A method of obtaining a polymer

 

(57) Abstract:

Usage: to obtain polystyrene with a high degree of syndiotactic used for the manufacture of films, sheets and foams. The essence of the invention: a method of obtaining a polymer with a stereoregular structure, exceeding by more than 50% syndiotactic racemic triad at 25 - 70 by the polymerization of styrene, n-methylstyrene or tert-butylstyrene in the presence of a titanium containing catalyst of the General formula , where Cp is cyclopentadiene or pentamethylcyclopentadiene: x is methyl, benzyl or trimethylsilylmethyl, A--Tetra(pentafluorophenyl) borate, at a molar ratio of monomer: titanium from 3700: 1 to 125700: 1. 3 table.

The invention relates to a method of polymerization vinylaromatic monomers, such as styrene, to obtain polymers having a high degree of syndiotactic. Such polymers can be successfully used for the manufacture of solid products, such as moldings, films, sheets and the foam by molding, casting or similar methods.

A method of obtaining polymers [1] from vinylaromatic monomers having a stereoregular structure with syndiotactic more than what this method uses a catalyst, representing the products of the interaction of compounds of titanium and alyuminiiorganicheskikh connection, preferably polymethylsiloxane. However, the known method requires the use of large quantities of polymethylsiloxane, which is expensive and requires expensive purification systems of the polymer to remove the remaining catalyst components due to the use of large quantities of polymethylsiloxane.

The invention provides a method of obtaining a high-purity polymer having a stereoregular structure, which is more than 50% higher than syndiotactic racemic triad, by the polymerization vinylaromatic monomer in the presence of a catalyst comprising a complex metal formula

[Cp. TiX2]+A-wherep- represents cyclopentadienyls group or pentamethyl cyclopentadienyls group;

X is methyl, benzyl or trimethylsilylmethyl;

AND-- gecoordineerde compatible anion salt of the acid of Barnstead, in particular Tetra (pentafluorophenyl)borate.

The method is carried out at a molar ratio of monomer: titanium from 3700: 1 to 125700: 1 at 25-70aboutC.

Effective the care, at least two components, discussed below. The first component is a derivative of titanium, comprising at least one Deputy, which is connected with the cation of the second component or alternatively subjected to oxidative activation. The first component capable of forming a cation coordination number which is one less than its valence. The second component is a salt of the acid Bronsted and necoordonarea compatible anion or alternative salt oxidizing cation and necoordonarea compatible anion.

Examples of derivatives of titanium compounds include Tetra-neopentylene, (Cyclopentadienyl)-dimethyl(isopropoxide), (cyclopentadienyl)dibenzyl(UseProxy) titanium, bis-(2,6-aminobutiramida-4-methyl(phenoxy)dibenzoylmethane, bis- (2,4,6-trimethylphenol)debenzylation, bismethoxy(phenylmethyl)titanium, trypanosomatidae, 4-(1-methyl-1)-4-methoxyphenyl(ethyl) phenoxycarbonylamino, the hydride transition, cyclopentadienylcobalt, cyclopentadienylzirconium etc.

Compounds that are effective as of the second component upon receipt of the catalyst used in building the invention may, in compliance is steamy gecoordineerde anion. In accordance with another variant of such compounds include oxidizing cation and a compatible gecoordineerde anion. Preferred anions that contain a single coordination complex.

Second components, comprising boron, are particularly useful for preparation of catalysts and can be represented by the following General formula:

[L-H]+[BO4] -in which L represents a neutral Lewis base;

[L - H]+- represents an acid Bronsted;

In - is boron in a valence equal to 3.

Illustrative, but not limiting examples of boron compounds which can be used as the second component include trialkylamine ammonium salts, such as tetraphenylboron of triethylamine, tetraphenylboron of Tripropylamine tetraphenylborate three(n-butyl)ammonium Tetra(n-collborate) trimethylammonium, tetracosapentaenoic of tributylamine, tetrakis-2,4-dimethylphenylamine of Tripropylamine, tetrakis-3,5-dimethylphenylamine of tributylamine, tetracy-3,5-dateformatlength of triethylamine and similar compound. Also acceptable are the salt of N, N-dialkylanilines, such as tetraphenylboron N, N-dimethylaniline">

Typically, the catalyst can be obtained by connecting two components in an appropriate solvent at a temperature of from - 100aboutWith up to 300aboutC. Catalytic system can also be formed on the spot, if its components are introduced directly into the polymerization process when used in the specified polymerization process suitable solvent or diluent containing monomer. However, preference is given to the formation of the catalyst in a separate stage in an appropriate solvent prior to its introduction into the stage of polymerization. The components of the catalyst are generally sensitive to moisture and oxygen, so they must be converted and transferred in an inert atmosphere, such as nitrogen, argon or helium.

The solvents are hydrocarbons with straight or branched chain, such as C6-12-alkanes (hexane, heptane, octane and the like substances); (C6-12cyclic and alicyclic hydrocarbons such as cyclohexane, Cycloheptane, methylcyclohexane, methylcycloheptane and similar compounds WITH6-12aromatic and alkyl substituted aromatic compounds such as benzene, toluene, xylene, decalin and similar compounds, and mixtures thereof.

The polymerization can be performed under conditions of suspension polymerization or polymerization in mass, including solid-phase polymerization. The polymerization is carried out at a temperature from 0 to 160aboutC, preferably from 25 to 100aboutC, preferably from 30 to 80aboutWith over a period of time sufficient to obtain the target polymer. The reaction time is from one minute to 100 hours, preferably from 1 to 10 hours the Polymerization is carried out at a pressure below atmospheric and at a pressure above atmospheric, in particular at a pressure in the range from 1 to 500 psig (100-3400 kPa). Preference is given to atmospheric or low pressure, for example (100-140 kPa).

The polymerization can be performed in the presence of an inert diluent or solvent or without it. Examples of appropriate diluents or solvents include6-20aliphatic, cycloaliphatic, aromatic and halogenated aliphatic or aromatic hydrocarbons, and mixtures thereof. Preferred diluents include6-10alkanes, toluene and mixtures thereof. Especially preferred diluent for the polymerization of imperialism". The solvent is used in amounts providing the monomer concentration is from 5 to 100 wt. % .

The molar ratio of vinyl aromatic monomer to catalyst (expressed as metal) may be from 100: 1 to 500,000: 1, preferably from 3700: 1 to 125700: 1. When using a solvent, the catalyst may be used in concentrations from 10-7up to 10-1mol per liter of solvent.

Used monomers and solvents are of sufficiently high purity so as to avoid deactivation of the catalyst. You can use any acceptable method of cleaning monomer, such as processing, leading to loss volatility, at low pressure, contacting the molecular sieve or alumina having a large surface area, deaeration, etc. in Addition, the reaction mixture you can add a small amount trialling aluminum compounds or similar acceptor to protect the catalyst from deactivation of contaminating impurities present in the reaction mixture.

Purification of the polymer is much easier than when carrying out the known method, since the proposed method is not used polyalkyloxy that dinani is by solvent extraction, such as hot high-boiling chlorinated solvents, acids and bases, such as caustic, followed by filtration.

P R I m e R 1. Obtaining a catalyst.

Into the flask containing the suspension 0,343 g of Tetra(pentafluorophenyl)-borate three(ethyl)ammonium in 10 ml of toluene, add 0.10 g of trimethylsilylamodimethicone at room temperature. The resulting mixture was stirred for 10 h, and then heated to 45aboutC for 1 h the Precipitate was not observed, the mixture is a dark solution. The solvent which is toluene is distilled off under vacuum, resulting in a get a black solid. This solid is washed three times with 5 ml petroleum ether and dried in vacuum. The target product is the composition, structure, identified by13With NMR, has the formula

[CpTiMe2]+[B(C6F5)4]-< / BR>
Getting syndiotactic polystyrene.

In a dry container with a volume of 20 ml download 0.025 g (28 mmol) of the catalyst, and then add 10.0 g (to 102.9 mmol) of styrene. Tank cover gasket with PTFE coating and metal corrugated cover, polehereteroy 70aboutWith over 3 h, terminate the polymerization by adding methanol. The insoluble product is off-white color is washed with methanol and dried in vacuum conditions, gain of 3.32 g of the target polymer. The polymer is not dissolved in methylene chloride and other conventional solvents intended for atactic polystyrene.

The obtained polystyrene has a melting point of 268about(Using differential scanning calorimetry) and indictations more than 95% , as measured by13WITH NMR. The average molecular weight of the polymer is equal to 382000.

P R I m e R s 2-11. Reaction conditions are similar to example 1, except that the use of other catalysts and ratio of reagents. Use the catalyst are given in table. 1. The melting point of the crystalline polymers are determined by differential scanning calorimetry, DSC. Syndiotactic determined using13WITH NMR. The results are shown in table. 1, in which a - SMTT = = Tetra(pentafluorophenyl)borate of cyclopentadienylzirconium, (Cf Ti/ CH3)2+TB-), SVTW = Tetra(pentafluorophenyl)borate of cyclopentadienylzirconium (Cf Ti/ CH2C6H52Si(CH3)32+TB-), STOPS = Tetra(pentafluorophenyl)-borate of cyclopentadienylmagnesium (Cf Ti/ CH2C6H5)(OCH3) -+TN-);

b - add 2 ml of o-dichlorobenzene;

- add 2 ml of chloroform.

d is obtained from Tetra(Penaflor)borate of diisopropylethylamine;

e - nephropathy catalyst.

P R I m e R s 12-15. Reaction conditions analogous to example 1, except that the reaction mixture also contains trialkyllead connection of aluminum. Used catalysts are described in the table. 2. Catalysts receive in accordance with example 1 or in example 15) by contacting equimolar amounts of dibenzylethylenediamine with Tetra(pentafluorophenyl)borate ferrocene in toluene. A second capacitance connected styrene and trialkyl connection of aluminum in 1M solution of toluene). This solution is added to a vessel containing complex titanium and carry out polymerization. The results are shown in table. 2.

P R I m e R 16. Dry chamber with argon atmosphere in a dry container with a volume of 20 ml download 2.2 mg (4.4 mmol) of bis-(2,4,6 - trimethylphenol)dibenzoylmethane and 3.8 mg (4.4 mcal) Tetra (pentafluoroethyl)borate fer is itate formed a dark insoluble oily product. In the bubble add styrene (10 ml, which is 87.4 mmol) and carry out the polymerization. This polymer is not soluble in methylene chloride, methylethylketone and other conventional solvents intended for atactic polystyrene. The melting point of the crystalline polymer 259aboutS, which corresponds to the polymer, syndiotactic of which exceeds 90% .

P R I m e R s 17-22. Polymerization of p-methylstyrene and tert-butylstyrene, catalyzed Tetra(platterful)borate of pentamethylcyclopentadienyl.

Load the amount of dry degassed monomer with achievement of the molar relationship monomer listed in table. 3. Using a syringe add 205 μl 0,0055 M solution of catalyst comprising the reaction product obtained from pentamethylcyclopentadienyl, Tetra(pentafluorophenyl)borate decamethylferrocene and 5 equivalents of triisobutylaluminum in toluene at room temperature. Then the container is placed in a water bath with a temperature of 70aboutWith 1 hour the Polymerization terminated by adding methanol. The polymer is washed with methanol and dried under reduced pressure.

The melting temperature of the crystalline polymers determine posredstwom OBTAIN a POLYMER with a stereoregular structure, exceeding more than 50% syndiotactic racemic triad, by the polymerization vinylaromatic monomer in the presence of a titanium containing catalyst, characterized in that, in order to obtain high-purity polymer, as vinylaromatic monomer used styrene, n-methylsterol, tert-butalbiral or their mixture as catalyst using the catalyst of the General formula [CpTi X2]+A-< / BR>
where Cp- cyclopentadiene or pentamethylcyclopentadiene;

X is methyl, benzyl or trimethylsilylmethyl;

AND-- Tetra(pentafluorophenyl)borate,

when a molar ratio of monomer : titanium 3700 : 1 - 125700 : 1 and the process is conducted at 25 - 70oC.

 

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11 cl, 1 tbl, 45 ex

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10 cl, 1 tbl, 20 ex

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4 ex

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2 cl, 1 tbl

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21 cl, 3 tbl, 3 ex

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EFFECT: enabled production of copolymers, which have real random distribution of butadiene and isoprene units.

2 cl, 2 tbl

FIELD: polymerization processes.

SUBSTANCE: invention relates to two-component composition used to initiate curing of one or more polymerizable monomers that are cured when affected by free radicals, which composition consists of organoborane-amino complex and an isocyanate capable of destroying organoborane-amino complex, wherein equivalent ratio of amine nitrogen atoms to boron atoms ranges from more than 4.0:1 to 20.0:1. In another embodiment of invention, subject of invention is two-component composition for use as sealing materials, coatings, primers for modifying polymer surfaces, and as molded resins, which composition consists of component 1: organoborane-amino complex wherein ratio of amine nitrogen atoms to boron atoms ranges from more than 4.0:1 to 20.0:1; component 2: one or more monomers, oligomers, or polymers having olefinic instauration, which are able of being subjected to free-radical polymerization; and effective amount of an isocyanate, which can initiate dissociation of complex to free borane for initiation of polymerization of one or more monomers, oligomers, or polymers having olefinic instauration, provided that complex dissociation initiator is stored separately from complex until initiation of polymerization becomes desirable. Such compositions are handling safe, i.e. they are not self-inflammable, stable at or near ambient temperature and so they do not initiate polymerization at or near ambient temperature in absence of complex dissociation initiator. Polymerized composition show good cohesion and adhesion strength. Described are polymerizable composition polymerization process, method of gluing two or more substrates using polymerizable composition; method of modifying polymer surface having low surface energy using polymerizable composition, as well as coating and laminate containing polymerizable composition.

EFFECT: enlarged resource of polymerizable compositions and expanded application areas thereof.

10 cl, 2 dwg, 4 tbl

FIELD: polymerization catalysts.

SUBSTANCE: proposed catalytic system used for production of polybutadienes is based on at least one conjugated diene monomer; organophosphorus acid salt of one or several rare-earth metals, said salt being suspended in at least one inert aliphatic or alicyclic saturated hydrocarbon solvent; alkylation agent selected from trialkylaluminum and dialkylaluminum hydride, wherein molar ratio of alkylation agent to rare-earth metal salt(s) exceeds 5:1; and hydrogen donor selected from alkylaluminum halides excepting alkylaluminum sesquihalides. Catalytic system is characterized by that concentration of rare-earth metal(s) is at least 0.005 mole/L. Polybutadienes obtained according to invention have polydispersity index below 2.1 and Mooney viscosity ML (1+4) at 100°C below 40.

EFFECT: improved physicochemical characteristics of polybutadienes.

14 cl, 2 tbl, 7 ex

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