| 4 | 55 | 15 | 100 | 10 | 11.81 | 150.35 |
Annotate: molecular weight is surveyed foot by GPC
Will be with CpZrCl
3The polymkeric substance that obtains for the reaction of catalyst MMA aqueous polymerization carries out the molecular weight distribution analysis.
Gpc analysis: under the above-mentioned condition, PMMA molecular weight distribution (MWD) is 3.50, is bimodal distribution.
Embodiment 5:
With metallocene CpZrCl
3Be catalyzer, catalysis St polymerization in aqueous phase system
Whole converging operation and reaction process are carried out under protection of inert gas, add metallocene catalyst CpZrCl in reactor successively
3, polymerization single polymerization monomer St 1g, stirred 1 hour, add the aqueous solution (5.77 * 10 of sodium laurylsulfonate
-3G SDS/10ml H
2O) continue to stir 1 hour, add St 1g.Put under the temperature of setting and react, behind the polymerization certain hour, the ethanol solution hydrochloride 20ml cancellation with 10% stops polymerization, add excess ethyl alcohol make polymkeric substance separate out immediately adularescent PS precipitation generates.Filter, PS removes catalyzer and the acid that participates in ethanol and distilled water wash repeatedly, 60 ℃ of following vacuum-dryings to constant weight.
Reaction conditions and result are 2g as the total consumption of table 5:(St monomer)
Table 5
| Embodiment | Temperature of reaction (℃) | Reaction times (h) | Mol (vinylbenzene)/mol (Cp TiCl 3) | The SDS aqueous solution (ml) | Conv./％( PS) | M w/(10 4) |
| 5 | 55 | 15 | 100 | 10 | 2.82 | 42.68 |
Annotate: molecular weight is measured by GPC
Will be with CpZrCl
3The polymkeric substance that obtains for the reaction of catalyst St aqueous polymerization carries out the molecular weight distribution analysis.
Gpc analysis: under the above-mentioned condition, PS molecular weight distribution (MWD) is 5.85.
Embodiment 6:
With metallocene Cp
2TiCl
2Be catalyzer, catalysis MMA polymerization in aqueous phase system
Whole converging operation and reaction process need not to carry out under protection of inert gas, add metallocene catalyst Cp in reactor successively
2TiCl
2, polymerization single polymerization monomer MMA 1g, stirred 1 hour, add the aqueous solution (5.77 * 10 of sodium laurylsulfonate
-3G SDS/10ml H
2O), continue to stir 1 hour, add MMA 1g.Put under the temperature of setting and react, behind the polymerization certain hour, the ethanol solution hydrochloride 20ml cancellation with 10% stops polymerization, add excess ethyl alcohol make polymkeric substance separate out immediately adularescent PMMA precipitation generates.Filter, PMMA removes residual catalyzer and acid with ethanol and distilled water wash repeatedly, 60 ℃ of following vacuum-dryings to constant weight.
Reaction conditions and result are as the total consumption 2g of table 6:(MMA monomer)
Table 6
| Embodiment | Temperature of reaction (℃) | Reaction times (h) | mol(MMA) /mol(Cp 2Ti Cl 2) | The SDS aqueous solution (ml) | Transformation efficiency Conv./% (PMMA) | Viscosity-average molecular weight M η/(10 4) |
| 6 | 55 | 15 | 100 | 10 | 78.65 | 18.23 |
Embodiment 7:
With metallocene ((CH
3)
2C) Cp
2TiCl
2Be catalyzer, catalysis MMA polymerization in aqueous phase system
Whole converging operation and reaction process are carried out under protection of inert gas, add metallocene catalyst ((CH in reactor successively
3)
2C) Cp
2TiCl
2, polymerization single polymerization monomer MMA 1g stirred 1 hour, added the aqueous solution (5.77 * 10 of sodium laurylsulfonate
-3G SDS/10ml H
2O), continue to stir 1 hour, add MMA 1g.Put under the temperature of setting and react, behind the polymerization certain hour, the ethanol solution hydrochloride 20ml cancellation with 10% stops polymerization, add excess ethyl alcohol make polymkeric substance separate out immediately adularescent PMMA precipitation generates.Filter, PMMA removes residual catalyzer and acid with ethanol and distilled water wash repeatedly, 60 ℃ of following vacuum-dryings to constant weight.
Reaction conditions and result are as the total consumption 2g of table 7:(MMA monomer)
Table 7
| Embodiment | Temperature of reaction (℃) | Reaction times (h) | mol(MMA)/ mol(((CH 3) 2C )Cp 2TiCl 2) | The SDS aqueous solution (ml) | Transformation efficiency Conv./% (PMMA) | Viscosity-average molecular weight M η/(10 4) |
| 7 | 55 | 15 | 100 | 10 | 91.65 | 53.23 |
Embodiment 8:
With metallocene [(CpTiCl
2)
2(η 5-η 5-C
5H
4(CH
2)
20 (CH
2)
2C
5H
4)] be catalyzer, catalysis MMA polymerization in aqueous phase system
Whole converging operation and reaction process are carried out under protection of inert gas, add metallocene catalyst [(CpTiCl in reactor successively
2)
2(η 5-η 5-C
5H
4(CH
2)
2O (CH
2)
2C
5H
4)], polymerization single polymerization monomer MMA 1g stirred 1 hour, added the aqueous solution (5.77 * 10 of sodium laurylsulfonate
-3GSDS/10ml H
2O), continue to stir 1 hour, add MMA 1g.Put under the temperature of setting and react, behind the polymerization certain hour, the ethanol solution hydrochloride 20ml cancellation with 10% stops polymerization, add excess ethyl alcohol make polymkeric substance separate out immediately adularescent PMMA precipitation generates.Filter, PMMA removes residual catalyzer and acid with ethanol and distilled water wash repeatedly, 60 ℃ of following vacuum-dryings to constant weight.
Reaction conditions and result are as the total consumption 2g of table 8:(MMA monomer)
Table 8
| Embodiment | Temperature of reaction (℃) | Reaction times (h) | mol(MMA)/mol([( CpTiCl 2) 2(η5-η5-C 5 H 4(CH 2) 2O(CH 2) 2 C 5H 4)]) | The SDS aqueous solution (ml) | Transformation efficiency Conv./% (PMMA) | Viscosity-average molecular weight M η/(10 4) |
| 8 | 65 | 15 | 100 | 10 | 66.85 | 188.91 |
Embodiment 9:
With metallocene [(CpTiCl
2)
2(η 5-η 5-C
5H
4(CH
2C
6H
4CH
2) C
5H
4)] (methylene radical on phenyl ring can for adjacent,, para-orientation) be catalyzer, catalysis MMA polymerization in aqueous phase system
Whole converging operation and reaction process are carried out under protection of inert gas, add metallocene catalyst such as contraposition [(CpTiCl in reactor successively
2)
2(η 5-η 5-C
5H
4(CH
2C
6H
4CH
2) C
5H
4)], polymerization single polymerization monomer MMA 1g, stirred 1 hour, add the aqueous solution (5.77 * 10 of sodium laurylsulfonate
-3GSDS/10ml H
2O), continue to stir 1 hour, add MMA 1g.Put under the temperature of setting and react, behind the polymerization certain hour, the ethanol solution hydrochloride 20ml cancellation with 10% stops polymerization, add excess ethyl alcohol make polymkeric substance separate out immediately adularescent PMMA precipitation generates.Filter, PMMA removes residual catalyzer and acid with ethanol and distilled water wash repeatedly, 60 ℃ of following vacuum-dryings to constant weight.
Reaction conditions and result are as the total consumption 2g of table 9:(MMA monomer)
Table 9
| Embodiment | Temperature of reaction (℃) | Reaction times (h) | mol(MMA)/mol([(Cp TiCl 2) 2(η5-η5-C 5H 4(C H 2C 6H 4CH 2)C 5H 4)]) | The SDS aqueous solution (ml) | Transformation efficiency Conv./% (PMMA) | Viscosity-average molecular weight M η/(10 4) |
| 9 | 55 | 15 | 100 | 10 | 76.85 | 288.71 |
Claims (5)
1, a kind of method of catalyzing water phase polymerization by metallocene catalyst, it is characterized in that: in reactor, add metallocene catalyst, elder generation's input polar monomer 1～2 weight part, stirred 0.5～3 hour, adding concentration is the sodium dodecyl sulfate aqueous solution of 0.2～2.0g/L, continue to stir 0.5～3 hour, add polar monomer 1～2 weight part; 30～85 ℃ carry out aqueous polymerization reaction 2.5～25h after, add the ethanolic soln termination reaction of hydrochloric acid, obtain polymer precipitation, obtain polymerisate through aftertreatment; Described polar monomer is one or more in methyl methacrylate, butyl methacrylate, methyl acrylate, butyl acrylate or the vinylbenzene; Count 1 gram with the polar monomer weight that drops into earlier, the consumption of described sodium dodecyl sulfate aqueous solution is 2.5～40ml; The total mole number of described polar monomer is 50～800: 1 with the ratio of the mole number of metallocene catalyst.
2, method according to claim 1, it is characterized in that: described metallocene catalyst structural formula is:
CpMCl
3
Or
Or
Or
Wherein Cp is cyclopentadienyl-C
5H
5
Cp
1, Cp
2, Cp
3Be separate not replacement or have Me or have Me
3Si is substituent to have cyclopentadiene, indenes or fluorene structured part;
X is (CH
3)
2C-or (CH
3)
2Si-;
X
1Be-(CH
2)
2O (CH
2)
2-,-(CH
2)
2S (CH
2)
2-or-CH
2C
6H
4CH
2-;
M is Ti, Zr or Hf.
3, method according to claim 1 is characterized in that: described aqueous polymerization reaction can be a kind of homopolymerization or the monomeric copolyreaction of various polarity of polar monomer, during the copolymerization of multiple monomer polarity between each comonomer weight ratio be 1: 1.
4, method according to claim 1, it is characterized in that: the reaction of described aqueous polymerization is during for a kind of polar monomer homopolymerization, the post-treating method that adopts is with the resulting polymers precipitation after filtering, with ethanol and distilled water wash polymkeric substance, is dried to constant weight then.
5, method according to claim 1, it is characterized in that: when described aqueous polymerization reaction is vinylbenzene and methyl methacrylate copolymer reaction, the post-treating method that adopts is with the resulting polymers precipitation after filtering, with ethanol and distilled water wash polymkeric substance, remove the homopolymer polystyrene with the hexanaphthene extracting, remove the homopolymer polymethylmethacrylate with the acetonitrile extracting again, be dried to constant weight then.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1450089A (en) * | 2002-04-10 | 2003-10-22 | 中国石油化工股份有限公司 | Metallocene titanium compound and use thereof |
| CN1590393A (en) * | 2003-09-03 | 2005-03-09 | 中国石油化工股份有限公司 | Cyclopentadienyl metal titanium compound and its use |
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|---|---|---|---|---|
| CN1450089A (en) * | 2002-04-10 | 2003-10-22 | 中国石油化工股份有限公司 | Metallocene titanium compound and use thereof |
| CN1590393A (en) * | 2003-09-03 | 2005-03-09 | 中国石油化工股份有限公司 | Cyclopentadienyl metal titanium compound and its use |
Non-Patent Citations (4)
| Title |
|---|
| 双核茂金属催化剂催化聚合反应进展. 班青，孙俊全.高分子通报，第6期. 2002 |
| 双核茂金属催化剂催化聚合反应进展. 班青，孙俊全.高分子通报，第6期. 2002 * |
| 茂型稀土金属有机配合物催化甲基丙烯酸酯类聚合研究进展. 罗梅，苏庆德，马怀柱.结构化学，第21卷第6期. 2002 |
| 茂型稀土金属有机配合物催化甲基丙烯酸酯类聚合研究进展. 罗梅，苏庆德，马怀柱.结构化学，第21卷第6期. 2002 * |
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