CN100371356C - Negative charged ion polymerization method of 2,2,2-Trifluorethylmethyl acrylate - Google Patents
Negative charged ion polymerization method of 2,2,2-Trifluorethylmethyl acrylate Download PDFInfo
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- CN100371356C CN100371356C CNB2006100894029A CN200610089402A CN100371356C CN 100371356 C CN100371356 C CN 100371356C CN B2006100894029 A CNB2006100894029 A CN B2006100894029A CN 200610089402 A CN200610089402 A CN 200610089402A CN 100371356 C CN100371356 C CN 100371356C
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Abstract
The present invention relates to an anionic polymerizing method of 2, 2, 2-trifluoro ethyl methyl acrylate, which belongs to the field of the anionic polymerization of high molecular material. The method comprises that organic copper which is prepared in advance is first added in a reacting container; then, organic lithium is added; the reaction is sustained for 2 to 30 minutes for generating the organic copper lithium; 2, 2, 2-trifluoro ethyl methyl acrylate monomers are added; the polyreaction is sustained for 2 to 120 minutes at-50 DEG C to 30 DEG C to obtain the poly2, 2, 2-trifluoro ethyl methyl acrylate. The present invention has the advantages of high initiation efficiency and high monomer converting efficiency.
Description
Technical field
The present invention relates to macromolecular compound synthetic field, particularly anionic polymerization field.
Background technology
In the article (T.Narita, T.Hagiware, H.Hamana, Masaru Goto, Makromol.Chem (1986) 187:731-737) that people such as Tadashi Narita deliver, point out (C with Zn
2H
5)
2And butyllithium (LiC
4H
9) LiZnC that makes
4H
9(C
2H
5)
2Make initiator initiated polymerization 2 in toluene solvant, 2,2-trifluoroethyl methacrylic ester (TFEMA), under 0 ℃ ,-20 ℃ and-78 ℃, what generate gathers 2,2,2-trifluoroethyl methacrylic ester (PTFEMA) monomer conversion is respectively 87.9%, 98% and 31.9%, it should be noted that, though under-20 ℃, obtain almost chemical quantitative monomer conversion, but these polymerization reaction times need 7 days, and this initiator system resulting polymers monomer conversion is 0 when being solvent with tetrahydrofuran (THF) (THF).The pointed initiator system of article is the situation of initiated polymerization TFEMA in toluene, THF equal solvent, comprises situations such as different initiators, different solvents, polymerization reaction time and monomer conversion.The polymerization time of this method is long.
Summary of the invention
The purpose of this invention is to provide a kind of when keeping high efficiency of initiation, high monomer transformation efficiency, polymerization time short 2,2,2-trifluoroethyl methacrylic ester (TFEMA) anionic polymerization method.
The present invention adds organic solvent in reaction vessel, add organic copper again, adds organolithium then and forms polymeric solution, and through 2～30 minutes, preferred 15～30 minutes, organic copper and organolithium reaction generated initiator organic copper lithium (RLi/A
2BCu); Adding concentration then is 2 of 3～21%wt, 2, (concentration value described here is according to formula to 2-trifluoroethyl methacrylate monomer: monomer mass/(monomer mass+solvent quality) * 100%-50 ℃～30 ℃ polymerizations, calculate), reacted preferred 40～90 minutes 2～120 minutes, generate poly-2,2,2-trifluoroethyl methacrylic ester, the preferred 6～18%wt of monomer concentration; The general formula of described organic copper is expressed as A
2BCu, wherein A is an organic group, B is phosphorus (P) atom or nitrogen (N) atom; The general formula of described organolithium is RLi, and wherein R is C
1-6Alkyl, phenyl, benzyl, allyl group or polymkeric substance short chain; The concentration of organolithium in described polymeric solution is 0.0105～0.042mol/L, and organic copper is (0.25～1.5) to the molar ratio of organolithium: 1, and preferred 1: 1.
Organic solvent is tetrahydrofuran (THF) (THF), N, one or more in dinethylformamide (DMF), the toluene.
Organic group A in the organic copper general formula is C
2-6Alkyl, phenyl (Ph-) or cyclohexyl (Cy-), preferred phenyl or cyclohexyl.
The aforementioned polymer short chain is isoprene short chain or polystyrene short chain.
R in the general formula of organolithium, preferred normal-butyl or isoprene short chain.When R was the isoprene short chain, the organolithium of generation was the two lithiums of isoprene short chain, can be by general formula Li-(Ip)
3-6-Li represents.
Cause the TFEMA polymerization with the initiator among the present invention, the monomer conversion height of resulting polymers PTFEMA (≈ 100%), polymerization time short (monomer conversion can reach at 100% o'clock in 40 minutes), the number-average molecular weight of resulting polymers PTFEMA (Mn) is 1 * 10
3～2 * 10
4, relative molecular weight distribution (MWD) is 1.23～1.29, efficiency of initiation is much in 60%, has very high industrial value.
Monomer conversion adopts weighting method to measure, and claims to such an extent that add monomeric weight (M before adding monomer
1), after treating to generate polymkeric substance fully, claim the weight (M of polymkeric substance after termination, the drying again
2), monomer conversion=M
2/ M
1* 100%.
The number-average molecular weight of initiator efficiency of initiation=theory/experiment gained number-average molecular weight * monomer conversion, experiment gained number-average molecular weight can obtain with the test of GPC gel chromatograph.
Description of drawings
Accompanying drawing 1 is 2,2, the monomer conversion-time relation figure of 2-trifluoroethyl methacrylic ester.
Embodiment
In order to further specify the present invention, following selected embodiment is provided, but in specific implementation, should be not limited to these embodiment that presents provides.
Employed organic copper uses existing method to make in the inventive method.Article (A.M.Augiar, J.Giaein, and A.Mills, J.org.Chem., 27,674 (1962)) referring to people such as A.M.Augiar.Organolithium also uses existing method to make or is commercial.
The preparation step of each embodiment all is to use conventional method with the polymerization bottle deoxygenation dehumidifying removal of impurity, charges into nitrogen then in polymerization bottle; The termination step methyl alcohol termination reaction of polyreaction must gather 2,2 through post precipitation vacuum-drying, 2-trifluoroethyl methacrylic ester; The condition of middle three steps and correspondence such as following; The PTFEMA polymkeric substance of TFEMA monomer conversion, initiator efficiency of initiation, generation adopts gel permeation chromatography number-average molecular weight Mn to see Table 1 among each embodiment, nucleus magnetic resonance (NMR) result proves that the gained reaction product is poly-2,2,2-trifluoroethyl methacrylic ester (PTFEMA).
Embodiment 1:
Under-50 ℃ of temperature, add the THF solvent that 30ml contains 0.63mmol diphenylphosphine copper (DPPCu);
N-Butyl Lithium (the n-BuLi) (Cu: Li=1: 1), reacted 15 minutes, generate organic copper lithium that adds 0.63mmol then;
Add refined 1.5mlTFEMA monomer, 40 minutes reaction times;
Embodiment 2:
Under-50 ℃ of temperature, add 30ml and contain 0.63mmol dicyclohexyl amine copper (Cy
2NCu) THF solvent;
Two lithium (the Li-(Ip) of isoprene short chain that add 0.63mmol then
3-6-Li) (Cu: Li=1: 1), reacted 20 minutes, generate organic copper lithium;
Add refined 1.5mlTFEMA monomer, reacted 40 minutes;
Embodiment 3:
Under-50 ℃ of temperature, add the THF solvent that 30ml contains 0.1575mmol diphenylphosphine copper (DPPCu);
N-Butyl Lithium (the n-BuLi) (Cu: Li=0.25: 1), reacted 15 minutes, generate organic copper lithium that adds 0.63mmol then;
Add refined 1.5mlTFEMA monomer, reacted 40 minutes;
Embodiment 4:
Under-50 ℃ of temperature, add the THF solvent that 30ml contains 0.63mmol diphenylphosphine copper (DPPCu);
N-Butyl Lithium (the n-BuLi) (Cu: Li=1.5: 1), reacted 15 minutes, generate organic copper lithium that adds 0.42mmol then;
Add refined 1.5mlTFEMA monomer, reacted 40 minutes;
Embodiment 5:
Under 0 ℃ of temperature, add the THF solvent that 30ml contains 0.63mmol diphenylphosphine copper (DPPCu);
N-Butyl Lithium (the n-BuLi) (Cu: Li=1: 1), reacted 15 minutes, generate organic copper lithium that adds 0.63mmol then;
Add refined 0.76mlTFEMA monomer, reacted 40 minutes;
Embodiment 6:
Under-50 ℃ of temperature, add the THF solvent that 30ml contains 0.315mmol diphenylphosphine copper (DPPCu);
N-Butyl Lithium (the n-BuLi) (Cu: Li=1: 1), reacted 15 minutes, generate organic copper lithium that adds 0.315mmol then;
Add refined 5.3mlTFEMA monomer, reacted 40 minutes;
Embodiment 7:
Under-50 ℃ of temperature, add the DMF solvent that 30ml contains 1.26mmol diphenylphosphine copper (DPPCu);
N-Butyl Lithium (the n-BuLi) (Cu: Li=1: 1), reacted 15 minutes, generate organic copper lithium that adds 1.26mmol then;
Add refined 1.5mlTFEMA monomer, reacted 40 minutes;
Embodiment 8:
Under-50 ℃ of temperature, add 30ml contain 0.63mmol diphenylphosphine copper (DPPCu) THF/ toluene (15/15, v/v) mixed solvent;
N-Butyl Lithium (the n-BuLi) (Cu: Li=1: 1), reacted 15 minutes, generate organic copper lithium that adds 0.63mmol then;
Add refined 1.5mlTFEMA monomer, reacted 40 minutes;
Embodiment 9:
Under 10 ℃ of temperature, add 30ml and contain 0.63mmol dicyclohexyl amine copper (Cy
2NCu) solvent of THF;
N-Butyl Lithium (the n-BuLi) (Cu: Li=1: 1), reacted 15 minutes, generate organic copper lithium that adds 0.63mmol then;
Add refined 1.5mlTFEMA monomer, reacted 40 minutes;
Embodiment 10:
Under-50 ℃ of temperature, add 30ml and contain 0.63mmol diethylamide phosphine copper (Et
2NCu) THF solvent;
N-Butyl Lithium (the n-BuLi) (Cu: Li=1: 1), reacted 15 minutes, generate organic copper lithium that adds 0.63mmol then;
Add refined 1.5mlTFEMA monomer, reacted 40 minutes;
Embodiment 11:
Under-10 ℃ of temperature, add 30ml and contain 0.63mmol di-t-butyl amine copper ((t-Bu)
2NCu) THF solvent;
N-Butyl Lithium (the n-BuLi) (Cu: Li=1: 1), reacted 15 minutes, generate organic copper lithium that adds 0.63mmol then;
Add refined 1.5mlTFEMA monomer, reacted 40 minutes;
Embodiment 12:
Under-50 ℃ of temperature, add 30ml and contain 0.63mmol di-t-butyl phosphine copper ((t-Bu)
2PCu) THF solvent;
Hexyl lithium (the C that adds 0.63mmol then
6H
13Li) (Cu: Li=1: 1), reacted 15 minutes, generate organic copper lithium;
Add refined 1.5mlTFEMA monomer, reacted 40 minutes;
Embodiment 13:
Under-20 ℃ of temperature, add 30ml and contain 0.63mmol dihexyl amine copper (C
6H
13)
2NCu) THF solvent;
Phenyl lithium (the C that adds 0.63mmol then
6H
5Li) (Cu: Li=1: 1), reacted 15 minutes, generate organic copper lithium;
Add refined 1.5mlTFEMA monomer, reacted 40 minutes;
Embodiment 14:
Under-50 ℃ of temperature, add the THF solvent that 30ml contains 0.63mmol diphenylphosphine copper (DPPCu);
Benzyl lithium (the C that adds 0.63mmol then
7H
7Li) (Cu: Li=1: 1), reacted 15 minutes, generate organic copper lithium;
Add refined 1.5mlTFEMA monomer, reacted 40 minutes;
Embodiment 15:
Under-50 ℃ of temperature, add the THF solvent that 30ml contains 0.63mmol diphenylphosphine copper (DPPCu);
Lithium methide (the CH that adds 0.63mmol then
3Li) (Cu: Li=1: 1), reacted 15 minutes, generate organic copper lithium;
Add refined 1.5mlTFEMA monomer, reacted 40 minutes;
Embodiment 16:
Under-50 ℃ of temperature, add the THF solvent that 30ml contains 0.63mmol diphenylphosphine copper (DPPCu);
Polystyryl lithium (the PStLi) (Cu: Li=1: 1), reacted 20 minutes, generate organic copper lithium that adds 0.63mmol then;
Add refined 1.5mlTFEMA monomer, reacted 40 minutes;
Embodiment 17:
Under-50 ℃ of temperature, add 30ml contain 0.63mmol diphenylphosphine copper (DPPCu) THF/ toluene/DMF (10/10/10, V/V/V) mixed solvent;
N-Butyl Lithium (the n-BuLi) (Cu: Li=1: 1), reacted 15 minutes, generate organic copper lithium that adds 0.63mmol then;
Add refined 1.5mlTFEMA monomer, reacted 40 minutes;
Embodiment 18:
Under-50 ℃ of temperature, add the THF solvent that 30ml contains 0.63mmol diphenylphosphine copper (DPPCu);
N-Butyl Lithium (the n-BuLi) (Cu: Li=1: 1), reacted 2 minutes, generate organic copper lithium that adds 0.63mmol then;
Add refined 1.5mlTFEMA monomer, 40 minutes reaction times;
Embodiment 19:
Under-50 ℃ of temperature, add the THF solvent that 30ml contains 0.63mmol diphenylphosphine copper (DPPCu);
N-Butyl Lithium (the n-BuLi) (Cu: Li=1: 1), reacted 30 minutes, generate organic copper lithium that adds 0.63mmol then;
Add refined 1.5mlTFEMA monomer, 40 minutes reaction times;
As can be seen from the above embodiments: adopt the organic copper lithium RLi/A among the present invention
2The BCu initiator system causes 2,2,2-trifluoroethyl methacrylate monomer, and monomer conversion mostly is 100%, and the initiator efficiency of initiation is much in 60%, and polymerization reaction time is short, and far above prior art, conversion of monomer efficient and time relation are seen accompanying drawing 1.
Table 1
| The embodiment sequence number | The TFEMA monomer conversion | The initiator efficiency of initiation | PTFEMA number-average molecular weight Mn |
| 1 | 100％ | 100％ | 2780 |
| 2 | 75％ | 59％ | 5620 |
| 3 | 100％ | 50％ | 5630 |
| 4 | 100％ | 93％ | 4220 |
| 5 | 90％ | 88.6％ | 1450 |
| 6 | 100％ | 100％ | 19880 |
| 7 | 100％ | 97％ | 1460 |
| 8 | 91％ | 61％ | 4220 |
| 9 | 100％ | 88％ | 3210 |
| 10 | 100％ | 71％ | 3980 |
| 11 | 100％ | 86％ | 3324 |
| 12 | 100％ | 95％ | 2970 |
| 13 | 100％ | 68％ | 4120 |
| 14 | 100％ | 75％ | 3760 |
| 15 | 80％ | 44％ | 5130 |
| 16 | 88％ | 62％ | 4000 |
| 17 | 95％ | 74％ | 3590 |
| 18 | 100％ | 82％ | 3430 |
| 19 | 100％ | 100％ | 2810 |
Claims (6)
1. one kind 2,2,2-trifluoroethyl methacrylic ester anionic polymerization method is characterized in that:
Add the organic copper for preparing in advance at the reaction vessel that organic solvent is housed earlier, add organolithium then and form polymeric solution, through 2～30 minutes, organic copper and organolithium reaction generated initiator organic copper lithium (RLi/A
2BCu) after, add mass percent concentration and be 3～21% 2,2,2-trifluoroethyl methacrylate monomer is carried out polyreaction under-50 ℃～30 ℃, 2～120 minutes reaction times, obtain poly-2,2,2-trifluoroethyl methacrylic ester; The general formula of described organic copper is expressed as A
2BCu, wherein A is C
2-6Alkyl, phenyl or cyclohexyl, B is phosphorus atom or nitrogen-atoms; The general formula of described organolithium is expressed as RLi, and wherein R is C
1-6Alkyl, phenyl, benzyl, allyl group, isoprene short chain or polystyrene short chain, the concentration of organolithium in described polymeric solution is 0.0105～0.042mol/L, organic copper is (0.25～1.5) to the molar ratio of organolithium: 1; Organic solvent is tetrahydrofuran (THF) (THF), N, any one or more in dinethylformamide (DMF), the toluene.
2. polymerization process according to claim 1 is characterized in that: the R in the described organolithium general formula is a normal-butyl.
3. polymerization process according to claim 1 and 2 is characterized in that: organic copper and organolithium reacted in organic solvent 15～30 minutes.
4. polymerization process according to claim 1 and 2 is characterized in that: monomer concentration is 6～18%wt.
5. polymerization process according to claim 1 and 2 is characterized in that: the time of polyreaction is 40～90 minutes.
6. polymerization process according to claim 1 and 2, organic copper is 1: 1 to the molar ratio of organolithium.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100894029A CN100371356C (en) | 2006-06-23 | 2006-06-23 | Negative charged ion polymerization method of 2,2,2-Trifluorethylmethyl acrylate |
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|---|---|---|---|
| CNB2006100894029A CN100371356C (en) | 2006-06-23 | 2006-06-23 | Negative charged ion polymerization method of 2,2,2-Trifluorethylmethyl acrylate |
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| CN100371356C true CN100371356C (en) | 2008-02-27 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5973086A (en) * | 1995-12-29 | 1999-10-26 | Council Of Scientific & Industrial Research | Process for the living anionic polymerization of alkyl (methacrylic) monomers using a novel initiator system |
| EP1085029A1 (en) * | 1999-09-20 | 2001-03-21 | Kuraray Co., Ltd. | Process for polymerizing a methacrylic ester or an acrylic ester |
| CN1412212A (en) * | 2001-10-11 | 2003-04-23 | 北京化工大学 | Preparation method of double functionality lithium system initiator |
| JP2004161986A (en) * | 2002-09-17 | 2004-06-10 | Lintec Corp | Living polymer of methacrylic acid (alkyl-substituted) aziridinylalkyl ester and method for producing the same |
| CN1603349A (en) * | 2003-09-29 | 2005-04-06 | 中国石油化工股份有限公司 | Method for polymerization of alpha, beta-unsaturated carbonyl and nitrile monomer |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5973086A (en) * | 1995-12-29 | 1999-10-26 | Council Of Scientific & Industrial Research | Process for the living anionic polymerization of alkyl (methacrylic) monomers using a novel initiator system |
| EP1085029A1 (en) * | 1999-09-20 | 2001-03-21 | Kuraray Co., Ltd. | Process for polymerizing a methacrylic ester or an acrylic ester |
| CN1412212A (en) * | 2001-10-11 | 2003-04-23 | 北京化工大学 | Preparation method of double functionality lithium system initiator |
| JP2004161986A (en) * | 2002-09-17 | 2004-06-10 | Lintec Corp | Living polymer of methacrylic acid (alkyl-substituted) aziridinylalkyl ester and method for producing the same |
| CN1603349A (en) * | 2003-09-29 | 2005-04-06 | 中国石油化工股份有限公司 | Method for polymerization of alpha, beta-unsaturated carbonyl and nitrile monomer |
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