CN1163278A - Controlled polymerizing and copolymerzing method for (methyl) propenyl and vinyl monomer and its products - Google Patents

Abstract

The process for the controlled radical (co)polymerization of (meth)acrylic and/or vinyl monomers is characterized in that the bulk, solution, emulsion or suspension polymerization or copolymerization is carried out, at a temperature at which can fall to 0 DEG C, of at least one of the said monomers in the presence of an initiating system comprising a radical-generating compound and at least one catalyst composed of a metal complex containing a ligand of the type[4-R3-2,6-(CH2NR1R2)2C6H2]-, in which: R1 and R2, which are identical or different, represent a branched or unbranched C1-C4 alkyl group or a phenyl group or alternatively R1 and R2 form, with the nitrogen atom to which they are connected, a cyclic amine or alternatively the two R2 groups, taken together, form a polymethylene bridge and R3 represents a hydrogen atom, an alkyl or benzyl group or an electron-donating or electron-withdrawing functional group.

Description

The in check polymerization of (methyl) propenyl and vinyl monomer or process for copolymerization and products thereof

The present invention relates to (methyl) propenyl and vinyl (for example, the vinyl aromatic (co) perfume base) monomeric controlled radical polymerization or process for copolymerization, and the polymkeric substance or the multipolymer that get therefrom.

Because available various polymerisable monomer is easy and simple to handle, and adopts different building-up process (emulsion-type, suspension type, this build, solution-type), the radical polymerization method has constituted one of present industrial the most frequently used polymerization process.But, in traditional radical polymerization method, be difficult to the size of controlling polymers chain link and the distribution of molecular weight.The polymkeric substance that makes thus has very long chain link and special little piece group (polymolecularity is higher), thereby causes generating the uppity material of its characteristic.In addition, monomeric continuous adding also can cause the generation of the mixture of homopolymer.

The catalytic polymerization technique of negatively charged ion and positively charged ion can be controlled this process definitely, yet the needed reaction conditions of this polymerization process always can be implemented on technical scale.In addition, some monomer can not carry out polyreaction with this technology.

Although the example of the monomeric controlled radical polymerization of (methyl) propenyl and vinyl aromatic (co) perfume base is arranged at present, wherein uses coordination compound RuCl especially ₂(PPh ₃) ₃(P=phosphorus, Ph=phenyl) and CuCl/2,2 '-pyridine, these catalyst systems are in the temperature more than 100 ℃, and do not have activator to participate under the condition of reaction polyreaction not being showed activity.But, when improving temperature of reaction, will produce heat excitation automatically, thereby cause weakening especially polyreaction control.

In addition, as everybody knows, for letex polymerization or suspension polymerization effect, major part is carried out in water-bearing media.This just need make polyreaction carry out being lower than under 100 ℃ of temperature condition, to guarantee the stable of these emulsions or suspension.

Certainly, above-mentioned temperature of reaction is can reduce, and still, therefore needs lewis acidic existence, and this will cause reacting in anhydrous medium.

Under the normal condition of polyreaction, catalyzer can not degraded by water.For the reaction of controlled polymerization better, therefore, preferably in homogeneous medium, react (that is to say, employing can be in organic medium dissolved catalyzer).

Therefore the objective of the invention is to solve the disadvantage of above-mentioned existence, and enforcement radical polymerization, this reaction can be controlled as ionic polymerization reaction under industrial acceptable synthesis condition and polycoordination reaction, therefore, it can synthesize homopolymer and irregular or its length is to give fixed segmented copolymer.

Generally speaking, the polymerization or the copolymerization method that the purpose of this invention is to provide (methyl) propenyl and/or vinyl monomer, growth that wherein can the controlling polymers chain link, this polymerization process carries out with this build, solution-type, emulsion-type or suspension-type, and this reaction just finishes after the monomer of whole participation reactions exhausts.

For this reason, be necessary to avoid or limit at least termination reaction, and must promote the rapid initiation of polymerization or co-polymerization because of chemosynthesis.

One of main purpose of the present invention provides, do not need traditional technology is carried out key technological transformation, can guarantee the control of molecular weight again with the condition preparation of technical scale and less expensive, stereoselectivity, the polymkeric substance of commercial requirements such as regioselectivity and distributivity thereof and the catalyzer of co-polymer and initiator.

For this reason, according to the controlled radical polymerization or the process for copolymerization that the present invention proposes (methyl) propenyl and/or vinyl monomer, wherein, can be under temperature be reduced to 0 ℃ condition, a kind of propellant and exciting of forming of at least a catalyzer under system participates in by at least a radical, at least one (methyl) propenyl and/or vinyl monomer are carried out the mass polymerization effect, solution polymerization effect, emulsion polymerization or suspension polymerization effect, this catalyzer is made up of the metal complex that contains following ligand:

[4-R ³-2,6-(CH ₂NR ¹R ²) ₂C ₆H ₂] ^-(I) R wherein ¹And R ²Being identical or inequality, can be the C of a straight or branched ₁-C ₄Alkyl or phenyl, perhaps a R ¹And R ²Form a cyclammonium with that nitrogen-atoms that they are connected, perhaps two R randomly ²Form a polymethylene bridge together, and R ³Represent hydrogen atom, alkyl or a benzyl or power supply or electrophilic functional group.

Advantageously, the ligand of the catalyzer of this polyreaction has chemical general formula one of as follows: Wherein, R ¹, R ²With R ³As above-mentioned qualification, in chemical formula (III), two amination groups of this ligand are connected with a chain link of being made up of the individual MU (methylene unit) of m (7-10).

According to a preferable embodiment of the present invention, the catalyzer of above-mentioned polymkeric substance has the following chemical general formula of one of them:

Wherein, R ¹, R ²And R ³As above-mentioned qualification;

M represents the metal of group VIII in the transition metal, particularly element classification periodictable,

X represents monatomic or polyatomic anion-radicals,

N represents 0.1 or 2 integer, and its value depends on the state of oxidation of metal M,

L is the stablizer ligand of Lewis base type, as a pyridine, phosphine or phosphorous acid ester group.

In chemical formula (I)-(V), as previously mentioned, R ¹With R ²Each represents methyl, ethyl, sec.-propyl, tertiary butyl and a phenyl or R ¹And R ²Form a pyrrolidyl or proline(Pro) ring with that nitrogen-atoms that their link to each other, perhaps two R randomly ²Constitute a polymethylene bridge together.

R ³Represent hydrogen atom or chlorine atom, perhaps cyano group, nitro, primary amino, secondary amino group or uncle's amino, C ₁-C ₅Alkoxyl group, C ₁-C ₅Alkyl, benzyloxy, benzyl, acid amides, ethanoyl or imines, above-mentioned metal M can be Ni, Pd, Pt, Co, Rh, Ir, Fe, Ru and Os.

Some catalyzer, especially the coordination compound of nickel is the known distinguishing catalyzer of people, and at J.Mol.Catal.45, P.169 (1988); J.Chem.Mater.Vol.6,1675 (1994), Nature 656, Vol.372 (1994); Recl-Trav.Chim.Pays-Bas 113, and P.267 (1994) and Organometallics Vol.13 are disclosed by G.Van Koten etc. on the publications such as 468 (1994).

More specifically, in the structural formula of represented catalyzer of chemical formula (I)-(V) and ligand, following substituting group is considered to highly significant:

R ¹=R ²=methyl,

R ¹=R ²=ethyl,

R ¹=methyl, R ²=sec.-propyl

R ¹=methyl, R ²=tertiary butyl

R ¹=methyl, R ²=phenyl

R ¹=R ²=phenyl

Work as R ¹And R ²Be connected when forming a pyrrolidyl or proline(Pro) with nitrogen-atoms, this catalyzer just has the asymmetry center, that is to say, has the opticity center of optically active isomer.When carrying out polyreaction with monomer, the transfer of this opticity just can cause the solid control to polyreaction or copolymerization;

-R ³Represent hydrogen or chlorine atom, or CN, NO ₂With NH ₂Base, RNH-, RR ' N=, RO-, R-, RC (O) NH-, RC (O)-, RR ' CN-base, wherein this substituent R and R ' can be methyl, ethyl, propyl group, butyl, sec.-propyl, isobutyl-, tertiary butyl, neo-pentyl or benzyl.

In addition, by means of R ³, R or R ', this catalyzer can carrier band or is plugged at least a organic or inorganic thing, silicon-dioxide preferably, polymer class, as at least a polysilane, this class of polysiloxane can constitute the catalyzer point of fixity.Come to this, when pegging graft some homogeneous catalyzer, people just can be in conjunction with the advantage of homogeneous katalysis (than highly selective and mild reaction conditions) with heterogeneity katalysis (recirculation).As an example, as people such as Lucia.A.Van de Kuil at Chem.Mater.Vol.6, P.1675 (1994), and G.Van Koten etc. is at Nature Vol.372, and P.659 (1994) had been described such: can be plugged into metal catalyst on the dendrimers of polysilane type or on the polymkeric substance of polysiloxane type.

-for metal M, when n=1, M=Ni ^II, Pd ^II, Pt ^II,

Co ^II、Ru ^II；

When n=2, M=Ni ^III, Fe ^IIIWhen M is Co ^IIOr Ru ^IIThe time, this catalyzer should be stablized (as the catalyzer of chemical formula V) by ligands such as pyridine, phosphorous acid ester or phosphines.

-X can be a halogen atom (as Cl, Br and I), nitro, nitrate radical, the conjugate base R of carboxylic acid ⁴COO ^-, R wherein ⁴Represent a hydrogen atom, C ₁-C ₁₄Alkyl, CF ₃Or CCl ₃(for example, acetate, formate, propionic salt and trifluoroacetate group) perhaps can also randomly be an alkylsulfonate R ⁵SO ₃-group, wherein R ⁵Expression C ₁-C ₁₄Alkyl or CF ₃, CF for example ₃SO ₃-group.

Above-mentioned catalyzer does not play the propellant of radical, thus it must with a kind of such compound combined action.Our guess since the transfer of redox atom promptly by follow also the interaction of the continuous oxidation addition of insert with the reduction elimination reaction that is used to generate definite polymkeric substance chain link.Therefore, when replenishing a certain amount of polymerisable monomer, can proceed polymerization like this.If above-mentioned monomer has same nature, so, just can obtain homopolymer; If adopt different monomer mixture for copolymerization, then can obtain irregular multipolymer, and for example fruit adds first kind of monomeric other monomer that be different from of doses again after first kind of monomeric polyreaction, so, just can obtain segmented copolymer.In order to prepare segmented copolymer, we can adopt two or more mixture of catalysts, wherein the monomer of second dosage can be different but belong under the condition that catalyzer that the scope of the invention limits participates in reaction and add, and this catalyzer should be more active than existing.Like this, we can repeat this we wish the operation of every kind of new sequence preparing.

According to the present invention, suitable free radical generating agent compound is the compound of halogen preferably, is wherein activated by the acceptance of electronics and/or the effect of emitting on the carbon atom of the alpha position of the halogen of this compound.

When the propellant of above-mentioned radical was simple function, it should be selected from the following halogen compounds:

A) haloform of following chemical formula or tetrahalomethanes: CYZ ₃, Y=Cl wherein, Br or H, Z=Cl or Br, for example tetracol phenixin, chloroform, carbon tetrabromide and bromo-trichloromethane;

B) the trichloromethyl derivative of following chemical formula: R ⁶CCl ₃, R wherein ⁶Expression phenyl, benzyl, benzyloxy, ethoxy carbonyl, acyl group, alkyl wherein have 1-4 carbon atom, methyl, Mi Ji, trifluoromethyl or nitro, for example, α, α, α-trichlorotoluene zotrichloride, α, α, α-tribromo-acetyl benzene, ethyl trichloroacetate, 1,1,1-trichloroethane, 1,1,1-three chloro-2-phenylethanes, trichloromethyl, 1,1,1-Refrigerant R 113 and trichloronitromethane;

C) alkyl halide wherein has electron-withdrawing group on the carbon of the alpha position of halogen, its chemical formula is as follows:

R wherein ⁷, R ⁸And R ⁹Be identical or inequality, each represents a hydrogen atom, C ₁-C ₁₄Alkyl, or aromatic base for example contains phenyl group, anthryl group, naphthylene group, R ¹⁰Expression C ₁-C ₁₄Alkyl, phenyl or isocyanate group, and Q represents chlorine atom or bromine atoms, perhaps trifluoracetic acid ester group (OCCF ₃) or trifluoromethanesulfonic acid base (O ₃SCF ₃), as 2 bromopropionic acid, 2-bromo-butyric acid, 2-bromocaproic acid, bromoacetonitrile, 2-bromopropionitrile, 2-bromine phenyl isopropyl ketone, and chloracetyl isocyanic ester;

D) have the halogenide of following chemical formula: R wherein ¹¹And R ¹²Be identical or different, represent C ₁-C ₁₄Alkyl or primary alcohol group-CH ₂OH, R ¹³Be a functional group, as hydroxyl, nitro, amino, the C that replaces or do not replace ₁-C ₁₄Alkoxyl group, acyl group, carboxylic acid or ester, and Q is as previously mentioned, can be 2-bromo-2-nitro-1, ammediol and 2-bromo-2-nitropropane;

E) halogenated lactone or lactam compound on alpha position are as α-bromo-Alpha-Methyl-r-butyrolactone or α-bromo-r-valerolactone, halogenated dodecanoic lactam or halogenated hexanolactam;

F) the benzyl halogen of following chemical formula, R wherein ¹⁴Represent a hydrogen atom, C ₁-C ₁₄Alkyl, or carboxylic acid, ester, nitrile or ketone group, R ¹⁵Represent a hydrogen atom, or C ₁-C ₁₄Alkyl, the amino, hydroxyl, the ethanoyl that replace or do not replace, nitro, C ₁-C ₁₄Alkoxyl group, or sulphonate-base (SO ₃ ^-Na ⁺Or K ⁺), and the meaning of Q is as previously mentioned.

G) N-halo succinimide is as N-bromine succinimide and N-halogen phthalimide, as N-bromine phthalimide;

H) its chemical formula is R ¹⁶SO ₂Alkyl-sulfonic acid halide of V, wherein R ¹⁶Expression C ₁-C ₁₄Alkyl, and V represents the chlorine or bromine atom.

We also consider to adopt the propellant of the radical of difunctionality type and multifunctional type; The propellant of the radical of difunctionality type can be by above-mentioned c)-propellant of the radical of two simple function types in h) forms, they are connected by a methene chain unit or the phenyl ring shown in following chemical formula, preferably connect on position between benzene:

A ¹-(CH ₂) _p-A ²With

The propellant compound of the radical of multifunctional type can be by above-mentioned c)-the propellant group of the radical of at least three simple function types in h) formed, and the phenyl ring of wherein ining succession between them for example has those of following chemical formula:

Wherein, A ¹, A ²And A ³Can be identical or inequality, each represents above-mentioned c)-the propellant group of the radical of a simple function type in h), p represents the integer of 1-14.

The difunctionality type compound of other taken place radical is haloform or tetrahalomethanes, and aforesaid a) and b) in the derivative of trichloromethyl, above-mentioned haloform and tetrahalomethanes similarly can be as the multifunctional type compounds that radical can take place.

People especially preferentially use the compound of following taken place radical: tetracol phenixin, ethyl trichloroacetate, 2-bromo-ethyl isobutyrate.In emulsion polymerization, we also can use sodium trichloroacetate, Tricholroacetic Acid potassium, chlorine two sodium fluoroethanoates, chlorine difluoro Potassium ethanoate and Sodium.alpha.-chloroacetate.

We also can use other the material of the same clan of difunctionality type compound, particularly acetic anhydride of taken place radical that is different from above-mentioned qualification, as sym-dichloroacetic anhydride and chlorine difluoroacetic acid acid anhydride.

The initiating method of another polyreaction is to go to cause this polyreaction by the free-radical initiator that often uses in radical polymerization.Below list the material that can be used as initiator family:

-azo-compound, for example, 2,2 '-azo-two isopropyl cyanides (AIBN) and 1,1-azo-two (cyclohexane nitrile) and 4,4 '-azo-two (4-cyano group amyl group) acid.

-superoxide, diacyl peroxide for example is as dibenzoyl superoxide and two lauroyl peroxides; Dialkyl peroxide is as di-tert-butyl peroxide and di-isopropyl superoxide; Two aromatic alkyl superoxides are as two p-isopropylbenzyl superoxide; Two carbonate superoxide; Cross (entirely) ester, as the peroxyacetic acid ester of tertiary butyl, the trimethylacetic acid ester excessively of tert-pentyl, the mistake-2-ethylhexanoate of butyl, benzene (first) acid esters excessively of crossing trimethylacetic acid ester and tertiary butyl of tertiary butyl; Hydroperoxide, as the hydroperoxide of tertiary butyl, and inorganic superoxide, as the persulphate of hydrogen peroxide and sodium and potassium.

According to (methyl) propenyl monomer, vinyl monomer ratio with respect to the propellant compound of radical, can give the chain length of determining polymkeric substance earlier, catalyzer is with respect to the molar ratio of the propellant compound of radical within the scope of the invention, and one or more monomers hold the balance with respect to molecular proportion of catalyst.That is to say that the molar ratio of the propellant compound of the relative radical of catalyzer is 0.01-100, preferred 0.1-5, and one or more monomers are 1-10 with respect to molecular proportion of catalyst, and 000, preferred 50-2,000.

The inventive method is with the maximum difference of the additive method that uses the known catalysts system: this temperature parameter is important in the extreme in polyreaction or copolymerization.In known catalytic reaction method, when not having activator to participate in reaction, about below 100 ℃ the time if temperature of reaction is in, the inactivation phenomenon will appear in this catalyzer.When if temperature is reduced to 50 ℃, adopt CuCl/2, the 2-pyridine catalyst is not perhaps having activator to participate in adopting RuCl under the condition of reaction ₂(PPh ₃) ₃Even polymerization through the reaction times in a few days, can not take place in catalyzer yet.We we can say that reaction conditions within the scope of the present invention is gentle.Because it is very uncommon, promptly under barometric point, when temperature dropped to 0 ℃, the catalyzer in synthesizing still can keep active.This advantage is very important, because help the solid control of polyreaction or copolymerization more under the situation that temperature reduces.On the other hand, block (that is to say when adopting one or more pure monomers) is identical with reaction conditions in solution, emulsion or the suspension polymerization basically.No matter adopt which type of reaction method, this temperature of reaction can be the same with all molar ratio.Operability at pure monomer is not in-problem, and must improve traditional radical polymerization effect.Owing to there is not termination reaction, the concentration in the active centre in whole polymerization or copolymerization process is stable, the rapid exothermic phenomenon (being the Trommsdorf effect) that occurs in traditional radical polymerization can not occur.Because polyreaction or copolymerization no longer are to carry out under the volatile condition of danger, therefore, this industrial method is that tool has greatly improved.Usually, this polyreaction or copolymerization are to carry out under 0 ℃-150 ℃ temperature, preferred 50 ℃-110 ℃, the inactivation effect of catalyzer can not occur at all.

According to initiating system of the present invention and water compatible.Therefore, under the condition that is with or without emulsifying agent participation reaction, can in water-bearing media, carry out polyreaction or copolymerization.Therefore, above-mentioned polyreaction of in water-bearing media, carrying out or can under the condition that has emulsifying agent to participate in, in emulsion (the propellant compound of water-soluble radical), carry out, or in suspension (the propellant compound of water-fast radical), carry out.Mentioned emulsifier can be an aniorfic surfactant, for example, Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, Sodium Lauryl Sulphate BP/USP and composition thereof, or its neutral type formula, as glycol ester, the ester of sorbitan and polyethylene glycol, single lauryl of polyethylene glycol and sorbitan for example, monopalmitate, stearate and oleic acid ester, the ester of polyethylene glycol and lipid acid, the stearate of polyethylene glycol for example, and the ether of polyethylene glycol and Fatty Alcohol(C12-C14 and C12-C18), for example cetyl ether of polyethylene glycol and stearyl ether.

Anionic emulsifier should use under the condition of pH＞7, thereby so that can not influence the structure of catalyzer it is lost activity.

If according to polymerization of the present invention or copolymerization is when carrying out in solution, also be suitable at a kind of following organic solvent certainly or belong under the condition that following organic solvent family mixture participates in reacting:

-aromatic hydrocarbon (proton is had inert from polarity): benzene, toluene, ethylbenzene, dimethylbenzene;

-chlorinated hydrocarbon (proton is had inert polarity): methylene dichloride, chlorobenzene;

-cyclic ethers (proton is had inert polarity): tetrahydrofuran (THF), diox;

-ester (polar): vinyl acetic monomer, cyclohexyl acetate;

-ketone (polar): ethyl methyl ketone, pimelinketone.

Above-mentioned organic solvents in particular is applicable to propenyl monomer (methacrylic ester, acrylate, vinyl cyanide) and ethene aromatic base monomer, as styrene-based monomers as monomeric polymerization or copolymerization.

In some cases, particularly in n-BMA and cinnamic polyreaction, we can use hexane and hexanaphthene; And in vinyl acetate between to for plastic acid and polymerization of acrylonitrile, we can use dimethyl formamide, dimethyl sulfoxide (DMSO), acetonitrile or acetone.

According to the present invention, above-mentioned polymerization or copolymerization similarly also can carry out under the condition of polar additive or polar additive mixture participation reaction.The existence of these additives can help adjusting some molecular parameters, reduces the distributivity of molecular weight more accurately, makes it near isometry molecularity (Mw/Mn=1).The polar additive that does not constitute limitation of the scope of the invention comprises acetonitrile (CH ₃CN), water, pyridine, tetrahydrofuran (THF), diethyl ether, dimethyl sulfoxide (DMSO), and acetone.Under above-mentioned all situations, these polar additives exist with trace; Therefore, as the existence of the water of polar additive, can't be not compatible with organic solvent.Usually, polar additive is 0-100 for the mol ratio of catalyzer, preferred 0-40.

Generally speaking, according to polymerization of the present invention or process for copolymerization, for no matter being equal polymerization reaction, still random copolymerization all is consistent.Yet when the preparation segmented copolymer, if when the later another kind of monomer that is added of first kind of monomeric polyreaction is different from first kind of monomer, experiment condition also can change so.For example, can change different temperature condition, the monomer of second dosage then can add with solvent etc.When preparing macromonomer or α, ω functional polymer (telechelic polymer), we also consider to change relevant experiment condition with same pattern.

In the presence of the initiating system of polymerization of recommending or copolymerization, can list (methyl) propenyl monomer and vinyl monomer (ethene aromatic base, vinyl acetate are as vinyl acetate) as the monomer of polymerization or copolymerization.

Equally also be applicable to the possibility fluorizated according to initiating system of the present invention, chain olefinic monomeric (being total to) polyreaction, for example, ethene, butylene, hexene, 1-octene.They equally also are applicable to have conjugated double bond monomeric (being total to) polyreaction, for example divinyl, isoprene.

According to propenyl monomer of the present invention, can select primary for use, secondary, the monomer that the acrylate of tertiary alkyl is used as (being total to) polymerization, wherein, this alkyl has 1-18 carbon atom, in case of necessity can be by for example at least one halogen atom, as fluorine, and/or at least one hydroxyl replaces, the monomer of enumerating especially comprises ethyl propenoate, propyl acrylate, isopropyl acrylate, butyl acrylate, vinylformic acid isobutyl vinegar, Ethyl acrylate, the special butyl ester of vinylformic acid, the own ester of vinylformic acid ethyl-2-, vinylformic acid ester in the ninth of the ten Heavenly Stems, lauryl acrylate, the stearyl acrylate ester, cyclohexyl acrylate, isodecyl acrylate, and phenyl acrylate, isobornyl acrylate, acrylic acid alkyl alkylthio ester, or alkoxyalkyl acrylate, vinyl cyanide and dialkyl group acrylic amide.

According to methylpropenyl monomer of the present invention, can select the methacrylic ester of alkyl for use, wherein, this alkyl contains 1-18 carbon atom, in case of necessity can be by for example at least one halogen atom, replace as fluorine and/or at least one hydroxyl, these alkyl comprise the methyl esters of methacrylic acid, ethyl ester, 2,2,2 trifluoroethyl esters, n-propyl, isopropyl ester, positive butyl ester, secondary butyl ester, the tert-butyl ester, n-pentyl ester, isopentyl ester, own ester, the own ester of ethyl-2-, cyclohexyl, monooctyl ester, different monooctyl ester, the last of the ten Heavenly stems ester, the beta-hydroxy ethyl ester, hydroxy propyl ester, the hydroxyl butyl ester, and glytidyl methacrylate, methacrylic acid norborneol ester, methacrylonitrile and dialkyl methyl acrylamide.

A tree name aromatic ethenyl monomer of the present invention, comprise aromatic base monomer with unsaturated ethylene thiazolinyl, for example vinylbenzene, vinyl methyl, αJia Jibenyixi, methyl-4-vinylbenzene, methyl-3-vinylbenzene, methoxyl group-4-vinylbenzene, methylol-2-vinylbenzene, ethyl-4-vinylbenzene, oxyethyl group-4-vinylbenzene, dimethyl-3,4-vinylbenzene, chloro-2-vinylbenzene, chloro-3-vinylbenzene, chloro-4-methyl-3-vinylbenzene, tertiary butyl-3-vinylbenzene, two chloro-2,4-vinylbenzene, two chloro-2,6-vinylbenzene, and vinyl-1-naphthalene.

According to the present invention, we are verified, by as catalyzer, the foregoing coordination compound that contains the metal of a ligand cooperates with the reasonable of propellant compound of the radical of polymerization, we can prepare definite, controllable homopolymer, segmented copolymer and irregular multipolymer, and macromonomer and α, ω functional polymer (telechelic polymer).And before this, be impossible synthesize to prepare the said products with traditional free polymerisation process.

The present invention also relates to polymkeric substance or multipolymer with method for preparing, wherein its molecular weight is controlled, and its polymolecularity is also narrower.

According to the inventive method prepared (methyl) propenyl monomer, the molecular weight Mn of polymer of vinyl monomer and multipolymer is approximately 400-1000,000 gram/mole, and its polymolecularity Mw/Mn is narrow especially, promptly less than 2, and to be advisable less than 1.5.In the radical polymerization category, it demonstrates bigger progress, since it only spends little time, just can make the distribution of molecular weight or polymolecularity Mw/ Mn less than 1.5 astoundingly.In addition, method of the present invention has extraordinary regioselectivity, that is to say, can its direction of utmost point Cui ground control in the diffusion process of monomeric unit.On the other hand, the bonding of chain just head links up to tail ground, and no longer is linking up mutually head to head as under traditional radical polymerization situation.So just help the thermostability of polymkeric substance and multipolymer and their preparation.Owing to do not have termination reaction, certainly will just eliminate the possibility of every other chain bonding head to head.

With existing ionic and radical polymerization together polymerisation process compare, method of the present invention possesses superiority as follows:

-good molecular Control: Mw/ Mn is narrower, until the effect of about Mw/ Mn=1.1, make theoretical value Mn and trial value Mn have good mutual relationship owing to free radical generating agent; Possibility with preparation segmented copolymer;

The polymerization reaction medium of-homogeneous;

-gentle temperature condition, 0 ℃-150 ℃;

-owing to therefore catalyzer used in the reaction can not have and the water-bearing media consistency because of the existence generation Degradation of water.Can carry out emulsion polymerization and suspension polymerization;

-might carry out solid control, that is to say that the stereospecific degree of mix control is controlled or controlled with the stereospecific degree entirely with the stereospecific degree.For this reason, we can use contains amine groups, and connects the obstruction methylene radical or block the catalyzer of (one side of blocking catalyzer) with the obstruction methylene radical between them, and the catalyzer of opticity;

-prepared polymkeric substance or multipolymer synthetic has good controlled, and its molecular weight can be 400-1,000,000 gram/mole, and preferred 4000-130,000 gram/mole;

-owing to there is not termination reaction (chemosynthesis and disproportionation), can improve the heat resistanceheat resistant degraded intensity of polymkeric substance and multipolymer, this intensity for example can be represented by thermo-gravimetric analysis;

-can make the new product that is difficult to prepare according to polymerization technique commonly used, for example, pure segmented copolymer, the irregular multipolymer of qualification, and the super polymers grafted of the tackiness agent of available for example controllable functions, antidetonation additive, emulsifying agent and interfacial agent.

According to existing reaction mechanism, all monomers can be consumed ideally, and promptly reaction yield can reach 100% (quantitatively).Yet it also may be owing to various reasons, reason especially as follows, and be lower than 100%.

-kinetics reason (sluggish);

-viscosity promptly hinders the crosslinked of monomeric diffusion and polymer chain.

This has just explained that most of example reaction earning rates generally are 80-90%.In fact, because the characteristic of the polymkeric substance of gained, reaction medium is glassingization (glass transition temperature is to be higher than polymeric reaction temperature) soon.

Usually, owing to there is termination reaction, therefore reacting earning rate also is to be lower than 100%; Yet, really not so according to method of the present invention; Because there is not above-mentioned termination reaction in it, or be not measure in test at least.

Below, we propose some examples that do not limit the scope of the invention, to describe the preparation according to the polymkeric substance and the multipolymer of the inventive method.

Example 1

The Polymerization of Methyl reaction

Under inert atmosphere, in the methyl methacrylate of 1.87 grams, add 33 milligram (10 ^-4Mole) catalyzer [Ni{2,6-[CH ₂N (CH ₃) ₂] ₂-C ₆H ₃Br].In above-mentioned catalyzer and monomeric test tube are housed, inject 11 milligrams of the toluene be dissolved in 0.34 gram (7.2 * 10 ^-5Mole) carbon tetrachloride solution.This test tube seals after exhaust, places 76-78 ℃ oil bath then, and carries out 19 hours polyreaction.Behind methanol extraction, can obtain polymkeric substance, analyze then.

The polymkeric substance earning rate is 84%.

Mn experimental value=32100 gram/moles (the Polymerization of Methyl thing of standard).

Mn theoretical value=28800 gram/moles.

Mw/ Mn＝1.28

Record above-mentioned numerical value with following method.We can use steric exclusion chromatography instrument (SEC), according to the size (hydrokinetics volume) of Polymerization of Methyl thing (PMMA) in solution, isolate macromolecular PMMA.Use then a kind of PMMA solvent (THF moving phase) elution it.The thickest molecule is at first come out by go-on-go, and the then last go-on-go of minimum molecule is gone out, and this is because the long cause (static phase) of stroke in the post hole.The PMMA or the polystyrene of (the measuring with other technologies) of known absolute magnitude are injected into (as standard) too, and can obtain working curve, we can calculate the relative molecular weight (Mn experimental value) of polymkeric substance thus, wherein, we want to know the size of molecular weight and the distribution or the polymolecularity (Mw/ Mn) of molecular weight.

Example 2

The Polymerization of Methyl reaction

Repeat as the operation in the example 1, but wherein in initial mother liquor (that is to say monomer, solvent and catalyzer) solution, add acetonitrile as polar additive.

[Ni{2,6-[CH ₂N (CH ₃) ₂] ₂C ₆H ₃Br]=33 milligram (10 ^-4Mole),

Methyl methacrylate=1.87 grams,

CCl ₄=11 milligram (7.2 * 10 ^-5Mole),

Toluene=0.34 gram,

CH ₃CN=78.6 milligram (1.9 * 10 ^-3Mole),

Polymerization reaction time=19 hour,

Oil bath temperature=76-78 ℃.

Mn tests=19000 gram/moles (PMMA of standard);

Mn theory=20500 gram/moles;

Earning rate=79%; Mw/ Mn=1.19.

Example 3

The polyreaction of Jia Jibingxisuanyizhi

Repeat operation as example 2

[Ni{2,6-[CH ₂N (CH ₃) ₂] ₂-C ₆H ₃Br]=33 milligram (10 ^-4Mole),

Jia Jibingxisuanyizhi=0.92 gram,

CCl ₄=3 milligram (2 * 10 ^-5Mole),

CH ₃CN=0.8 milligram (2 * 10 ^-5Mole),

Toluene=0.17 gram,

Polymerization reaction time=37.5 hour,

Oil bath temperature=76-78 ℃.

Mn tests=21400 gram/moles (PMMA of standard);

Mn theory=41500 gram/moles; Earning rate=90%; Mw/ Mn=1.14.Example 4

The Polymerization of Methyl reaction

Repeat operation as example 2

[Ni{2,6-[CH ₂N (CH ₃) ₂] ₂-C ₆H ₃Br]=33 milligram (10 ^-4Mole),

Methyl methacrylate=1.87 grams,

CCl ₄=11 milligram (7.2 * 10 ^-5Mole),

Toluene=0.34 gram,

CH ₃CN=78.6 milligram (1.9 * 10 ^-3Mole),

Polymerization reaction time=216 hour,

Oil bath temperature=50 ℃.

Mn tests=9300 gram/moles (PMMA of standard);

Mn theory=9400 gram/moles;

Earning rate=36%; Mw/ Mn=1.14.

Example 5

The polyreaction of n-BMA

Repeat operation as example 2

[Ni{2,6-[CH ₂N (CH ₃) ₂] ₂-C ₆H ₃Br]=33 milligram (10 ^-4Mole),

N-BMA=1.78 grams,

CCl ₄=1.1 milligram (7.2 * 10 ^-5Mole),

Toluene=0.34 gram,

CH ₃CN=0.16 milligram (3.8 * 10 ^-3Mole),

Polymerization reaction time=76 hour,

Oil bath temperature=76-78 ℃.

Mn tests=11900 gram/moles (PMMA of standard);

Mn theory=22800 gram/moles;

Earning rate=92%; Mw/ Mn=1.15.

Example 6

The irregular copolymerization of methyl methacrylate/Jia Jibingxisuanyizhi

Repeat operation as example 2, but wherein with the mixture of methacrylic ester as starting material.

[Ni{2,6-[CH ₂N (CH ₃) ₂] ₂C ₆H ₃Br]=33 milligram (10 ^-4Mole),

Methyl methacrylate=0.94 gram,

Jia Jibingxisuanyizhi=1 gram,

CCl ₄=11 milligram (7.2 * 10 ^-5Mole),

Toluene=0.34 gram,

CH ₃CN=0.16 milligram (3.8 * 10 ^-3Mole),

Polymerization reaction time=68 hour,

Oil bath temperature=76-78 ℃.

Mn tests=13400 gram/moles (PMMA of standard);

Mn theory=24400 gram/moles;

Earning rate=90%; Mw/ Mn=1.14.

Example 7

Cinnamic polyreaction

The operation of weight such as example 1

[Ni{2,6-[CH ₂N (CH ₃) ₂] ₂C ₆H ₃Br]=21.8 milligram (6.62 * 10 ^-5Mole),

Vinylbenzene=0.54 gram,

CCl ₄=7.69 milligram (4.99 * 10 ^-5Mole),

The THF=0.62 gram,

Polymerization reaction time=42 hour,

Oil bath temperature=70 ℃ (21 hours), ℃ (21 hours) then=110.

Earning rate=92%;

Mn tests=18200 gram/moles; Mn theory=10000 gram/moles;

Mw/ Mn＝1.68。

Example 8

The Polymerization of Methyl reaction

Repeat operation as example 2

[Ni{2,6-[CH ₂N (CH ₃) ₂] ₂C ₆H ₃Br]=33 milligram (10 ^-4Mole),

Methyl methacrylate=1.87 grams,

(CH ₃) ₂C (Br) CO ₂C ₂H ₅=14.78 milligram (7.56 * 10 ^-5Mole),

CH ₃CN=78.6 milligram (1.9 * 10 ^-3Mole),

Toluene=0.4 milliliter,

Polymerization reaction time=23 hour,

Oil bath temperature=80 ℃,

Mn tests=21400 gram/moles (polystyrene standard);

Mn theory=17500 gram/moles; Earning rate=67%; Mw/ Mn=1.11.

Example 9

The Polymerization of Methyl reaction

Repeat operation as example 1

[Ni{2,6-[CH ₂N (CH ₃) ₂] ₂C ₆H ₃Br]=33 milligram (10 ^-4Mole),

Methyl methacrylate=1.87 grams,

(CH ₃) ₂C (Br) CO ₂C ₂H ₅=14.78 milligram (7.56 * 10 ^-5Mole),

Toluene=0.4 milliliter,

Polymerization reaction time=24 hour,

Oil bath temperature=80-82 ℃.

Mn tests=21900 gram/moles (polystyrene standard);

Mn theory=18200 gram/moles; Earning rate=70%;

Mw/ Mn＝1.11。

Example 10

The Polymerization of Methyl reaction

Repeat operation as example 1

[Ni{2,6-[CH ₂N (CH ₃) ₂] ₂C ₆H ₃Br]=47 milligram (1.42 * 10 ^-4Mole),

Methyl methacrylate=5.61 grams,

(CH ₃) ₂C (Br) CO ₂Ethyl=7 milligrams (3.6 * 10 ^-5Mole),

Toluene=0.2 milliliter,

Polymerization reaction time=43 hour,

Oil bath temperature=80 ℃.

Mn tests=117600 gram/moles (polystyrene standard);

Mn theory=136000 gram/moles; Earning rate=87%;

Mw/ Mn＝1.61。

Example 11

The Polymerization of Methyl reaction

Repeat operation as example 1

[Ni{4-CH ₃O-2,6-[CH ₂N (CH ₃) ₂] ₂C ₆H ₂Br]=36 milligram (10 ^-4Mole),

Methyl methacrylate=1.87 grams,

(CH ₃) ₂C (Br) CO ₂C ₂H ₅=23.4 milligram (1.19 * 10 ^-4Mole),

Toluene=0.26 gram,

Polymerization reaction time=23 hour,

Oil bath temperature=80 ℃.

Mn tests=14700 gram/moles (polystyrene standard);

Mn theory=10300 gram/moles; Earning rate=66%;

Mw/ Mn＝1.09。

Example 12

The Polymerization of Methyl reaction

Repeat operation as example 1

[Ni{2,6-[CH ₂N (CH ₃) ₂] ₂C ₆H ₃Br]=6.6 milligram (2 * 10 ^-5Mole),

Methyl methacrylate=1.87 grams,

(CH ₃) ₂C (Br) CO ₂C ₂H ₅=39 milligram (1.99 * 10 ^-4Mole),

Toluene=0.5 milliliter,

Polymerization reaction time=22.5 hour,

Oil bath temperature=80 ℃.

Mn tests=8500 gram/moles (polystyrene standard);

Mn theory=4900 gram/moles; Earning rate=52%;

Mw/ Mn＝1.16。

Example 13

The Polymerization of Methyl reaction

Repeat operation as example 1

[Ni{2,6-[CH ₂N (CH ₃) ₂] ₂C ₆H ₃Cl]=28.5 milligram (10 ^-4Mole),

Methyl methacrylate=1.87 grams,

(CH ₃) ₂C (Br) CO ₂C ₂H ₅=23.4 milligram (1.19 * 10 ^-4Mole),

Toluene=0.26 gram,

Polymerization reaction time=23 hour,

Oil bath temperature=80 ℃.

Mn tests=12900 gram/moles (polystyrene standard);

Mn theory=10700 gram/moles; Earning rate=68%;

Mw/ Mn＝1.11。Example 14

The Polymerization of Methyl reaction

Repeat operation as example 2

[Ni{2,6-[CH ₂N (CH ₃) ₂] ₂C ₆H ₃Br]=33 milligram (10 ^-4Mole),

Methyl methacrylate=1.87 grams,

CH ₃The CH=78 milligram,

EtO (CO) (Cl ₃)=7.65 milligrams (4 * 10 ^-5Mole),

Toluene=0.4 milliliter,

Polymerization reaction time=26 hour,

Oil bath temperature=80 ℃.

Mn tests=19500 gram/moles;

Mn theory=27250 gram/moles; Earning rate=58%;

Mw/ Mn=1.14 (standard P MMA).

Example 15

The Polymerization of Methyl reaction

Repeat operation as example 1

[Ni{2,6-[CH ₂N (CH ₃) ₂] ₂C ₆H ₃Br]=33 milligram (10 ^-4Mole),

Methyl methacrylate=1.87 grams,

[(CH ₃) ₂C (COC ₆H ₅) Br] (bromide of phenyl isopropyl ketone)=18.53 milligrams,

Polymerization reaction time=15 hour,

Oil bath temperature=80 ℃.

Mn tests=12250 gram/moles;

Mn theory=28400 gram/moles; Earning rate=54%;

Mw/ Mn=1.1 (standard P MMA).

Example 16

The Polymerization of Methyl reaction

Repeat the operation of example 1

[Ni{2,6-[CH ₂N (CH ₃) ₂] ₂C ₆H ₃Br]=0.34 gram (10 ^-3Mole),

Methyl methacrylate=1.87 grams,

(CH ₃) ₂C (Br) CO ₂C ₂H ₅=172 milligrams,

Toluene=1 milliliter,

Polymerization reaction time=19 hour,

Oil bath temperature=60 ℃.

Mn tests=3600 gram/moles;

Mn theory=2100 gram/moles; Earning rate=95%;

Mw/ Mn=1.2 (standard P MMA).

Example 17

Repeat operation as example 1

[Ni{2,6-[CH ₂N (CH ₃) ₂] ₂C ₆H ₃Br]=0.34 gram (10 ^-3Mole),

Methyl methacrylate=1.87 grams,

CCl ₄=0.144 gram,

Toluene=1 milliliter,

Polymerization reaction time=19 hour,

Oil bath temperature=60 ℃.

Mn tests=1250 gram/moles;

Mn theory=1980 gram/moles; Earning rate=100%;

Mw/ Mn=1.2 (standard P MMA).

Example 18

The bulk polymerization of methyl methacrylate

Repeat operation, but do not have toluene as example 1

[Ni{2,6-[CH ₂N (CH ₃) ₂] ₂C ₆H ₃Br]=29 milligram (8.79 * 10 ^-2Mole),

Methyl methacrylate=4.58 grams,

(CH ₃) ₂C (Br) CO ₂C ₂H ₅=7.64 milligram (3.92 * 10 ^-5Mole),

Polymerization reaction time=43 hour,

Oil bath temperature=80 ℃.

Example 19

Methyl methacrylate dash polyreaction in rare medium:

Repeat operation as example 1.

[Ni{2,6-[CH ₂N (CH ₃) ₂] ₂C ₆H ₃) Br]=29 milligram (8.79 * 10 ^-2Mole),

Methyl methacrylate=4.58 grams,

(CH ₃) ₂C (Br) CO ₂C ₂H ₅=7.64 milligram (3.92 * 10 ^-5Mole),

Toluene=5 milliliter,

Polymerization reaction time=43 hour,

Oil bath temperature=80 ℃.

Experimental result (standard P MMA)

Example	Yield (%)	Mn theory (gram/mole)	Mn tests (gram/mole)	? Mw/ Mn
					?18	?77	??89800	??97900	?1.64
?19	?50	??58900	??64800	?1.16

Example 20

Under 20 ℃ of conditions, at CH ₃CH participates under the reaction conditions, the bulk polymerization of methyl methacrylate:

Repeat operation as example 2

[Ni{2,6-[CH ₂N (CH ₃) ₂] ₂C ₆H ₃Br]=32 milligram (9.7 * 10 ^-5Mole),

Methyl methacrylate=1.68 grams,

CH ₃CN=79 milligram (1.9 * 10 ^-3Mole),

(CH ₃) ₂C (Br) CO ₂C ₂H ₅=15.7 milligram (8 * 10 ^-5Mole),

Polymerization reaction time=79 hour,

Oil bath temperature=20 ℃.

Mn tests=12700 gram/moles;

Mn theory=6200 gram/moles; Earning rate=31.4%;

Mw/ Mn=1.09 (standard P MMA).In example 21 and 22,, there be not CH with different temperature condition ₃CN participates under the condition of reaction, the preparation polymethylmethacrylate:

Example 21

Repeat the operation of example 1

[Ni{2,6-[CH ₂N (CH ₃) ₂] ₂C ₆H ₃Br]=38 milligram (1.15 * 10 ^-5Mole),

Methyl methacrylate=1.87 grams,

(CH ₃) ₂C (Br) CO ₂C ₂H ₅=18.72 milligram (9.6 * 10 ^-5Mole),

Example 22

Repeat the operation of example 1

[Ni{2,6-[CH ₂N (CH ₃) ₂] ₂C ₆H ₃Br]=38 milligram (1.15 * 10 ^-5Mole),

Methyl methacrylate=1.87 grams,

(CH ₃) ₂C (Br) CO ₂C ₂H ₅=18.72 milligram (9.6 * 10 ^-5Mole),

Experimental result table (standard P MMA)

Example	Temperature ℃	Yield (%)	Polymerization reaction time (hour)	Theoretical gram/the mole of Mn	Mn tests gram/mole	Mw/ Mn
							?21	?60	??30	????7	??5850	???7400	?1.28
?22	?80	??38.5	????5	??7500	???11100	?1.18

Hence one can see that for we, and the raising of said temperature can improve yield.Temperature heals, and then polymolecularity is just little for height.

Example 23

Repeat operation, but implement bulk polymerization as example 1.

[Ni{2,6-[CH ₂N (CH ₃) ₂] ₂C ₆H ₃Br]=1.48 milligram (4.48 * 10 ^-6Mole),

Methyl methacrylate=0.88 gram,

(CH ₃) ₂C (Br) CO ₂C ₂H ₅=8.9 milligram (4.56 * 10 ^-5Mole),

Oil bath temperature=70 ℃.

Example 24

Repeat operation as example 23

[Ni{2,6-[CH ₂N (CH ₃) ₂] ₂C ₆H ₃Br]=28.2 milligram (8.54 * 10 ^-5Mole),

Methyl methacrylate=0.84 gram,

(CH ₃) ₂C (Br) CO ₂C ₂H ₅=8.4 milligram (4.3 * 10 ^-5Mole), oil bath temperature=70 ℃.

Example 25

Repeat operation as example 23

[Ni{2,6-[CH ₂N (CH ₃) ₂] ₂C ₆H ₃Br]=15.7 milligram (4.75 * 10 ^-5Mole),

Methyl methacrylate=1.87 grams,

(CH ₃) ₂C (Br) CO ₂Ethyl=18.7 milligrams (9.58 * 10 ^-5Mole),

Oil bath temperature=70 ℃.

Experimental result table (standard P MMA)

Example	Polymerization reaction time (hour)	Yield (%)	Mn theory (gram/mole)	Mn tests (gram/mole)	?? Mw/ Mn
						?23 ?24 ?25	?47 ?3.5 ?4.5	59 43.7 25	??11500 ??8500 ??4870	??13550 ??10400 ??7500	??1.25 ??1.19 ??1.23

Example 26

Cinnamic bulk polymerization:

Repeat operation, but implement bulk polymerization as example 1

[Ni{2,6-[CH ₂N (CH ₃) ₂] ₂C ₆H ₃Br]=43 milligram (1.3 * 10 ^-4Mole),

Vinylbenzene=0.9 gram,

[(C ₆H ₅) CH (CH ₃) Cl]=6.11 milligram (4.35 * 10 ^-5Mole),

Polymerization reaction time=63 hour,

Oil bath temperature=90 ℃.

Mn tests=20600 gram/moles;

Mn theory=13950 gram/moles; Earning rate=67%;

Mw/ Mn=1.55 (standard P S).

Example 27

The bulk polymerization of n-BMA:

The operation of weight such as example 1, but implement bulk polymerization

[Ni{2,6-[CH ₂N (CH ₃) ₂] ₂C ₆H ₃Br]=33.8 milligram (10 ^-4Mole),

N-BMA=1.78 grams,

(CH ₃) ₂C (Br) CO ₂C ₂H ₅=17.47 milligram (8.95 * 10 ^-5Mole),

Polymerization reaction time=5 hour,

Oil bath temperature=95 ℃.

Mn tests=21400 gram/moles;

Mn theory=18500 gram/moles; Earning rate=93.2%;

Mw/ Mn=1.14 (standard P MMA).

Example 28 (Comparative Examples)

Repeat operation, but do not make the propellant compound (CCl of free radical as example 2 ₄)

[[Ni{2,6-[CH ₂N (CH ₃) ₂] ₂C ₆H ₃Br]]=43.7 milligrams,

Methyl methacrylate=0.936 gram,

Toluene=0.4 milliliter,

CH ₃CN=1.64 milligram (4 * 10 ^-5Mole),

Polymerization reaction time=22 hour,

Oil bath temperature=78 ℃.

Yield=15%,

Mn tests=245000 gram/moles;

Mn theory=3500 gram/moles;

Mw/ Mn＝3.1。

Example 29 (Comparative Examples)

Repeat operation as example 2, but catalyzer of no use:

Methyl methacrylate=0.936 gram,

CCl ₄=6.16 milligram (4 * 10 ^-5Mole),

CH ₃CN=1.64 milligram (4 * 10 ^-5Mole),

Toluene=0.4 milliliter,

Polymerization reaction time=22 hour,

Oil bath temperature=78 ℃.

Yield=0%,

Example 30-32 relates under the condition that AIBN participates in reacting, the bulk polymerization of methyl methacrylate.

Example 30

Repeat operation as example 1, comprising following component:

[Ni{2,6-[CH ₂N (CH ₃) ₂] ₂C ₆H ₃Br]=75.1 milligram (1.83 * 10 ^-4Mole),

AIBN=9.1 milligram (5.54 * 10 ^-5Mole),

Methyl methacrylate=0.936 gram,

Polymerization reaction time=45 hour,

Oil bath temperature=85 ℃.

Mn tests=7800 gram/moles;

Mn theory=5650 gram/moles;

Yield=67.3%;

Mw/ Mn=1.2 (standard P MMA).

Example 31

Repeat operation as example 30

[Ni{2,6-[CH ₂N (CH ₃) ₂] ₂C ₆H ₃Br]=20.5 milligram (5 * 10 ^-5Mole),

AIBN=3.77 milligram (2.3 * 10 ^-5Mole),

Methyl methacrylate=0.936 gram,

Polymerization reaction time=48 hour,

Oil bath temperature=85 ℃.

Mn tests=27500 gram/moles;

Mn theory=13700 gram/moles; Yield=68%;

Mw/ Mn=1.06 (standard P MMA).

Example 32

At [Ni{2,6-[CH ₂N (CH ₃) ₂] ₂C ₆H ₃O ₂CCF ₃] participate under the condition of reaction the Polymerization of Methyl reaction

[Ni{C ₆H ₃[CH ₂N (CH ₃) ₂] ₂-2,6}O ₂CCF ₃]=0.116 gram (3.19 * 10 ^-4Mole),

(CH ₃) ₂C (Br) CO ₂Ethyl=51.88 milligrams (2.65 * 10 ^-4Mole),

Methyl methacrylate=0.56 gram,

Toluene=1 milliliter,

Polymerization reaction time=45 hour,

Oil bath temperature=80 ℃.

Mn tests=2600 gram/moles;

Mn theory=2100 gram/moles; Yield=100%;

Mw/ Mn=1.3 (standard P MMA).

Example 33

The bulk polymerization of methyl methacrylate:

Repeat operation, but implement bulk polymerization as example 32:

[Ni{2,6-[CH ₂N (CH ₃) ₂] ₂C ₆H ₃O ₂CCF ₃]=0.116 gram (3.19 * 10 ^-4Mole),

(CH ₃) ₂C (Br) CO ₂C ₂H ₅=17.38 milligram (8.91 * 10 ^-5Mole),

Methyl methacrylate=1.49 grams,

Polymerization reaction time=20.5 hour,

Oil bath temperature=7O ℃.

Example 34

The bulk polymerization of methyl methacrylate repeats the operation as example 33, but polymerization reaction time is 28 hours

Experimental result (standard P MMA)

Example	Yield (%)	Polymerization reaction time (hour)	Mn theory (gram/mole)	Mn tests (gram/mole)	? Mw/ Mn
						?33 ?34	??39 ??48	?20.5 ?28	???7155 ???8900	??13500 ??16500	?1.25 ?1.21

Example 35

Again add the example of same monomer:

This example shows according to method of the present invention there is not termination reaction.It shows: after first sequence polyreaction, if add an amount of monomer in addition, just can add monomer again.

[Ni{2,6-[CH ₂N (CH ₃) ₂] ₂C ₆H ₃Br]=43.5 milligrams

Methyl methacrylate=0.936 gram (first dosage)

CCl ₄=6.16 milligram (4 * 10 ^-5Mole)

The milliliter of toluene=O.4,

CH ₃CN=1.64 milligram (4 * 10 ^-5Mole),

Polymerization reaction time=22 hour,

Oil bath temperature=78 ℃.

Yield=80%,

Mn tests=12300 gram/moles;

Mw/ Mn＝1.16。

Add the monomer of second dosage then, and proceed polyreaction:

Methyl methacrylate=0.936 gram

Polymerization reaction time=23 hour,

Oil bath temperature=78 ℃

Yield=85%; Mn experiment (multipolymer)=22800 gram/mole;

Mw/ Mn＝1.25。

Example 36

Again add the example of methyl methacrylate:

First preface is drawn:

[Ni{2,6-[CH ₂N (CH ₃) ₂] ₂C ₆H ₃Br]=63 milligram (2.2 * 10 ^-4Mole),

Methyl methacrylate=0.936 gram,

(CH ₃) ₂C (Br) CO ₂C ₂H ₅=18.8 milligram (9.6 * 10 ^-5Mole),

Toluene=1 milliliter,

Polymerization reaction time=45 hour,

Oil bath temperature=80 ℃.

Yield=94%,

Mn tests=12250 gram/moles; Mn theory=9700 gram/moles;

Mw/ Mn=1.09 (standard P MMA).

Second sequence:

Methyl methacrylate=0.936 gram,

Toluene=1 milliliter,

Polymerization reaction time=47 hour,

Oil bath temperature=80 ℃.

Yield=100%,

Mn tests=27800 gram/moles; Mn theory=19400 gram/moles;

Mw/ Mn=1.12 (standard P MMA).

Example 37

The example of the block copolymerization reaction of n-BMA and methyl methacrylate:

First sequence: bulk polymerization

[Ni{2,6-[CH ₂N (CH ₃) ₂] ₂C ₆H ₃Br]=0.141 gram (4.2 * 10 ^-4Mole),

N-BMA=1.78 grams,

(CH ₃) ₂C (Br) CO ₂C ₂H ₅=33.94 milligram (1.74 * 10 ^-4Mole),

Polymerization reaction time=29 hour,

Oil bath temperature=60 ℃.

Yield=100%,

Mn tests=11100 gram/moles; Mn theory=10300 gram/moles;

Mw/ Mn=1.18 (standard P S).

Second preface is drawn:

Methyl methacrylate=1.87 grams,

The THF=3 milliliter,

Polymerization reaction time=42 hour,

Oil bath temperature=60 ℃.

Yield=70%,

Mn tests=23200 gram/moles; Mn theory=17800 gram/moles;

Mw/ Mn=1.15 (standard P S).

Claims (23)

1, the monomeric in check radical polymerization or the process for copolymerization of (methyl) propenyl and/or vinyl, temperature it is characterized in that under can be reduced to 0 ℃ temperature condition, in the presence of the initiating system that comprises a radical generation compound and at least a catalyzer, above-mentioned at least a monomer is carried out body, solution, emulsion or suspension polymerization or copolymerization, this catalyzer is made up of the metal complexes that contains a ligand, and the structure of this ligand is as follows:

[4-R ³-2，6-(CH ₂NR ¹R ²) ₂C ₆H ₂] ^-??????????????????(I)

Wherein:

R ¹And R ²Can be identical or different, represent a side chain or straight chain C ₁-C ₄Alkyl, or phenyl, perhaps a R ¹And R ²Form a cyclammonium with the nitrogen-atoms that their connect, perhaps two R randomly ²Together, form a polymethylene bridge,

R ³Represent a hydrogen atom, alkyl, or benzyl, or power a son or an electrophilic functional group.

2, according to the method for claim 1, the ligand that it is characterized in that the catalyzer that polyreaction or copolymerization are used has following one of them chemical general formula

Wherein:

R ¹, R ²With R ³Limit as described above; M is the integer of 7-10.

3, according to the method for any one claim in the claim 1 and 2, the catalyzer that it is characterized in that polyreaction has following one of them chemical general formula:

Wherein,

R ¹, R ², R ³Limit as described above;

M represents a transition metal, the metal of group VIII on the element classification periodictable especially, Ni for example, Pd, Pt, Co, Rh, Ir, Fe, Ru and Os;

X represents monatomic or polyatomic anionic group, preferably halogen atom, nitro, nitrate radical, a R ⁴COO ^-, R wherein ⁴Expression hydrogen atom, C ₁-C ₁₄Alkyl, CF ₃Or CCl ₃, perhaps R ⁵SO ₃ ^-, R wherein ⁵Represent a C ₁-C ₁₄Alkyl or CF ₃

N represents 0,1 or 2 integer;

L represents the stablizer ligand of Lewis base type, preferred pyridyl, phosphine (phosphuret-(t)ed hydrogen) or phosphite group.

4, require the method for any one claim among the 1-3 according to aforesaid right, it is characterized in that: in above-mentioned chemical formula (I)-(V),

R ¹And R ²Represent methyl, ethyl, sec.-propyl, tertiary butyl and a phenyl separately, or form a pyrrolidyl or proline(Pro) ring, perhaps randomly make this two R with the nitrogen-atoms that they are connected ²Form a polymethylene bridge together;

R ³Represent a hydrogen atom, chlorine atom or C ₁-C ₅Alkyl, benzyl or cyano group, nitro, amino (primary, secondary, uncle's type), C ₁-C ₅Alkoxyl group, benzyloxy, amide group, acyl group or imido grpup.

5,, it is characterized in that this catalyzer is the R that is stated from or is engaged in this ligand according to the method for claim 3 ³On the substituent organic or inorganic group, preferably on the polymeric groups that is selected from polysilane or polysiloxane.

6,, it is characterized in that this metal M is Ni according to the method for claim 3 ^II, Ni ^III, Pd ^II, Pt ^II, Ru ^IIOr Fe ^III

7,, it is characterized in that this catalyzer is [Ni{2,6-[CH according to the method for any one claim among the claim 3-6 ₂N (CH ₃) ₂] ₂C ₆H ₃Br], [Ni{2,6-[CH ₂N (CH ₃) ₂] ₂C ₆H ₃Cl] or [Ni{4-CH ₃O-2,6-[CH ₂N (CH ₃) ₂] ₂-C ₆H ₂Br].

8, according to the method for any claim among the claim 1-7, the generation compound that it is characterized in that this radical is a halogen compounds, and described compound is activated by power supply of this halogen atom of alpha position compound or a plurality of these carbon of halogen atom and/or electrophilic effect.

9,, it is characterized in that this radical generation compound is the simple function group halogen compounds that is selected from as shown in following according to the method for claim 8

A) have the haloform or the tetrahalomethanes CYZ of following chemical formula ₃, Y=Cl wherein, Br or H, Z=Cl or Br;

B) has the trichloromethyl derivative R of following chemical formula ⁶CCl ₃, R wherein ⁶Represent a phenyl, benzyl, benzyloxy, acyl group, alkyl wherein contains 1-14 carbon atom, ethyl OC (O), CH ₃, base, CF ₃Or NO ₂

C) have the alkylogen of following chemical formula:

Wherein, R ⁷, R ⁸And R ⁹Represent a hydrogen atom, C separately ₁-C ₁₄Alkyl or aromatic base, R ¹⁰Be C ₁-C ₁₄Alkyl, phenyl or isocyanate group, Q represents Cl, Br, OOCCF ₃Or O ₃SCF ₃

D) have the alkylogen of following chemical formula:

Wherein, R ¹¹And R ¹²Being identical or inequality, can be a C ₁-C ₁₄Alkyl or primary alconol base-CH ₂OH, R ¹³Be a hydroxyl, nitro, amino (replacement or unsubstituted), C ₁-C ₁₄Alkoxyl group, acyl group, carboxylic acid, ester, and Q limits as described above;

E) on alpha position by halogenated lactone or lactam compound, α-bromo-Alpha-Methyl-gamma-butyrolactone and α-bromo-γ-Wu Neizhi for example;

F) benzyl halide of following formula:

R wherein ¹⁴Represent a hydrogen atom, C ₁-C ₁₄Alkyl, or carboxylic acid, ester, nitrile or a ketone groups, R ¹⁵Represent a hydrogen atom or C ₁-C ₁₄Alkyl, hydroxyl, acyl group, amine, nitro, C ₁-C ₁₄Alkoxyl group or sulfonate group, Q are to limit as described above;

G) N-halo succinimide and N-halo phthalimide,

H) has chemical formula R ¹⁶SO ₂The heteroaryl-alkylsulfonyl halides of V, wherein ¹⁶Represent a C ₁-C ₁₄Alkyl, V are chlorine or bromine atoms.

10, according to the method for claim 8, it is characterized in that this radical generation compound is the difunctionality base, and by two aforesaid c)-radical generating group of h) monofunctional formed, they are connected by a methene chain unit or phenyl ring (preferably position on) betwixt, by the monochloroacetic acid acid anhydride, connected by chlorine difluoro acetic anhydride, or by aforesaid a) with b) haloform that is limited or the derivative of tetrahalomethanes or a kind of trichloromethyl be connected.

11, according to the method for claim 8, it is characterized in that this radical generation compound is a multiple functional radical, and by at least three aforesaid c)-radical generating group of h) monofunctional formed, wherein connected by a phenyl ring or aforesaid a) specified haloform, tetrahalomethanes between them.

12,, it is characterized in that this radical generation compound is tetracol phenixin, ethyl trichloroacetate, 2-bromo-ethyl isobutyrate according to the method for claim 9.

13,, it is characterized in that this radical generation compound is sodium trichloroacetate, Tricholroacetic Acid potassium, chlorine two sodium fluoroethanoates, chlorine difluoro Potassium ethanoate and Sodium.alpha.-chloroacetate according to the method for claim 8.

14,, it is characterized in that this radical generation compound is selected from superoxide and azo-compound, dibenzoyl superoxide or 2 particularly, 2 '-azo-two isopropyl cyanides according to the method for any one claim among the claim 1-7.

15,, it is characterized in that preferably under 50 ℃-110 ℃ temperature condition, carrying out described polymerization or copolymerization at 0 ℃-150 ℃ according to the method for any one claim among the claim 1-14.

16, according to the method for any claim among the claim 1-15, it is characterized in that above-mentioned polymerization or copolymerization carry out in the presence of at least one polar additive, this polarity is added agent and is selected from acetonitrile, water, pyridine, tetrahydrofuran (THF), diethyl ether, dimethyl sulfoxide (DMSO), acetone and composition thereof.

17,, it is characterized in that the mol ratio of this catalyzer and radical generation compound is 0.01-100, preferred 0.1-5 according to the method for any claim among the claim 1-16.

18, according to the method for any one claim among the claim 1-17, it is characterized in that the mol ratio of these one or more monomers and catalyzer is 1-10,000, preferred 50-2000.

19, according to the method for any one claim among the claim 1-18, the mol ratio that it is characterized in that polar additive and catalyzer is 0-100, preferred 0-40.

20,, it is characterized in that this polymerizable or copolymerizable monomer comprise a monomer at least, are selected from methacrylic ester, acrylate, aromatic ethylene radical derivative and vinyl acetate according to the method for any one claim among the claim 1-19.

21,, it is characterized in that this monomer is selected from methyl methacrylate, Jia Jibingxisuanyizhi, n-BMA, vinyl cyanide and vinylbenzene according to the method for claim 20.

22, according to the method for any one claim among the claim 1-21 prepared polymkeric substance or multipolymer, it is characterized in that its dispersion amount Mn=400-1,000,000 gram/mole, its polymolecularity Mw/ Mn＜2.

23, according to the prepared segmented copolymer of method of any one claim among the claim 1-21, it is characterized in that its molecular weight Mn=400-1,000,000 gram/mole, and its polymolecularity Mw/ Mn＜2.