CN101987877B - Cationic polymerization method of isotactic polymer - Google Patents
Cationic polymerization method of isotactic polymer Download PDFInfo
- Publication number
- CN101987877B CN101987877B CN200910090732A CN200910090732A CN101987877B CN 101987877 B CN101987877 B CN 101987877B CN 200910090732 A CN200910090732 A CN 200910090732A CN 200910090732 A CN200910090732 A CN 200910090732A CN 101987877 B CN101987877 B CN 101987877B
- Authority
- CN
- China
- Prior art keywords
- alcohol
- polymerization
- polymerization method
- monomer
- phenol
- 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.)
- Active
Links
Images
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to a cationic polymerization method of an isotactic polymer. Polystyrene with crystallization property, which as high conversion rate, high molecular weight (weight average molecular weight Mw=1*105-3.5*105) and high isotacticity (the highest upper limit of the melting temperature can each 230 DEG C), and derivatives thereof can be obtained by carrying out styrene cation isotactic polymerization in a monomer solution comprising a monomer of styrene and the derivatives thereof and a solvent by adopting an initiation system comprising a cation source initiator, Lewis acid as well as a phenols, ethers, amine, amide or pyridine accessory ingredient. The isotacticity of polymerization products can be adjusted in a certain range, and meanwhile, the favorable crystallization property of the polymerization product can endow materials with higher use temperature and good physical and mechanical properties.
Description
Technical field
The present invention relates to a kind of cationic polymerization process of three-dimensional polymer, be specifically related to vinylbenzene and verivate thereof are carried out the upright structure polymerization of positively charged ion, preparation HMW, stereoregulated PS and verivate thereof.
Background technology
The crystal property of PS and its stereoregular degree have substantial connection, and isotactic or syndiotactic polystyrene have high heat distortion temperature, high melting temperature, high-crystallinity, high tensile, high-modulus and excellent electric insulation performance and corrosion resistance nature.Isotactic or syndiotactic polystyrene mainly are to prepare through coordination (orientation) polymerization and the upright structure polymerization method of negatively charged ion at present.In polycoordination, adopt titanium system, vanadium system, nickel system or rare-earth system catalyzer to come synthesing isotactic polystyrene, adopting titanium is that metallocene catalyst comes synthesis of syndiotactic polystyrene; In anionoid polymerization, mainly adopt the PS of the synthetic certain degree of isotacticity of BuOLi/BuLi initiator system.
Adopt the synthetic tacticity polymer of cationic polymerization process that report is also arranged.Document [Ouchi M, SueokaM, Kamigaito M, Sawamoto M.J Polym Sci, Part A:Polym Chem, 2001,39 (7): 1060-1066; 1067-1074] propose, with two phenoxy titanium dichloride [TiCl
2(OAr)
2] cause vinyl ether monomers altogether and carry out cationoid polymerisation, synthesize the polyvingl ether of certain degree of isotacticity.Document [Kunitake T, Tsugawa S.Macromolecules, 1975,8 (6): 709; Kawamura T, Uryu T, Seki T, Matsuzaki K.Polym J, 1983,15 (2): 107-110] the middle proposition, for α-Jia Jibenyixidanti, at AlCl
3, FeCl
3, GaCl
3, SnBr
4, SnCl
4, SnBrCl
3, SnClBr
3, ZrCl
4, InCl
3, InBr
3, TiCl
3, TaCl
3, NbCl
5, BCl
3, BF
3Deng can carrying out cationoid polymerisation under the Louis acid catalysis, but speed of reaction is extremely slow, polyreaction hundreds of hour, and monomer conversion is less than 50% also, and molecular weight is low, and the syndiotactic regularity of uncontrollable poly alpha methylstyrene product.
Though there is bibliographical information to adopt BCl
3, SnCl
4Or TiCl
4Can realize the living cationic polymerization of vinylbenzene and verivate (like vinylbenzene, p-methylstyrene) thereof for coinitiator; But all obtain random polystyrene and verivate thereof [referring to Faust R; Kennedy J P.Polym Bull, 1988,19 (1): 21; Nagy A, Majoros I, Kennedy J P.J Polym Sci, Part A:Polym Chem, 1997,35 (16): 3341-3347; Kostjuk S V, Yu A, Dubovik A Y, Vasilenko I V, Frolov A N, KaputskyF N.Eur Polym J, 2007,43,968-979].And realize the upright structure polymerization of positively charged ion for styrene monomer and verivate thereof; Be one of goal in research of this area always, also obtained some progress in recent years, document [Vijayaraghavan R; MacFarlane D R.Macromolecules; 2007,40:6515] propose to cause vinylbenzene altogether and in ionic liquid [N-butyl-N-crassitude] [two trifluoromethane sulfonic acid amine], carry out cationoid polymerisation with dioxalic acid boric acid (HBOB), obtain the part syndiotactic polystyrene; And because this initiator system is highly stable and to the particular requirement of polymerization temperature; Make catalyst levels big (catalyzer/monomer mole ratio＞0.03), molecular weight of product is very low, weight-average molecular weight M
w＜3000.Document [Bueno C, Cabral V F, Cardozo-Filho L, Dias M L, Antunes O A C; J of supercritical Fluids.2009,48:183-187] report with AlCl
3Cause vinylbenzene altogether and in ionic liquid [1-normal-butyl-3-Methylimidazole] [phosphofluoric acid] or methylene dichloride, carry out cationoid polymerisation; Under monomer transforms near 100%; Mainly obtain the random polystyrene product, wherein only contain an isotactic sequence and a rule sequential structure of very small amount, be difficult to improve tacticity; And polymer molecular weight is also lower, weight-average molecular weight M
w＜25000, be difficult to use as material.It is thus clear that above-mentioned two pieces of document described vinylbenzene cationoid polymerisation systems and polymerization method; The tacticity of the polymkeric substance that obtains is not high; Molecular weight is lower again; Therefore the crystal property that does not all present the PS product, and polymerisate only reaches under higher degree and the sufficiently high situation of molecular weight in its taxis and just can present crystal property.In addition, adopt the ionic liquid solution cost high, be not easy to make.Therefore, can't reach the employing cationic polymerization process in the existing public technology and prepare PS HMW, high tacticity, that have crystal property.
Summary of the invention
The present invention provides a kind of cationic polymerization process of three-dimensional polymer; Can in OOS (nonionic liquid), carry out the upright structure polymerization of positively charged ion of vinylbenzene and derivatives monomer thereof; The PS and the verivate thereof that obtain HMW, high tacticity, have the well-crystallized performance; And transformation efficiency is high, and tacticity can be regulated, and polymerization time is short, cost is low.
Main technical schemes of the present invention: in monomer solution by monomer and solvent composition; Initiator system with cationic source initiator, Lewis acid and organic coordination compound formation; Trigger monomer carries out cationoid polymerisation under 0 ℃～-100 ℃ polymerization temperatures, and Lewis acid and monomeric mol ratio are 0.5 * 10
-3～9.0 * 10
-3, initiator and lewis acidic mol ratio are 0.1～2.0, organic coordination compound and lewis acidic mol ratio are 0.1～1.2, wherein:
Described monomer is vinylbenzene and verivate thereof;
Described solvent is the mixed solvent of stable hydrocarbon and halohydrocarbon, and the proportioning of stable hydrocarbon and halohydrocarbon was regulated in the scope at 1: 9～9: 1;
Described Lewis acid structural formula: ZL
n, Z is Al, B or Sn in the formula, L is halogen F, Cl or Br, n=3 or 4;
Described organic coordination compound is one or more the combination in ether, amine, acid amides, alcohol, phenol or the pyridine compounds and their.
Cationic source initiator of the present invention is one or more combinations in water, HCl, carboxylic acid or the tertiary alkyl compound, and wherein the tertiary alkyl structural formula of compound is following:
R in the formula
1, R
2And R
3Be C
1～C
10Alkyl, aryl or aralkyl, X is halogen, ester group, ether or hydroxyl, i is a positive integer, R
1, R
2And R
3Can be identical or different.Preferred tertiary Butyryl Chloride, 2-chloro-2,4,4-trimethylpentane, cumyl chlorine, to dicumyl chlorine, tert.-butyl acetate, acetate cumyl ester, oxalic acid to dicumyl ester, water or HCl as initiator.
Initiator, Lewis acid and organic coordination compound can be pre-configured in the initiator system of the present invention, but also original position generates.The tacticity of polymerisate can be regulated in certain limit through the kind and the proportioning that change polymerization temperature, solvent burden ratio and initiator, Lewis acid and organic coordination compound.
Monomer solution of the present invention, be by the monomer of vinylbenzene and verivate thereof and solvent by the usual method configuration, monomer concentration is confirmed preferred 0.1mol/L～2.0mol/L according to polymerization needs usually.
Described vinylbenzene and verivate optimization styrene thereof, alpha-methyl styrene, p-vinyl toluene, p-ethyl styrene, p-propylstyrene are or/and the p-butylstyrene.
Described saturated hydrocarbon solvent is one or more in pentane, hexane, heptane, octane, hexanaphthene or the methylcyclohexane; Halohydrocarbon is one or more in methyl chloride, methylene dichloride, trichloromethane, ethylene dichloride, trichloroethane, methylene fluoride, C2H4F2 C2H4F2, trifluoromethane, the HFC-143a.
The proportioning of described stable hydrocarbon and halohydrocarbon is regulated in proper range, and in order to regulate the polymerization tacticity, optimum ratio is 3: 7～8: 2.
Preferred-20 ℃～-90 ℃ of polymerization temperature scope of the present invention is with initiator system and the collaborative adjusting of monomer solution, the upright structure extent of polymerization of control.
Coinitiator according to the invention is preferably AlCl
3, BF
3Or SnCl
4, act on the monomeric upright structure extent of polymerization of adjusting simultaneously with described organic coordination compound.
In organic Synergist S-421 95 according to the invention, the ether compound general formula is R
4-O-R
5, R wherein
4And R
5Be alkyl, aryl, aralkyl, substituted alkyl, substituted aryl or the substituted aralkyl of 1～10 carbon atom, R
4And R
5Can be identical or different, the substituting group of straight or branched.
Ether compound is one or more combinations in methyl ether, ether, butyl ether, amyl ether, hexyl ether, 2-methyl butyl ether, 3-methyl butyl ether, 1-ethyl propyl ether, methyl ethyl ether, methyl-propyl ether, methyl butyl ether, propyl group butyl ether, propyl group amyl ether, butyl amyl ether, methyl phenyl ether, ethylphenyl ether, propyl group phenyl ether, n-butyl phenyl ether, 2-methyl phenyl ether, 3-methyl phenyl ether, 1-ethylphenyl ether, butyl phenylate or amyl group phenyl ether preferably, and most preferably ether, butyl ether, methyl-phenoxide are or/and phenyl ethyl ether.
In organic Synergist S-421 95 according to the invention, the aminated compounds general formula is N (R
6R
7R
8)
3, R wherein
6, R
7And R
8Be alkyl, aryl, aralkyl, substituted alkyl, substituted aryl, substituted aralkyl or the acyl group of the straight or branched of H (hydrogen) or 1～10 carbon atom, R
6, R
7And R
8It can be substituting group identical or different, straight or branched.
Aminated compounds is preferably from amylamine, dimethyl propylamine, dimethyl butylamine, hexylamine, octylame, aniline, benzene methanamine, monomethylaniline, phenylethylamine, amphetamine, PHENTERMINE, pentanoic, triphenylamine, methyl substituted aniline, methyl substituted pentanoic, methyl substituted triphenylamine, N; Dinethylformamide, N; N-N,N-DIMETHYLACETAMIDE, N; One or more combinations in N-DEF, N-phenyl formamide, the phenyl acetanilide,Phenacetylaniline, most preferably aniline, pentanoic, triphenylamine, N-phenyl formamide are or/and phenyl acetanilide,Phenacetylaniline.
In organic Synergist S-421 95 according to the invention; Alcohol compound is more than one combinations of a kind of mistake in methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, the trimethyl carbinol, Pentyl alcohol, primary isoamyl alcohol, tertiary amyl alcohol, n-hexyl alcohol, isohexyl alcohol, uncle's hexanol, n-Heptyl alcohol, iso-heptanol, uncle's enanthol, n-Octanol, isooctyl alcohol, uncle's octanol, phenylcarbinol, phenylethyl alcohol, phenylpropyl alcohol, benzene butanols preferably, and most preferably methyl alcohol, ethanol, n-propyl alcohol are or/and propyl carbinol.
Phenolic cpd is selected from one or more combinations in phenol, methylphenol, xylenol, ethylphenol, diethyl phenol, propylphenol, dipropyl phenol, butylphenol, dibutyl phenol, octyl phenol or the dioctyl phenol in organic Synergist S-421 95 according to the invention, and preferred ortho-cresol, meta-cresol are or/and p-cresol.
In organic Synergist S-421 95 according to the invention; Pyridine compounds and their is selected from pyridine, picoline, lutidine, vinyl pyridine, 3-methyl-2-phenylpyridine, 2,6-lutidine, 2-methyl-6-ethylpyridine, 2,6-parvoline, 2-methyl-6-tert butyl yl pyridines or 2; One or more combinations in the 6-di-tert-butyl pyridine; Preferred 2, the 6-lutidine is or/and 2, the 6-di-tert-butyl pyridine.
Polymerization reaction time of the present invention is 1～60min, preferred 1～40min, and through in system, introducing the material that makes catalyst deactivation, for example water, alcohol, ether, acetonitrile, amine or inorganic base aqueous solution were so that the polymerization termination after polymerization was accomplished.After stopping polymerization, remove unreacted monomer and solvent,, use vacuum drying oven dry at last with ethanol or water repetitive scrubbing polymerisate.
The molecular weight of polymerisate of the present invention and MWD are with the test of GPC method, and as standard specimen, the fusing point of product is measured with DSC with standard P S, and crystal property is used polarized light microscope observing, and the stereoregular structure of product is used
13C-NMR characterizes (deuterium is made solvent for orthodichlorobenzene, mark in TMS does).Because the stereoregular degree of product is high more, melt temperature is high more.For example: for PS, when degree of isotacticity near 100% the time, melt temperature is near 240 ℃; The softening temperature of random polystyrene is generally 60 ℃～90 ℃.Therefore can embody stereoregular degree of the present invention with melt temperature.
Effect of the present invention: the initiator system that the present invention adopts suitable cationic source initiator, Lewis acid and corresponding Synergist S-421 95 to form; In the styrene monomer solution (nonionic liquid) of common organic mixed solvent configuration, can carry out the upright structure polymerization of vinylbenzene or derivatives thereof positively charged ion; Polymerization time is short, transformation efficiency is high, monomer even can almost completely transform with interior at 1min; Obtain HMW (weight-average molecular weight M
w1 * 10
5～3.5 * 10
5), the PS and the verivate thereof of high taxis, the high melting temperature upper limit can reach near 230 ℃ (generally when degree of isotacticity near 100% the time, melt temperature is near 240 ℃); And the present invention is through changing the kind and the proportioning of polymerization temperature, solvent burden ratio and initiator, Lewis acid and organic coordination compound, the tacticity that can regulate polymerisate in certain limit; Because molecular weight and isotactic sequential structure content are high, polymerisate of the present invention has good crystal property (seeing accompanying drawing 1), and crystallization phases is that the several approximately μ m of diameter are big or small, and then gives material and possess higher use temperature and excellent physical and mechanical properties; And initiator system consumption of the present invention is low, and reactive behavior is high, and raw material is easy to get, and cost is low.
Description of drawings
Fig. 1 is the POM photo of polymerisate.
Embodiment
Be used to explain that through following some preferable representative example of the present invention can better understand the present invention; Although provided these embodiment; But also should comprise: do not departing under the scope of the invention condition, disclosed method is carried out the obvious various changes of those skilled in the art.
[embodiment 1] is under the high pure nitrogen protection; (cinnamic concentration is 0.68mol/L to the monomer solution of 20ml vinylbenzene/hexanes/ch; Hexane and methylene dichloride proportioning are 4: 6) the middle initiator system of forming by 0.016mmol water, 0.08mmol aluminum chloride and 0.04mmol triphenylamine that adds, at-80 ℃ of following polyreaction 30min, add ethanol then and stop polymerization; Deviate from solvent and unreacted monomer through alkali cleaning, washing, polymkeric substance places 40 ℃ of following dry 8h of vacuum drying oven.Monomer conversion is 99%, and the polymerisate weight-average molecular weight is 2.6 * 10
5, fusion range is 156 ℃～205 ℃.
[embodiment 2] are under the high pure nitrogen protection; (concentration of styrene is 0.68mol/L to the monomer solution of 20ml vinylbenzene/hexanes/ch; Hexane and methylene dichloride proportioning are 8: 2) the middle initiator system of forming by 0.016mmol water, 0.08mmol aluminum chloride and 0.04mmol triphenylamine that adds, at-80 ℃ of following polyreaction 30min.Termination and post-treating method are with embodiment 1.Monomer conversion is 32%, and the polymerisate weight-average molecular weight is 1.9 * 10
5, fusion range is 163 ℃～211 ℃.
[embodiment 3] are under the high pure nitrogen protection; (concentration of styrene is 0.68mol/L to the monomer solution of 20ml vinylbenzene/hexanes/ch; Hexane and methylene dichloride proportioning are 6: 4) the middle initiator system of forming by 0.024mmol water, the initiation of 0.08mmol aluminum chloride and 0.04mmol triphenylamine that adds, at-40 ℃ of following polyreaction 30min.Termination and post-treating method are with embodiment 1.Monomer conversion is 63%, and the polymerisate weight-average molecular weight is 1.7 * 10
5, fusion range is 196 ℃～228 ℃.
[embodiment 4] are under the high pure nitrogen protection; (concentration of styrene is 0.68mol/L to the monomer solution of 20ml vinylbenzene/hexanes/ch; Hexane and methylene dichloride proportioning are 6: 4) the middle initiator system of forming by 0.022mmol water, 0.029mmol aluminum chloride and 0.015mmol triphenylamine that adds, at-80 ℃ of following polyreaction 30min.Polymerization termination and post-treating method are with embodiment 1.Monomer conversion is 60%, and the polymerisate weight-average molecular weight is 2.6 * 10
5, fusion range is 139 ℃～188 ℃.
[embodiment 5] are under the high pure nitrogen protection; (concentration of styrene is 0.68mol/L to the monomer solution of 20ml vinylbenzene/hexanes/ch; Hexane and methylene dichloride proportioning are 6: 4) the middle initiator system of dicumyl chlorine, 0.08mmol aluminum chloride and 0.064mmol ether being formed by 0.01mmol water, 0.08mmol that adds, at-80 ℃ of following polyreaction 30min.Polymerization termination and post-treating method are with embodiment 1.Monomer conversion is 99%, and the polymerisate fusion range is 175 ℃～210 ℃.
[embodiment 6] are under the high pure nitrogen protection; (concentration of styrene is 0.68mol/L to the monomer solution of 20ml vinylbenzene/hexanes/ch; Hexane and methylene dichloride proportioning are 6: 4) the middle initiator system of dicumyl chlorine, 0.08mmol aluminum chloride and 0.016mmol ortho-cresol being formed by 0.03mmol water, 0.08mmol that adds, at-80 ℃ of following polyreaction 30min.Polymerization termination and post-treating method are with embodiment 1.Monomer conversion is 91%, and the polymerisate fusion range is 153 ℃～203 ℃.
[embodiment 7] are under the high pure nitrogen protection; (concentration of styrene is 0.68mol/L to the monomer solution of 20ml vinylbenzene/hexanes/ch; Hexane and methylene dichloride proportioning are 6: 4) the middle initiator system of dicumyl chlorine, 0.08mmol aluminum chloride and 0.048mmol Acetanilide being formed by 0.020mmol water, 0.08mmol that adds, at-80 ℃ of following polyreaction 30min.Polymerization termination and post-treating method are with embodiment 1.Monomer conversion is 100%, and the polymerisate fusion range is 129 ℃～198 ℃.
[embodiment 8] are under the high pure nitrogen protection; (concentration of styrene is 0.68mol/L to the monomer solution of 20ml vinylbenzene/hexanes/ch; Hexane and methylene dichloride proportioning are 6: 4) the middle adding by 0.030mmol water, 0.08mmol to dicumyl chlorine, 0.08mmol aluminum chloride and 0.03mmol 2; The initiator system that the 6-di-tert-butyl pyridine is formed is at-80 ℃ of following polyreaction 30min.Polymerization termination and post-treating method are with embodiment 1.Monomer conversion is 100%, and the polymerisate weight-average molecular weight is 2.0 * 10
5, fusion range is 153 ℃～196 ℃.
[embodiment 9] are under the high pure nitrogen protection; (concentration of styrene is 0.68mol/L to the monomer solution of 20ml vinylbenzene/hexanes/ch; Hexane and methylene dichloride proportioning are 6: 4) the middle adding by 0.035mmol water, 0.08mmol to dicumyl chlorine, 0.08mmol aluminum chloride, 0.008mmol triphenylamine and 0.032mmol2; The initiator system that the 6-di-tert-butyl pyridine is formed is at-80 ℃ of following polyreaction 30min.Polymerization termination and post-treating method are with embodiment 1.Monomer conversion is 84%, and the polymerisate weight-average molecular weight is 1.1 * 10
5, fusion range is 147 ℃～195 ℃.Fig. 1 is the POM photo of present embodiment polymerisate.
[embodiment 10] are under the high pure nitrogen protection; (concentration of styrene is 0.68mol/L to the monomer solution of 20ml vinylbenzene/hexanes/ch; Hexane and methylene dichloride proportioning are 6: 4) the middle initiator system of forming by 0.028mmol water, 0.084mmol boron trifluoride and 0.008mmol methyl alcohol that adds, at-80 ℃ of following polyreaction 30min.Polymerization termination and post-treating method are with embodiment 1.The polymerisate fusion range is 101 ℃～112 ℃.
[embodiment 11] are under the high pure nitrogen protection; (p-vinyl toluene concentration is 0.2mol/L to the monomer solution of 20ml p-vinyl toluene/hexanes/ch; Hexane and methylene dichloride proportioning are 6: 4) the middle initiator system of dicumyl chlorine, 0.08mmol aluminum chloride and 0.032mmol triphenylamine being formed by 0.017mmol water, 0.08mmol that adds, at-80 ℃ of following polyreaction 30min.Polymerization termination and post-treating method are with embodiment 1.Monomer conversion is 98%, and the polymerisate fusion range is 130 ℃～140 ℃.
[embodiment 12] are under the high pure nitrogen protection; (concentration of styrene is 1.0mol/L to the monomer solution of 20ml vinylbenzene/hexanes/ch; Hexane and methylene dichloride proportioning are 6: 4) the middle initiator system of dicumyl chlorine, 0.08mmol aluminum chloride and 0.032mmol triphenylamine being formed by 0.017mmol water, 0.08mmol that adds, at-80 ℃ of following polyreaction 30min.Polymerization termination and post-treating method are with embodiment 1.Monomer conversion is 97%, and the polymerisate fusion range is 131 ℃～140 ℃.
Claims (10)
1. the cationic polymerization process of a three-dimensional polymer; It is characterized in that: in the monomer solution of monomer and solvent composition; Initiator system with cationic source initiator, Lewis acid and organic coordination compound formation; Trigger monomer carries out cationoid polymerisation under 0 ℃～-100 ℃ polymerization temperatures, and obtaining weight-average molecular weight is 1 * 10
5～3.5 * 10
5High tacticity polymer, wherein: Lewis acid and monomeric mol ratio are 0.5 * 10
-3～9.0 * 10
-3, initiator and lewis acidic mol ratio are 0.1～2.0, and organic coordination compound and lewis acidic mol ratio are 0.1～1.2, and described monomer is vinylbenzene and verivate thereof; Described solvent is the mixed solvent of stable hydrocarbon and halohydrocarbon, and the proportioning of stable hydrocarbon and halohydrocarbon was regulated in the scope at 1: 9～9: 1; Described Lewis acid structural formula is: ZL
n, Z is Al, B or Sn in the formula, L is halogen F, Cl or Br, n=3 or 4; Described organic coordination compound is more than one the combination in ether, amine, acid amides, alcohol, phenol or the pyridine compounds and their.
2. according to the polymerization method of claim 1, it is characterized in that described cationic source initiator is more than one combinations in water, HCl, carboxylic acid or the tertiary alkyl compound, wherein the tertiary alkyl structural formula of compound is following:
R in the formula
1, R
2And R
3Be C
1～C
10Alkyl, aryl or aralkyl, X is halogen, ester group, ether or hydroxyl, i is a positive integer.
3. according to the polymerization method of claim 1, it is characterized in that described Lewis acid is AlCl
3, BF
3Or SnCl
4
4. according to the polymerization method of claim 1, it is characterized in that described ether compound general formula is R
4-O-R
5, R wherein
4And R
5Be alkyl, aryl, substituted alkyl or the substituted aryl of 1～10 carbon atom.
5. according to the polymerization method of claim 1, it is characterized in that described aminated compounds general formula is N (R
6R
7R
8)
3, R wherein
6, R
7And R
8Alkyl, aryl, substituted alkyl, substituted aryl or substituted acyl group for H or 1～10 carbon atom.
6. according to the polymerization method of claim 1; It is characterized in that described alcohol compound is selected from more than one combinations in methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, the trimethyl carbinol, Pentyl alcohol, primary isoamyl alcohol, tertiary amyl alcohol, n-hexyl alcohol, isohexyl alcohol, uncle's hexanol, n-Heptyl alcohol, iso-heptanol, uncle's enanthol, n-Octanol, isooctyl alcohol, uncle's octanol, phenylcarbinol, phenylethyl alcohol, phenylpropyl alcohol, the benzene butanols; Described phenolic cpd is selected from more than one combinations in phenol, methylphenol, xylenol, ethylphenol, diethyl phenol, propylphenol, dipropyl phenol, butylphenol, dibutyl phenol, octyl phenol or the dioctyl phenol.
7. according to the polymerization method of claim 1; It is characterized in that; Described pyridine compounds and their is selected from pyridine, picoline, lutidine, vinyl pyridine, 3-methyl-2-phenylpyridine, 2; 6-lutidine, 2-methyl-6-ethylpyridine, 2,6-parvoline, 2-methyl-6-tert butyl-pyridinium or 2, more than one combinations in the 6-di-tert-butyl pyridine.
8. according to the polymerization method of claim 1, it is characterized in that described stable hydrocarbon is more than one in pentane, hexane, heptane, octane, hexanaphthene or the methylcyclohexane; Halohydrocarbon is more than one in monochloro methane, methylene dichloride, trichloromethane, ethylene dichloride, trichloroethane, methylene fluoride, C2H4F2 C2H4F2, trifluoromethane, the HFC-143a; The proportioning of stable hydrocarbon and halohydrocarbon was at 3: 7～8: 2.
9. according to the polymerization method of claim 1, it is characterized in that polymerization temperature is at-20 ℃～-90 ℃.
10. according to the polymerization method of claim 1, it is characterized in that described vinylbenzene and verivate thereof comprise that vinylbenzene, alpha-methyl styrene, p-vinyl toluene, p-ethyl styrene, p-propylstyrene are or/and the p-butylstyrene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910090732A CN101987877B (en) | 2009-08-07 | 2009-08-07 | Cationic polymerization method of isotactic polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910090732A CN101987877B (en) | 2009-08-07 | 2009-08-07 | Cationic polymerization method of isotactic polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101987877A CN101987877A (en) | 2011-03-23 |
| CN101987877B true CN101987877B (en) | 2012-10-17 |
Family
ID=43744684
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910090732A Active CN101987877B (en) | 2009-08-07 | 2009-08-07 | Cationic polymerization method of isotactic polymer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101987877B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103897087B (en) * | 2012-12-26 | 2016-06-29 | 彤程化学（中国）有限公司 | The cationic polymerization process of α-methyl styrene/styrol copolymer |
| CN105440186B (en) * | 2014-08-14 | 2018-04-10 | 中国科学院长春应用化学研究所 | A kind of functionalization height is entirely the same as polystyrene and preparation method thereof |
| CN106146244B (en) * | 2015-03-23 | 2019-02-26 | 彤程化学（中国）有限公司 | The preparation method of tire tread aromatic hydrocarbon resin |
| CN112979851B (en) * | 2021-02-22 | 2021-12-10 | 扬州市职业大学(扬州市广播电视大学) | Catalytic system for synthesizing polyacrylamide and synthesis method of polyacrylamide |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1070920A (en) * | 1992-11-10 | 1993-04-14 | 北京化工学院 | Olefin polymerization catalyst system |
| CN101225131A (en) * | 2007-12-26 | 2008-07-23 | 江南大学 | Cationic photoinitiator polystyrene or copolymer iodonium salt thereof and preparation method thereof |
-
2009
- 2009-08-07 CN CN200910090732A patent/CN101987877B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1070920A (en) * | 1992-11-10 | 1993-04-14 | 北京化工学院 | Olefin polymerization catalyst system |
| CN101225131A (en) * | 2007-12-26 | 2008-07-23 | 江南大学 | Cationic photoinitiator polystyrene or copolymer iodonium salt thereof and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| JP平9-132614A 1997.05.20 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101987877A (en) | 2011-03-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | Well‐defined polyolefin/poly (ε‐caprolactone) diblock copolymers: New synthetic strategy and application | |
| CN101987877B (en) | Cationic polymerization method of isotactic polymer | |
| WO2013039152A1 (en) | Polyolefin having terminal double bond, and method for producing same | |
| Wang et al. | Synthesis of AB (BA), ABA and BAB block copolymers of tert‐butyl methacrylate (A) and ethylene oxide (B) | |
| CN101987876B (en) | Controllable cation polymerizing method of vinyl monomers | |
| Xiong et al. | Chemically recyclable copolyesters from bio-renewable monomers: controlled synthesis and composition-dependent applicable properties | |
| Liu et al. | Reversible Addition Fragmentation chain Transfer (RAFT) polymerization with a polymeric RAFT agent containing multiple trithiocarbonate groups | |
| US20170298168A1 (en) | Glucose-based block copolymers | |
| Lu et al. | Morphology and phase behavior of blends of a styrenic block copolymer ionomer and polycaprolactone | |
| Gao et al. | ABA type liquid crystalline triblock copolymers by combination of living cationic polymerizaition and ATRP: synthesis and self-assembly | |
| Bergius et al. | Synthesis and characterisation of end-functionalised poly (N-vinylpyrrolidone) additives by reversible addition–fragmentation transfer polymerisation | |
| Zhang et al. | Synthesis and properties of a new high-temperature liquid crystalline thermoplastic elastomer based on mesogen-jacketed liquid crystalline polymer | |
| Yu et al. | Difunctional initiator based on 1, 3‐diisopropenylbenzene. IV. Synthesis and modification of poly (alkyl methacrylate‐b‐styrene‐b‐butadiene‐b‐styrene‐b‐alkyl methacrylate (MSBSM)) thermoplastic elastomers | |
| CN1982350A (en) | Production of soft-segment total saturated block copolymer | |
| Liu et al. | Synthesis and characterization of graft copolymers poly (ethylene oxide)-g-[poly (ethylene oxide)-b-poly (ε-caprolactone)] with double crystallizable side chains | |
| Wu et al. | Synthesis of linear isotactic-rich poly (p-methylstyrene) via cationic polymerization coinitiated with AlCl3 | |
| Yang et al. | The synthesis of poly (3, 4‐dihydroxystyrene) and poly [(sodium 4‐styrenesulfonate)‐co‐(3, 4‐dihydroxystyrene)] | |
| CN109553714B (en) | Preparation method of oligomer for improving wet skid resistance of rubber | |
| EP0984991B1 (en) | Long chain branched syndiotactic vinyl aromatic polymers | |
| JP2002220427A (en) | Vinyl block copolymer | |
| Ishizu et al. | Synthesis and morphology of BAB type poly (styrene‐b‐2‐methyl‐2‐oxazoline) block copolymers | |
| Weidner et al. | Synthesis and characterization of 3‐aryl‐2‐(polystyryl) cyclopropenones via cyclopropenium ion substitution on polystyrene | |
| Ye et al. | Synthesis and application as polymer electrolyte of hyperbranched copolyethers derived from cationic ring-opening polymerization of 3-{2-[2-(2-methoxyethoxy) ethoxy] ethoxy} methyl-and 3-hydroxymethyl-3′-methyloxetane | |
| Dimitrov et al. | Synthesis and ATRP of novel fluorinated aromatic monomer with pendant sulfonate group | |
| CN118271496A (en) | Isoalkenyl terpolymer containing oxygen polar groups and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |