CN1208361C - Method for preparing 4-vinylpyridine using single component rare earth organic compound as catalyst - Google Patents

Method for preparing 4-vinylpyridine using single component rare earth organic compound as catalyst Download PDF

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CN1208361C
CN1208361C CN 03132168 CN03132168A CN1208361C CN 1208361 C CN1208361 C CN 1208361C CN 03132168 CN03132168 CN 03132168 CN 03132168 A CN03132168 A CN 03132168A CN 1208361 C CN1208361 C CN 1208361C
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rare earth
vinylpridine
thf
ether
substituted
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CN1478799A (en
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姚英明
沈琪
罗云杰
张振琴
邓明宇
薛明强
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Suzhou University
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Abstract

The present invention discloses a method of preparing poly(4-vinylpyridine) by adopting a rare earth organic compound as a catalyst. 4-vinylpyridine monomers, a catalyst and a solvent are adopted for forming a polymerization system; the polymerization is carried out under the condition of inert atmosphere; polymerization temperature is from 15DEGC to 120 DEG C, wherein the catalyst is a kind of rare earth organic complex. The method has the characteristics of high catalyst activity, high yield of polymers, moderate polyreaction conditions and superior molecular weight of obtained polymers.

Description

Single-component rare earth organic compounds catalysis 4-vinylpridine polymeric method
Technical field
The present invention relates to the preparation method of a kind of poly-(4-vinylpridine), particularly relate to a kind of method that adopts rare earth organic complex as the polycoordination method preparation poly-(4-vinylpridine) of catalyzer.
Background technology
Poly-(4-vinylpridine) is later on a kind of water-soluble polymers by the quaternary amine salinization, can be used as polyelectrolyte; Nitrogen-atoms on the pyridine ring has strong coordination ability, can with a series of metal coordinations, form metal-containing polymer, thereby poly-(4-vinylpridine) can also be used for and high molecular weight reactive as catalyst-supporting support organic.Therefore, poly-(4-vinylpridine) is a kind of functional high molecule material with extensive use.
In the prior art, the method for synthetic poly-(4-vinylpridine) mainly contains free radical polymerization, anionic initiation polymerization and polycoordination.
Wherein, the anionic initiation polyreaction as, at Varshney, S.K.; Zhong, X.F.; Eisenberg, A.; Macromolecules discloses a kind of anionic initiation polymeric method in 1993,26,701., and used anionic initiator is respectively alpha-methyl styrene base lithium (α-MS -Li +), 1,2-phenylbenzene-3-methyl amyl lithium (DPP -Li +), perhaps diphenyl methyl potassium (Ph 2CH -K +), solvent for use can be tetrahydrofuran (THF) (THF), tetrahydrofuran (THF) and 6-methyl phosphonic triamide (HMPT), the perhaps mixed solvent of tetrahydrofuran (THF) and dimethyl formamide (DMF), these systems can also can cause the copolymerization of 4-vinylpridine and methacrylic ester at-78 ℃ of living polymerizations that cause 4-vinylpridine.At Creutz, S.; Teyssie, P.; Jerome, R.; Macromolecules, 1997,30,1. in, the anionic initiation polymeric method under higher relatively temperature is disclosed, used initiator is diphenyl methyl lithium (Ph 2CH -Li +).Solvent for use is the mixed solvent (volume ratio is 9/1) of pyridine and tetrahydrofuran (THF).This system can also can cause the copolymerization of 4-vinylpridine and methacrylic tert-butyl acrylate at 0 ℃ of living polymerization that causes 4-vinylpridine.Initiated polymerization will be anionic initiation polymeric defective under lower temperature.
The report of radical polymerization has, at Xia, and J.H.; Zhang, X.; Matyjaszewski, K.; Macromolecules, 1999,32,3531. in the literary composition, disclose and adopted the method for atom transfer radical polymerization to cause the 4-vinylpridine polymerization, the polymerization system that adopts is respectively 1-phenylethyl bromine (PEBr)/cuprous bromide (CuBr)/2,2 '-dipyridyl (bpy), 1-phenylethyl bromine (PEBr)/cuprous bromide (CuBr)/N, N, N ', N ", N "-pentamethyl-dimethylene triamine (PMDETA), 1-phenylethyl chlorine (PECl)/cuprous chloride (CuCl)/N, N, N ', N "; N "-pentamethyl-dimethylene triamine (PMDETA), 1-phenylethyl chlorine (PECl)/cuprous chloride (CuCl)/three-[2-(dimethyl amido) ethyl] amine (TREN), solvent is a Virahol, these systems can cause the 4-vinylpridine polymerization at 40 ℃.At Fischer, A.; Brembilla, A.; Lochon.P.; Macromolecules, 1999,32,6069. in, disclosing with the nitroxyl free radical is that medium causes 4-vinylpridine polymeric method, used free radical system is 2,2,6,6-tetramethyl-piperidyl oxygen (TEMPO)/benzoyl peroxide (BPO), this system can cause the 4-vinylpridine polymerization at 138 ℃.This free radical polymerization, its defective be polymerization temperature than higher, need the heating, poor controllability even improved controllable free-radical initiated polymerization was arranged afterwards, also exists transformation efficiency low, problems such as the metallic compound content in the product is big influence the use of polymerisate.
And in the reaction of present polycoordination, that adopts is binary catalyst system, and typical report has Wang Xiaoju, Qu Yahuan, Jiang Guihua, Liaoning Normal University's journal (natural science edition), 1999,22,228, the complex-catalyzed 4-vinylpridine polymerization of rare earth chloride dimethyl sulfoxide (DMSO), used catalyst system is Neodymium trichloride dimethyl sulfoxide (DMSO) title complex (NdCl 34DMSO)/triisobutyl aluminium (AlBu i 3), solvent for use is a toluene, this system can be in the polymerization of 50 ℃ of catalysis 4-vinylpridines, [4-VP]/[Nd]=4750,5h, C=6%; Wang Xiaoju, Qu Yahuan, Chen Ruizhan, petrochemical complex, 1999,28,537, the research of neodymium chloride complex catalysis 4-vinylpyridine kinetics of polymerization reaction, used catalyst system is Neodymium trichloride dimethyl sulfoxide (DMSO) title complex (NdCl 34DMSO)/triisobutyl aluminium (AlBu i 3), solvent for use is a toluene, finds that the concentration of polymerization rate and 4-vinylpridine and Neodymium trichloride all is the one-level relation; Wang Xiaoju, in common vetch, Chen Ruizhan, Journal of Molecular Catalysis, 2001,15,222, the katalysis of neodymium chloride complex in the 4-vinylpyridine polyreaction, used catalyst system is poly-(styrene-propene acid amides) load Neodymium trichloride (PSAMNdCl 3)/triisobutyl aluminium (AlBu i 3); Neodymium trichloride acrylamide title complex (NdCl 33PA)/triisobutyl aluminium (AlBu i 3); Neodymium trichloride dimethyl sulfoxide (DMSO) title complex (NdCl 34DMSO)/triisobutyl aluminium (AlBu i 3), transformation efficiency can surpass 40% under certain condition; Wang Xiaoju, Qu Yahuan, Chen Ruizhan, China's rare-earth journal, 2000,18,82, the research of the complex-catalyzed 4-vinylpyridine polyreaction of Neodymium trichloride acrylamide, the binary system that research Neodymium trichloride acrylamide title complex and aluminum alkyls are formed is to 4-vinylpyridine polymeric catalytic activity, and wherein aluminum alkyls is respectively triisobutyl aluminium (AlBu i 3), diisobutyl aluminum (Bu i 2AlH), triethyl aluminum (AlEt 3).And performance is active, easily burns, and has influenced actual use; Simultaneously, its reaction conversion ratio is low, generally is no more than 40%.
Summary of the invention
The object of the invention provides a kind of polymerization process of 4-vinylpridine, adopts single-component catalyst to realize the polycoordination of 4-vinylpridine, improves the yield of activity of such catalysts and polymkeric substance.
For achieving the above object; the technical solution used in the present invention is: a kind of 4-vinylpridine polymeric method; adopt the 4-vinylpridine monomer; catalyzer and solvent composition polymerization system; under inert atmosphere, carry out polymerization; polymerization temperature is 15 ℃ to 120 ℃; wherein; described catalyzer is the rare earth organic complex that includes metal nitrogen key or metal carbon bond; described solvent is not for containing the organic solvent of reactive hydrogen; the pKa value of solvent less than with the pKa value of the part of rare-earth ion coordination; wherein, the necessary deoxygenation of polymerization system; dewater, with rare gas element (as argon gas or nitrogen) protection.
In the technique scheme, the polymeric reaction temperature scope from 25 ℃ to 50 ℃ effect preferable.
In the technique scheme, described " pKa value " is used to express the acidity of compound, and be relevant with the dissociation constant of hydrogen, is the logarithmic negative of the dissociation constant of hydrogen, and the pKa value is big more, and the acidity of compound is more little, and its contained hydrogen is got over torpescence.Described catalyzer is a rare earth organic complex, the rare earth organic complex here is meant real (narrow sense) rare earth organic complex, comprising the rare earth compound that includes metal nitrogen key or metal carbon bond, rather than refer to comprise the rare earth compound of metal oxygen key.Catalyzer can be trivalent rare earth organic compound, bivalent rare earth organic compound, also can be alkoxyl group or aryloxy rare earth organic compounds.Comprising:
Described catalyzer is that general formula is [R 1NC (NR 2 2) NR 1] 2MR 3(S) trivalent rare earth organic compound, wherein R 1Be alkyl, cycloalkyl or trialkyl silyl; R 2Be alkyl or aryl; R 3Be alkyl, aryl, hydrogen or amido; M is scandium, yttrium or lanthanon; S is ether (Et 2O), tetrahydrofuran (THF), glycol dimethyl ether or Tetramethyl Ethylene Diamine (TMEDA).
Described catalyzer is that general formula is Cp ' 2The trivalent rare earth organic compound of MR (S), wherein Cp ' is cyclopentadienyl, substituted cyclopentadienyl, indenyl (Ind) or substituted indenyl, R is alkyl, aryl, hydrogen or amido; M is scandium, yttrium or lanthanon; S is ether, tetrahydrofuran (THF), glycol dimethyl ether or Tetramethyl Ethylene Diamine.
Described catalyzer is that general formula is [(R 1) CN (Ar) CHC (R 1) N (Ar)] MR 2 nX 2-n(S) trivalent rare earth organic compound, wherein R 1Be the methyl or the tertiary butyl; Ar is aryl or substituted aryl; R 2Be alkyl, fragrant organic compounds, wherein R 1Be the methyl or the tertiary butyl; Ar is aryl or substituted aryl; R 2Be alkyl, aryl or amido; M is scandium, yttrium or lanthanon; X is a halogen; N=1 or 2; S is ether, tetrahydrofuran (THF), glycol dimethyl ether or Tetramethyl Ethylene Diamine.
Described catalyzer be general formula be [Cp ' 2M (S) n] [BPh 4] the Tricationic rare earth organic compounds, wherein Cp ' is cyclopentadienyl, substituted cyclopentadienyl, indenyl or substituted indenyl; M is scandium, yttrium or lanthanon; S is ether, tetrahydrofuran (THF) or glycol dimethyl ether; N=1 or 2.
Described catalyzer is that general formula is the bivalent rare earth organic compound of [(R) CN (Ar) CHC (R) N (Ar)] LnL (S), and wherein R is the methyl or the tertiary butyl; Ar is aryl or substituted aryl; L is cyclopentadienyl, substituted cyclopentadienyl, indenyl, substituted indenyl, aryloxy or amido; Ln is samarium, europium or ytterbium; S is ether, tetrahydrofuran (THF) or glycol dimethyl ether.
Described catalyzer is that general formula is Cp " 2The bivalent rare earth organic compound of Ln (S) or alkane (virtue) oxygen base rare earth compound, wherein Cp " be cyclopentadienyl, substituted cyclopentadienyl, indenyl, substituted indenyl, alkoxyl group, aryloxy or substituted aryloxy; Ln is samarium, europium or ytterbium; S is ether, tetrahydrofuran (THF), glycol dimethyl ether or Tetramethyl Ethylene Diamine.
Described catalyzer be general formula be [Cp ' 2Ln (μ-X)] 2[M (S) n] 2The bivalent rare earth organic compound, wherein Cp ' is cyclopentadienyl, substituted cyclopentadienyl, indenyl or substituted indenyl; Ln is samarium, europium or ytterbium; X is a halogen; M is lithium, sodium or potassium; S is ether, tetrahydrofuran (THF), glycol dimethyl ether or Tetramethyl Ethylene Diamine; When S is ether or tetrahydrofuran (THF), n=4 or 6; When S is glycol dimethyl ether or Tetramethyl Ethylene Diamine, n=3.
In the technique scheme, described solvent can be that aromatic hydrocarbons is toluene, benzene, also can be tetrahydrofuran (THF) (THF), glycol dimethyl ether (DME).
In the technique scheme, catalyst consumption and polymerization temperature have very big influence to polyreaction in the described polymerization system, under comparatively high temps, when the mol ratio of monomer and catalyzer is lower than 500: 1, implode can take place.
Because the technique scheme utilization, the present invention compared with prior art has following advantage:
1. the catalytic activity of the used single-component rare earth catalyst of the present invention makes the yield of poly-(4-vinylpridine) improve greatly far above the activity of known two component rare earth catalysts.
2. because catalyzer of the present invention is a single-component catalyst, avoid using aluminum alkyls (R 3Al), make the cost of preparation poly-(4-vinylpridine) significantly reduce as promotor.
3. because catalyzer of the present invention is a single-component catalyst, the structure of catalyzer is clear, the activity center is single, structure by regulating catalyzer (promptly changing the structure that is connected on the part around the central metal) is to change activity of such catalysts, understand catalyst structure and catalytic activity relation and with the molecular weight of resulting polymers and the relation of molecular weight distribution, thereby make gained gather the molecular weight and the easier control of molecular weight distribution of (4-vinylpridine) easily.
Since among the present invention the polymerization system that adopts be a homogeneous system, thereby make the efficient of catalyzer improve a lot.
Among the present invention different rare earth compound can be in very wide polymerization temperature scope the polymerization of catalysis 4-vinylpridine.
Embodiment
The invention will be further described below in conjunction with embodiment, and [η] of listed polymkeric substance adopts Ubbelohde viscometer to record in dehydrated alcohol in the time of 25 ℃ among the embodiment, and viscosity-average molecular weight is [η]=2.5 * 10 by formula -4M η 0.68Calculate.
Embodiment one: the polymerization bottle of band stirrer adds the toluene of a certain amount of 4-vinylpridine and aequum under argon shield after deoxygenation, removing water treatment, and polymerization bottle is placed 25 ℃ oil bath, adds [(i-PrN) with syringe 2CN (SiMe 3) 2] 2Nd (μ-Me) 2Li (TMEDA).After polyreaction is carried out 15 minutes, use the methyl alcohol termination reaction, the polymkeric substance methanol extraction in vacuum-drying, calculates transformation efficiency.The results are shown in table 1.
Table 1[(i-PrN) 2CN (SiMe 3) 2] 2Nd (μ-Me) 2The consumption of Li (TMEDA)
The 4-VP polymeric is influenced
Numbering [monomer]/[catalyzer] yield (%) M η(10 -4)
1 700 99 1.53
2 1000 100 1.01
3 1500 100 3.01
4 2500 100 3.58
5 4000 80 5.33
[monomer]=20%
Embodiment two: present embodiment has illustrated that central metal is to the influence of guanidine radicals rare earth methyl compound when the catalysis 4-VP polymerization.Other condition and operation are with embodiment one.
Table 2 central metal influences at catalysis 4-VP polymeric guanidine radicals rare earth methyl compound
Numbering catalyzer [monomer]/[catalyzer] yield (%) M η(10 -4)
1 1 1000 100 1.01
2 1 1500 100 3.01
3 1 2000 97 4.42
4 1 4000 80 5.33
5 2 1000 100 7.23
6 2 1500 82 7.29
7 2 2000 54 10.49
8 MeLi 700 0 -
Catalyzer: [(i-PrN) 2CN (SiMe 3) 2] 2Ln (μ-Me) 2Li (TMEDA) (Ln=Nd (1), Yb (2))
Embodiment three: present embodiment has illustrated the influence of catalyst structure to trivalent rare earth organic compound catalysis 4-VP polymerization activity, and except that indicating especially, other condition and operation are with embodiment one.
The different trivalent rare earth organic compound of table 3 catalysis 4-VP polymeric result
[monomer]/[urge the temperature yield
The numbering catalyzer
Change agent] (℃) (%)
[(i-PrN) 2CN(SiMe 3) 2] 2Yb(μ-
1 1000 25 100
Me) 2Li(TMEDA)
2 [(iPrN) 2CN(SiMe 3) 2] 2YN(iPr) 2 500 40 79.2
[N(C 6H 3iPr 2-
3 700 15 46.2
2，6)(SiMe 3)] 2YbMe(μ-Me)Li(THF) 3
4 [(Bu tCp) 2Nd(μ-Me)] 2 200 15 100
5* [(MeCp) 2Yb(THF) 2][BPh 4] 200 90 90.2
6* [(Bu tCp) 2Yb(THF) 2][BPh 4] 200 90 54.0
* polymerization time is 2 hours
Embodiment four: present embodiment listed the bivalent rare earth organic compound [(Me) CN (2,6-Pr i 2C 6H 3)] 2CH}Yb (Ind) is catalysis 4-VP polymeric result (THF).Other condition and operation are with embodiment one.
Show 4{[(Me) and CN (2,6-Pr i 2C 6H 3)] 2CH}Yb (Ind) is catalysis 4-VP polymeric result (THF)
Numbering [monomer]/[catalyzer] monomer concentration time (min) yield (%)
1 500 10％ 10 14.8
2 500 30％ 5 68.5
3 500 30％ 15 97.1
4 4000 50％ 5 100
Embodiment five: present embodiment has been listed different bivalent rare earth compound for catalysis 4-VP polymeric results, and except that indicating especially, other condition and operation are with embodiment one.
The different bivalent rare earth compound for catalysis of table 5 4-VP polymeric result
The numbering catalyst temperature (℃) time yield (%)
{[(Me)CN(2，6-Pr i 2C 6H 3)] 2CH}Yb(Ind)(THF
1 25 5min 68.5
)
{[(Me)CN(2，6-Pr i 2C 6H 3)] 2CH}Yb(ArO)(THF
2 25 5min 15.4
)
{[(Me)CN(2，6-Pr i 2C 6H 3)] 2CH}Yb(MeCp)(TH
3 25 5min 100
F)
4 (Bu tCp) 2Sm(THF) 3 40 60h 62.0
5* {[2，2’-CH 2(OC 6H 3Bu t-6-Me-4) 2]Yb(THF) 2} 2 25 30min 93.4
6 [(Me 2PhC)Cp 4Yb 2(μ-Cl) 2][Li(DME) 3] 2 25 5min 100
[monomer]=30%, * [monomer]=50%

Claims (10)

1. 4-vinylpridine polymeric method, adopt 4-vinylpridine monomer, catalyzer and solvent composition polymerization system, under inert atmosphere, carry out polymerization, polymerization temperature is 15 ℃ to 120 ℃, it is characterized in that: described catalyzer is the rare earth organic complex that includes metal nitrogen key or metal carbon bond, described solvent is not for containing the organic solvent of reactive hydrogen, the pKa value of solvent less than with the pKa value of the part of rare-earth ion coordination.
2. 4-vinylpridine polymeric method according to claim 1 is characterized in that: the temperature range of described polyreaction is from 25 ℃ to 50 ℃.
3. 4-vinylpridine polymeric method according to claim 1 and 2 is characterized in that: described catalyzer is that general formula is [R 1NC (NR 2 2) NR 1] 2MR 3(S) trivalent rare earth organic compound, wherein R 1Be alkyl, cycloalkyl or trialkyl silyl; R 2Be alkyl or aryl; R 3Be alkyl, aryl, hydrogen or amido; M is scandium, yttrium or lanthanon; S is ether, tetrahydrofuran (THF), glycol dimethyl ether or Tetramethyl Ethylene Diamine.
4. 4-vinylpridine polymeric method according to claim 1 and 2 is characterized in that: described catalyzer is that general formula is Cp ' 2The trivalent rare earth organic compound of MR (S), wherein Cp ' is cyclopentadienyl, substituted cyclopentadienyl, indenyl or substituted indenyl; R is alkyl, aryl, hydrogen or amido; M is scandium, yttrium or lanthanon; S is ether, tetrahydrofuran (THF), glycol dimethyl ether or Tetramethyl Ethylene Diamine.
5. 4-vinylpridine polymeric method according to claim 1 and 2 is characterized in that: described catalyzer is that general formula is [(R 1) CN (Ar) CHC (R 1) N (Ar)] MR 2 nX 2-n(S) trivalent rare earth organic compound, wherein R 1Be the methyl or the tertiary butyl; Ar is aryl or substituted aryl; R 2Be alkyl, aryl or amido; M is scandium, yttrium or lanthanon; X is a halogen; N=1 or 2; S is ether, tetrahydrofuran (THF), glycol dimethyl ether or Tetramethyl Ethylene Diamine.
6. 4-vinylpridine polymeric method according to claim 1 and 2 is characterized in that: described catalyzer be general formula be [Cp ' 2M (S) n] [BPh 4] the Tricationic rare earth organic compounds, wherein Cp ' is cyclopentadienyl, substituted cyclopentadienyl, indenyl or substituted indenyl; M is scandium, yttrium or lanthanon; S is ether, tetrahydrofuran (THF) or glycol dimethyl ether; N=1 or 2.
7. 4-vinylpridine polymeric method according to claim 1 and 2 is characterized in that: described catalyzer is that general formula is the bivalent rare earth organic compound of [(R) CN (Ar) CHC (R) N (Ar)] LnL (S), and wherein R is the methyl or the tertiary butyl; Ar is aryl or substituted aryl; L is cyclopentadienyl, substituted cyclopentadienyl, indenyl, substituted indenyl, aryloxy or amido; Ln is samarium, europium or ytterbium; S is ether, tetrahydrofuran (THF) or glycol dimethyl ether.
8. 4-vinylpridine polymeric method according to claim 1 and 2 is characterized in that: described catalyzer is that general formula is Cp " 2The bivalent rare earth organic compound of Ln (S) or alkane (virtue) oxygen base rare earth compound, wherein Cp " be cyclopentadienyl, substituted cyclopentadienyl, indenyl, substituted indenyl, alkoxyl group, aryloxy or substituted aryloxy; Ln is samarium, europium or ytterbium; S is ether, tetrahydrofuran (THF), glycol dimethyl ether or Tetramethyl Ethylene Diamine.
9. 4-vinylpridine polymeric method according to claim 1 and 2 is characterized in that: described catalyzer be general formula be [Cp ' 2Ln (μ-X)] 2[M (S) n] 2The bivalent rare earth organic compound, wherein Cp ' is cyclopentadienyl, substituted cyclopentadienyl, indenyl or substituted indenyl; Ln is samarium, europium or ytterbium; X is a halogen; M is lithium, sodium or potassium; S is ether, tetrahydrofuran (THF), glycol dimethyl ether or Tetramethyl Ethylene Diamine; When S is ether or tetrahydrofuran (THF), n=4 or 6; When S is glycol dimethyl ether or Tetramethyl Ethylene Diamine, n=3.
10. 4-vinylpridine polymeric method according to claim 1 and 2 is characterized in that: described solvent can be that aromatic hydrocarbons is toluene, benzene, also can be tetrahydrofuran (THF), glycol dimethyl ether.
CN 03132168 2003-07-02 2003-07-02 Method for preparing 4-vinylpyridine using single component rare earth organic compound as catalyst Expired - Fee Related CN1208361C (en)

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