Method for preparing styrene polymers

FIELD: chemistry of polymers, chemical technology.

SUBSTANCE: invention describes a method for preparing styrene polymers by emulsion polymerization reaction in the presence of emulsifying agent and cobalt-organic initiating agent with tridentate ligands alkyl-{2-[(2-aminoethyl)imino]pent-3-ene-4-olate}(1,2-ethanediamine)cobalt (III) halides. As an initiating agent methods involves using a mixture consisting of initiating agent with alkyl ligand of normal structure and initiating agent with alkyl ligand of branched structure wherein their the sum concentration is 0.05-0.2 mas. p. per 100 p. p. of monomer and their ratio is from 2:1 to 9:1. The process is carried out at temperature 10-80°C and pH 4-10. Invention provides reducing the inductive period and possibility for using monomers with industrial treatment degree, i. e. stabilizing agent-containing monomers.

EFFECT: improved method for preparing.

5 cl, 1 tbl, 9 ex

 

The invention relates to the field of polymer chemistry, and in particular to methods for producing polymers of styrene and its copolymers with other vinyl monomers and danami.

A method of obtaining polystyrene latex emulsion polymerization in the presence of complexes of alkylate(III) tridentate ligands as initiators of polymerization (A.S. USSR №1816764, bull. 19 from 23.05.93). However, when using this method, there is an induction period of about 0.5 to 1 hour, which increases the total time of polymerization.

The closest in technical essence and the achieved result is a method of producing polymers of styrene by emulsion polymerization in the presence of an emulsifier and a radical initiator, and the initiator used complexes of alkylate(III) tridentate ligands (RF Patent 2070202, bull. No. 34 from 10.12.96). However, when using this method also observed a significant induction period, increasing the duration of the process. In addition, this process uses purified from stabilizer monomer, while in conditions of industrial production, it is desirable to avoid the need for purification of the monomer from the stabilizer.

The stabilizers of polymers (for example, hydroquinone and tert-butylpyrocatechol) are inhibitors of radical the processes, including radical polymerization. Therefore, the presence of the stabilizer in the monomer leads to a prolonged (up to several hours) induction period, significantly increasing the total time of polymerization, and therefore, additional energy costs. In this part of the initiator is spent on unproductive interaction with the inhibitor, resulting in reduced conversion of monomer.

Object of the invention is the improvement of the technology of emulsion polymerization of unsaturated monomers, namely the reduction of induction period, and the use of monomers of industrial purity, i.e. containing the stabilizer.

This technical result is achieved by the fact that obtaining polymers of styrene by the method of emulsion polymerization is carried out in the presence of emulsifier and the mixture cobaltorganic the initiators of the General formula I (symbolic formula[RCo(acacen)(en)]Br), where R2-C16-alkyl, and according to the invention as an initiator, a mixture of such initiators with alkyl ligand branched structure and an alkyl ligand normal structures (complexes Ib and Ia, respectively) at a ratio of 1:2 to 1:9, respectively, and their total concentration is 0.05 -0,2 parts by weight per 100 wt. including the monomer. Specifically, in a method of producing poly is ' according to the invention as an initiator Ib use complex with ISO-propyl, tsiklogeksilnogo or second-aktiline ligand.

The polymerization or copolymerization is carried out at a temperature of 10-80°and pH 4-10.

Comparative analysis of the prototype allows us to conclude that when carrying out emulsion polymerization of unsaturated monomers for the first time used a mixture of initiators - complexes of cobalt with tridentate Schiff base and alkyl ligands normal and branched structures in a wide range of ratios between them.

The comparison with the known technical solutions (A.S. USSR 1816764, RF patent 2070202) showed that the use of a mixture of the above initiators allows you to completely eliminate or significantly reduce the induction period emulsion polymerization even when using monomers containing a stabilizer, and in some cases increase the conversion rate of the monomer.

Synthesis of complexes I - (alkyl{2-[(2-amino-ethyl)imino]Penta-3-EN-4-OST}(1,2-amandemen)cobalt(III) bromide (symbolic formula [RCo(acacen)(en)]Br), as well as their main characteristics are described in the patent of the Russian Federation 2070202. the pH of the emulsion system in the polymerization process is supported by a well-known buffer systems.

The invention is illustrated by the following examples.

Example 1 (prototype)

In the reactor with stirrer mix 100 wt. including styrene, purified twice re what odensala under vacuum, with a water phase containing 4 wt. including pentanesulfonate sodium (E-30), 0.1 wt. including the initiator complex Ia with ethyl ligand ([C2H5Co(acacen)(en)]Br) and 200 wt. including water. The process is carried out under stirring in nitrogen atmosphere at a temperature of 15°C and pH 7 for 5.5 hours until the conversion of 94%. The induction period is 50 minutes

Example 2 (comparative)

In the reactor with stirrer mix 100 wt. including styrene, containing 0.01% of hydroquinone, with an aqueous phase containing 4 wt. including E-30, 0.1 wt. including the initiator complex Ib with ISO-propyl ligand ([(CH3)2SNCO(assep)(EP)]EDD) and 200 wt. including water. The process is carried out under stirring in nitrogen atmosphere at a temperature of 15°C and pH 7 for 3 hours to a conversion of 65% (the process does not occur). The induction period is 10 minutes

Example 3 (invention)

In the reactor with stirrer mix 100 wt. including styrene, containing 0.01% of hydroquinone, with an aqueous phase containing 4 wt. including E-30, the initiator comprising of 0.075 wt. including complex Ia with ethyl ligand ([C2H5With(assep)(EP)]EDD) and 0.025 wt. including complex Ib with ISO-propyl ligand ([(CH3)2SNCO(assep)(EP)]EDD), and 200 wt. including water. The process is carried out under stirring in nitrogen atmosphere at a temperature of 15°C and pH 7 for 3 hours to a conversion of 97%. The induction period is missing.

Examples 4-9 (invention)

Polymerize the Oia conducted similarly to examples 1-3, to change the type and purity of the monomers, temperature, pH, concentration of ingredients and the use of a mixture of complexes I with different structures and different ratios between them.

The application for the patent of the Russian Federation "Method of producing polymers of styrene"

1. A method of producing polymers of styrene by emulsion polymerization in the presence of emulsifier and coalitionism initiator of General formula I

where R is C1-C16-alkyl,

characterized in that as the initiator, a mixture consisting of the above stated coalitionism initiator with alkyl ligand (R) branched structure and the same initiator with alkyl ligand (R) normal structure, at a ratio of 1:2 to 1:9, respectively, and their total concentration is 0.05 to 0.2 parts by weight per 100 parts by weight of monomer.

2. A method of producing polymers of styrene under item 1, characterized in that as the initiator with alkyl ligand branched structures use complexes I, where R is isopropyl, cyclohexyl or second-octyl.

3. A method of producing polymers of styrene according to claims 1 to 3, characterized in that the preferred ratio between the initiator with alkyl ligand branched structure and an initiator with alkyl ligand is normally the first structure is a ratio of 1:3.

4. A method of producing polymers of styrene according to claims 1 to 4, characterized in that the process is carried out at a temperature of 10-80°C.

5. A method of producing polymers of styrene according to claims 1 to 5, characterized in that the process is carried out at pH 4-10.



 

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FIELD: organometallic polymerization catalysts.

SUBSTANCE: invention relates to alkylcobalt(III) complexes with tridentate Schiff's bases wherein alkyl ligand contains functional group, notably hydroxyl, carboxyl, or amino group, in accordance with general formula:

(I),

in which W represents two-moiety unsaturated hydrocarbon bridge group expressed by formula =C(H)=C(CH3)- (propene-1,2-diyl) or o-C6H4 (o-phenylene); X is OH, NH2 or COONa; Y monovalent anion: Cl-, Br-, NO3- or ClO4-; and Z polymethylene bridge group (CH2)n, wherein n=3-11 when X = OH or NH2 and n=2-11 when X = COONa. The complex are used as initiators of emulsion polymerization and copolymerization of diene and vinyl monomers to produce reactive bifunctional oligomers and polymers with terminal functions, which oligomers and polymers are suitable for further conjugation with corresponding reagents.

EFFECT: extended choice of specific polymerization catalysts.

3 tbl, 30 ex

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< / BR>
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The invention relates to plastics industry, and in particular to methods of producing foam and suspension of polystyrene polymerization in aqueous suspension

FIELD: organometallic polymerization catalysts.

SUBSTANCE: invention relates to alkylcobalt(III) complexes with tridentate Schiff's bases wherein alkyl ligand contains functional group, notably hydroxyl, carboxyl, or amino group, in accordance with general formula:

(I),

in which W represents two-moiety unsaturated hydrocarbon bridge group expressed by formula =C(H)=C(CH3)- (propene-1,2-diyl) or o-C6H4 (o-phenylene); X is OH, NH2 or COONa; Y monovalent anion: Cl-, Br-, NO3- or ClO4-; and Z polymethylene bridge group (CH2)n, wherein n=3-11 when X = OH or NH2 and n=2-11 when X = COONa. The complex are used as initiators of emulsion polymerization and copolymerization of diene and vinyl monomers to produce reactive bifunctional oligomers and polymers with terminal functions, which oligomers and polymers are suitable for further conjugation with corresponding reagents.

EFFECT: extended choice of specific polymerization catalysts.

3 tbl, 30 ex

FIELD: chemistry of polymers, chemical technology.

SUBSTANCE: invention describes a method for preparing styrene polymers by emulsion polymerization reaction in the presence of emulsifying agent and cobalt-organic initiating agent with tridentate ligands alkyl-{2-[(2-aminoethyl)imino]pent-3-ene-4-olate}(1,2-ethanediamine)cobalt (III) halides. As an initiating agent methods involves using a mixture consisting of initiating agent with alkyl ligand of normal structure and initiating agent with alkyl ligand of branched structure wherein their the sum concentration is 0.05-0.2 mas. p. per 100 p. p. of monomer and their ratio is from 2:1 to 9:1. The process is carried out at temperature 10-80°C and pH 4-10. Invention provides reducing the inductive period and possibility for using monomers with industrial treatment degree, i. e. stabilizing agent-containing monomers.

EFFECT: improved method for preparing.

5 cl, 1 tbl, 9 ex

FIELD: polymers, chemical technology.

SUBSTANCE: invention describes a method for preparing frothing polystyrene by polymerization of styrene for two stages. At the first stage forpolymerization is carried out in the presence of antipyrene, a chain growth regulator, benzoyl peroxide as a polymerization initiating agent. At the second stage the suspension polymerization is carried out in aqueous medium in the presence of polyvinyl alcohol as a stabilizing agent, chain growth regulator, tert.-butylperbenzoate as initiating agent and frothing agent. The forpolymerization stage is carried out in the presence of water and dicumyl peroxide as antipyrene synergist is added additionally, and O,O-tert.-myl-O-(2-hexyl)-monoperoxycarbonate is used a additional initiating agent in the following ratio of components relatively to styrene mass, %: benzoyl peroxide : O,O-tert.-myl-O-(2-hexyl)-monoperoxycarbonate : tert.-butylperbenzoate = (0.24-0.25):(0.04-0.06):(0.04-0.10), respectively. Method provides intensification of the styrene polymerization process, improvement of granulometric composition of preparing polystyrene and reducing specific energy consumptions in manufacturing frothing polymer granules.

EFFECT: improved preparing method.

3 ex

FIELD: hydrogenation-dehydrogenation catalysts.

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18 cl, 2 ex

FIELD: polymer production.

SUBSTANCE: object of invention are particle of foaming polystyrene showing improved foaming ability and strength. Process of invention comprises: (i) polymerization of mixture containing polystyrene granules, styrene monomer, cross-linking agent, foaming substance, poly(oxyethylenesorbitol monolaurate) added when degree of polymerization reaches 70-90% in amount 0.05 to 0.15 wt parts per 100 wt parts monomers, and polyethylene wax synthesized from formaldehyde in amount 0.05 to 0.2 wt parts per 100 wt parts monomers; and (ii) coating the mixture with containing substance. Described is also foaming polystyrene resin composition containing wax Sasol.

EFFECT: improved foaming ability and moldability, and increased strength.

8 cl, 1 tbl, 8 ex

FIELD: chemistry.

SUBSTANCE: described is a free-radical polymerisation method in which at least one polymerisable monomer reacts in the presence of at least one organic peroxide selected from a group, wherein the organic peroxide is obtained using a continuous method ex situ using closed plate heat exchanger. Described also is method for suspension polymerisation of vinyl chloride, as well as a method for suspension polymerisation of styrene in the presence of at least one organic peroxide selected from a group, wherein the organic peroxide is obtained using a continuous method ex situ using a closed plate heat exchanger. Described is a method for polymerisation of acrylic monomers in the presence of at least one organic peroxide selected from a group, wherein the peroxide is obtained using a continuous method ex situ using a closed plate heat exchanger. Described also is a free-radical polymerisation method in which a polymerisable monomer reacts in the presence of at least one organic peroxide selected from a group, wherein said method comprises steps (a)-(d) realised at the same place: a) obtaining a selected organic peroxide via a continuous method using a closed plate heat exchanger, b) feeding, if necessary, reaction mixture (a) into a purification apparatus, c) feeding the organic peroxide obtained at step (a) or step (b) into a polymerisation reactor, d) free-radical polymerisation of at least one polymerisable monomer in the presence of one or more organic peroxides fed at step (c). The invention also describes thermoplastic polymers and/or elastomers obtained using methods described above.

EFFECT: use, in free-radical polymerisation systems, of organic peroxides obtained directly where free-radical polymerisation takes place.

13 cl, 2 dwg, 3 ex

FIELD: chemistry.

SUBSTANCE: method of producing monodispersed carboxylated polymer microspheres in form of an aqueous suspension is characterised by that a solution in a vinyl monomer of a surfactant - α,ω-bis-(10-carboxydecyl)polydimethylsiloxane, containing from 6 to 60 siloxane links and taken in amount of 0.5-1.9%, or mixture thereof with polyoxyalkylene polysiloxane of formula , where m=8-64, n=4-8, p=15-20, q=15-20, in amount of 0.9-2.6% of the weight of the monomer, is intensely stirred in bidistilled water in the atmosphere of inert gas while heating the mixture to 50-75°C and volume ratio of monomer to water in the range of 1:(2-9), with preliminary addition into the reaction mass of 0.8-1.3% (of the weight of the monomer) radical polymerisation initiators - mixture of potassium persulphate and dinitrile of azo-bis-isobutyric acid or benzoyl peroxide, to form an oil-in-water emulsion, followed by polymerisation for 2-5 hours under the action of the initiator of a drop of the monomer to polymer particles, while raising temperature by 10°C per hour until the end of the process.

EFFECT: method of producing monodispersed carboxylated polymer microspheres with concentration of carboxyl groups on the surface of the microspheres, which meets requirements for immunoreagent carriers; the suspension is stable in physiological solutions.

1 cl, 5 dwg, 11 ex

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