SU763363A1 - Method of preparing copolymers - Google Patents

Description

The invention relates to the field of producing copolymers that can be used in the production of materials for the paint industry as a film-forming agent: 5 substances in varnishes and varnishes.

A well-known technical solution is the method of polymerization of dienes (including piperylene with styrene) in bulk in the presence of Li-alkyl £ 1], 10 or polymerization at (-) 50-150 ° C of isoprene or piperylene with styrene in the presence of alphilic catalysts in a nitrogen atmosphere in aliphatic alicyclic or aromatic <5 solvents in the presence of a polymerization regulator [2].

A known method of polymerization of conjugated dienes (butadiene, isoprene, piperylene) or mixtures thereof with mono-20 measures (styrene, butene-1, etc.) in a hydrocarbon solvent at 4070 ° C in the presence of a catalyst: a) Na-organic compounds of the formula NaR, where R-C ^ u is alkyl and b) C ₄ . _u - 25

potassium tri-alcoholate. The diene polymers obtained by this method have a molecular weight in the range of 250001000000, more preferably 100000500000 C3]. thirty

However, the polymer obtained by the known method has a high molecular weight, which does not allow ^{1 to} use it as a film-forming material in the paint industry.

The closest technical solution is a method for producing copolymers by copolymerization of a mixture of styrene-containing xylene fraction of crude benzene - and piperylene-containing fraction with so Kip. 38-165 ° C, containing 33-40% trans-piperylene and 18-23% cis-piperylene fractions when heated 125-130 ° C in the presence of a catalyst - hyperysis [4].

The disadvantage of this method is that coatings based on these copolymers do not have sufficiently high physical and mechanical properties: these coatings dry in 72 hours, and stickiness remains, coating hardness is 0.08-0.12.

The purpose of the invention is to improve the physico-mechanical properties of the coating based on these copolymers.

This goal is achieved by the fact that in the method for producing copolymers * by copolymerizing a mixture of styrene-containing and piperylene-containing fractions by heating in the presence of catalyst I, .48.78-74.8% of the weight of the initial mixture of styrene rectification bottoms is used as styrene-containing fractions, as piperylene-containing - 24.7-48.78% of the weight of the initial mixture technical. piperylene containing 60.1-60.9% trans piperylene and 28.39-30.39% cispiperylene, and the process is carried out in an organic solvent medium in the presence of a Friedel-Crafts catalyst or zeolite at 80-200 ° FROM.

Technical piperylene is a by-product of SC production and has approximately the following composition, wt.%: 15 trans-piperylene cis-piperylene Amylene Isoprene Diethyl ether Cyclopentadiene

VAT product

60.1-60.9

28.39-30.39

7.01-7.42

2.16-2.76

0.1-0.06

0.1-0.4.

Styrene rectification (CORS) is a dark brown viscous liquid. VAT product contains the following substances, wt.%: Styrene 20-30, "x-methylstyrene 5-7; P> methylstyrene 0.5-1.8; naphthalene 0.1-0.5; diphenyl, diphenylmethane, dibenzyl-1-4, trans-stilbene 3-5, polystyrene 30-50, the rest is heavy oil.

Coatings based on the copolymers obtained according to the invention dry out in 3-6 hours and have a hardness of 0.30.5.

Example 1. 1.23 wt.% AlSC and 50 ml of toluene are charged into the reactor and stirred for 10-30 minutes. A mixture of wt.% 40 74.07 CORS and 24.7 wt.% Of technical piperylene is poured into the reactor in te. 1-2 hours. The temperature of the reaction mixture is 30 ° C. The process is carried out for 4-5 hours. The reaction mass is treated with isopropyl alcohol (in a ratio of 1: 1 by volume) in order to decompose the catalyst complex and isolate the polymer directly in the reactor. Then remove the solvent and low molecular weight compounds by vacuum distillation at a temperature in the mass of 180-200 ° C. A dark brown polymer with a molecular weight of 1100 is obtained.

Example 2. The experiment is carried out as in example 1 with a ratio of

tov, wt.%: VAT product 48.78 Piperylene 48.78 AI C1 _g 2.44 Molecular polymer mass 1500.) - Example 3. In reactor loading ut 2.44 wt.% AlCI-jH 50 ml of toluene and mix 10-30 min Mixture

48.78 wt.% Bottoms and '48, 78 wt.% Technical piperylene are transferred to the reactor within 1-2 hours. The temperature of the polymerization process is 40 ° C. Further processing is carried out according to example 1. The molecular weight of 1000.

Example 4. The reaction is carried out as described in example 1, with a ratio of components, wt.%: VAT residue 74.8 piperylene 24.96 ·, AlClij 0.249. The molecular weight of the polymer is 1100.

Example 5. The reaction is carried out according to example 1 at a temperature of 18-20 ° C and the ratio of components wt.%: VAT product 74.8, piperylene 24.96, AIC 0.249. The molecular weight of the polymer is 980.

Example 6. In the reactor is placed 2.44 wt.% Zeolite, still residue rectification of styrene '

48.78 wt.%, Technical piperylene

48.78 wt.% And stirred under heating at a temperature of 30-120 ° C for 5-10 hours, at a temperature of 120-160 ° C for 1015 hours and at a temperature of 160-200 ° C for 1015 hours. Then, unreacted products are distilled off at 180-200 ° C under vacuum. The resulting polymer was dissolved in xylene, and the catalyst was separated by filtration. The molecular weight of the polymer is 1300.

Example 7. In the reactor is placed 2.44 wt.% Zeolite, distillation distillation residue styrene 48.78 wt.%, Technical piperylene 48.78 wt.% And stirred with heating at a temperature of 80 ° C for 2 hours, at 120 ° C 3 hours, at 150 ° С - 4 hours, at 200 ° С -5 hours

Then unreacted products are distilled off at 180-200 ° C under vacuum. The molecular weight of the polymer is 1600.

The copolymers are dark brown hard resins with a softening point of the ring and ball method 65-125 ° C. From a 40% solution of resins in xylene (toluene), films are completely dried out in 3-6 hours with the formation of a smooth smooth shiny surface. The film hardness is 0.3-0.5 according to the pendulum device, the elasticity on the flexibility scale is 3-5 mm. ;

The structure of the obtained polymer was studied using IR spectroscopy. Spectra were recorded on IKS-22 in the region of 2000-700 cm ¹ in the form of a film of carbon tetrachloride. The obtained polymers basically have a styrene form (to a greater extent), which is confirmed by absorption in the frequency range 1595, 1480, 1440, 1152, 1023 cm ¹ and trans form (intense absorption in the region of 960 cm ¹ ).

A method for producing a polymer by reacting a still of distillation of styrene rectification with dienes contained in technical piperylene in the presence of a catalyst gives the following advantages:

- a low molecular weight polymer is synthesized, the solution of which in xylene or toluene is a varnish. Lacquer films have good decorative and protective properties)

- shows the way to use cheap waste from the production of SK plants)

- obtaining cheap paints and varnishes;

- the possibility of repeated use of the zeolite catalyst.

newer than these copolymers, 48.78-74.8% of the weight of the initial mixture of bottoms of styrene rectification is used as the styrene-containing fraction, and 24.7-48.78% of the weight of the initial mixture of technical piperylene containing piperylene-containing fraction.

60.1-60.9% of trans-piperylene and 28.3930.39% of cis-piperylene, and the process is carried out in an organic solvent in the presence of a Friedel-Crafts catalyst or zeolite at 80200 ° C.

Claims (4)

The invention relates to the field of producing copolymers that can be used in the manufacture of materials for a paint and varnish industry as a film-forming substance in drying oils and varnishes. A known technical solution is the method of polymerizing dienes (including piperylene with styrene) in the mass in the presence of L-alkyl tl 3, or polymerizing with (-) SO-ISO C isoprene or piperylene with styrene in the presence of alfilic catalysts in a nitrogen atmosphere in aliphatic alicyclic or aromatic solvents in the presence of a polymerization regulator 2. A known method for the polymerization of conjugated dienes (bootchen, isoprene, piperylene) or their mixture with monomers (styrene, butene-1, etc.) in a hydrocarbon solvent at 4070® C in the presence of a catalyst: a) Na-organic compounds of the formula NaR, where R is Ci., O is alkyl, and b) C. X. is potassium tert alcohol. The diene polymers obtained by this method have a molecular weight in the range of 25,000,100,000,000, preferably 100,000,500,000 cps. However, the polymer obtained by a known method has a high molecular weight, which does not allow its use as a film-forming material in paintwork lacquer. The closest technical solution is a method of obtaining copolymers by copolymerizing a mixture of styrene-containing xylene fraction of crude benzene and piperylene-containing fraction with so-called boiling point. 38-165 ° C, containing 33-40% trans-piperylene and 18-23% cis-piperylene - fractions when heated to 125-130 ° C in the presence of a catalyst - hyperise The disadvantage of this method is that coatings based on these copolymers have insufficiently high physicomechanical properties: these coatings dry out in 72 hours, with tackiness remaining, and the hardness of the coating is 0.08-0.12. The purpose of the invention is to improve the physicomechanical properties of the coating based on these copolymers. This goal is achieved by the fact that in the process of obtaining copolymers by copolymerizing a mixture of styrene-containing and piperylene-containing fractions with heating in the presence of a catalyst, 48.78-74.8% of the weight of the initial mixture of cubes of styrene rectification residues are used as the piperiline fraction of the mixture of styrene, and as a piperiline. - 24.7-48.78 by weight of the initial mixture technical. piperylene containing 60.1-60.9% trans-piperylene and 28.39-30.39% cis piperylene, and the process is carried out in medium organic solvent in the presence of a Friedel-Craftsa catalyst or zeolite at 80-200 ° WITH. Technical piperylene is a by-product of SC production and has approximately the following composition, wt.%: Trans-Piperi60, 1-60.9 28.39-30.39 cis-Piperylene 7.01-7.42 Amylenes 2.16-2 , 76 Isoprene Diethyl 0.1-0.06 Cyclopenta0, 1-0.4. The distillation product of styrene distillation (CORS) is a dark brown viscous liquid. The bottoms product contains the following substances, wt%: styrene 20-30, x-methylstyrene 5-7; P-methylstyrene 0.5-1.8; naphthalene 0.1-0.5; diphenyl, diphenylmethane, dibenzyl-1-4, trans-stilbene 3-5, polystyrene 30-50 The rest is heavy oil. The coatings based on copolymers obtained according to the invention dry out within 3-6 hours and have a hardness of 0.30, 5. Example 1. The reactor is charged with 1.23% by weight of A1Cl, and 50 ml of toluene and stirred for 10-30 minutes. The mixture, weight 74.07%, and 24.7% by weight, of technical piperylene is poured into the reactor for 1-2 hours. The reaction mixture temperature is 30 ° C. The process is carried out for 4-5 hours. The reaction mass is treated with isopropyl alcohol (1: 1 ratio by volume) in order to decompose the catalyst complex and isolate the polymer directly in the reactor. The solvent and the low molecular weight compounds are then removed by vacuum distillation at a bulk temperature of 180-200 ° C. A dark brown polymer with a molecular weight of 1100 is obtained. Example 2. The experiment is carried out as in Example 1 with a ratio of components, wt.%: The bottom product Piperylene AIC1.J, Molecular 1500.1 polymer weight. , 44 wt.% 50 ml of toluene and stirred for 10-30 minutes. A mixture of 18.78% by weight of the bottom residue and 48.78% by weight of technical piperylene is transferred to the reactor within 1-2 hours. The temperature of the polymerization process. The treatment is then carried out as in Example 1. The molecular weight is 1000. Example 4. The reaction is carried out as described in Example 1, with a ratio of components, wt.%: Bottom residue 74.8 piperylene 24.96, Ale IT, 0.249. The molecular weight of polymer is 1100. Example 5. The reaction is carried out as in example 1 at a temperature of 18-20 ° C and a component ratio of wt.%: Bottom product 74.8, piperylene 24.96, AlClj 0.249. Molecular weight of polymer 980. Example 6. 2.44% by weight of zeolite, distillation residue of styrene 43.78% by weight, technical piperylene, 48.78% by weight, are added to the reactor and stirred while heating at 30-120 ° C 5-10 hours, at a temperature of 120-160 ° С 1015 hours and at a temperature of 160-200 ° С 1015 hours. Then unreacted products are distilled off at 180-200 ° С under vacuum. The polymer obtained is dissolved in xylene, the catalyst is separated by filtration. Molecular weight of polymer is 1300. Example 7. 2.44% by weight of zeolite, distillation residue of styrene 48.78% by weight, technical piperylene 48.78% by weight and stirred at 80 ° C for 2 hours are placed in a reactor and stirred for 2 hours. at 120 ° C for 3 h, at 150 ° C for 4 h, at 200 ° C for 5 h. Then the unreacted products are distilled off at 180–200 ° C under vacuum. The molecular weight of polymer is 1600. The copolymers are dark brown solid resins using the softening method according to the ring method and Shar 65-125 ° C. From a 40% strength solution of resin in xylene (toluene), films are obtained that dry completely in 3-6 hours to form a smooth, smooth, shiny surface. The hardness of the film is 0.3–0.5 for a materiel, elasticity on a scale of flexibility of 3-5 mm. The structure of the obtained polymer was studied using IR spectroscopy. The spectra were taken on an IKS-22 in the region of 2000–700 cm as a film of carbon tetrachloride. The polymers obtained are basically styrene-shaped (in: greater degree), which is confirmed by absorption in the frequency range 1595, 1480, 1440, 1152, 1023 cm and the trans form (intense absorption in the range 960 cm). The method of obtaining the polymer by the interaction of the cubic residue of the distillation of styrene with the dienes contained in technical piperylene in the presence of a catalyst provides the following advantages: - a low molecular weight polymer is synthesized, the solution of which in xylene or toluene is a varnish. Lacquer films have good decorative properties (the properties are}) - the way of using the cheap: Waste from manufacturing plants of the UK is shown; - getting cheap paints and varnishes ;; i - the possibility of repeated use of zeolite catalyst. Formula of the invention By copolymerizing the mixture styrene-containing and piperyl-containing fractions when heated in the presence of a catechizer, differ in that with the aim of improving the physicomechanical properties of coatings based on these copolymers, as styrene soda 48.78-74.8% of the weight of the initial mixture of bottom bottoms of styrene distillation is used as the neighing fraction, as 24, 7-48.78% of the weight of the initial technical piperylene mixture containing 60.1-60.9% of trans-piperylene and 28,3930, 39% cis-piperylene, and the process is carried out in an organic solvent medium in the presence of Friedel-Crafts catalyst or zeolite at 80,200 ° C. Sources of information taken into account during the examination 1. ODE patent 3770710, cl . 260-837, publ. 1973. 2. Japanese Patent 16172, cl. 26 (3) B 114, publ. 1972. 3. Patent IT No. 3775392, cl. 260-94.2, pub. 1973. 4. USSR author's certificate No. 540467, cl. C 08 F 212/08, 1974 (prototype).