CS241206B1 - Synthetical resin on base of polymers' non-saturated copolymers with monomers and method of their production - Google Patents

Abstract

The purpose of the invention is to improve and broaden the scope of unsaturated hydrocarbon properties resins being processed especially for paints, printing and printing marking paints, adhesives, sealants, paper size and additives to rubber compounds and plastics wt. Its essence is that the resin radical polymerization 5 to 5 is prepared 98 wt. unsaturated hydrocarbon parts copolymers of average molecular weight weight of 500 to 5,000 and iodine number 30 to 150 g of Ji / 100 g with 2 to 95 wt. unsaturated parts compounds from the group of alkyl esters acrylic and methacrylic having from 2 to 8 carbon atoms in the alkyl group, styrene and its derivatives. The procedure is such that the mixture of unsaturated hydrocarbon copolymers a unsaturated compounds are subjected to temperature 60-160 ° C in the presence of initiators radical polymerization and optionally organic solvents or water; the addition of additives from the group of accelerators, regulators polymerization, emulsifiers and preservatives colloid reaction that ends after reaching the degree of conversion of the reactants at least 98.5%.

Description

The present invention relates to synthetic resins. based on the reaction products of unsaturated hydrocarbon copolymers with olefinically unsaturated monomers and a process for their preparation.

Unsaturated hydrocarbon copolymers are low molecular weight copolymers of mixtures of unsaturated hydrocarbons that fall off during cracking (Kirk-Othmer: Encyclopedia of Chemical Technology, J. Wiley and Sons, N. York 1980, 3rd ed., Vol. 12, pp. 852-869) . Depending on the composition of the hydrocarbon feedstocks, reactive and non-reactive resins of different chemical compositions and properties are obtained. They are widely used in the plastics, paint and rubber industries.

To improve or achieve new properties, the hydrocarbon copolymers are physically or chemically modified. Physical modifications consist in combination with other polymers with which they are compatible. Unsaturated hydrocarbon copolymers are more frequently modified chemically by reaction with various compounds. For example, modifications have been described with drying and semi-drying natural oils or. their acids (European Patent No. 5,010, German Patent No. 2,246,283). oil alkyds (French Patent No. 1,545,632), unsaturated polyesters (Japanese Patent No. 8,221,413), polyepoxides (German Patent No. 2,821,301), polyisocyanates (British Patent No. 1095,981) and other reactive low molecular weight i These modifications greatly increase the reactivity and hardenability of the unsaturated hydrocarbon copulomers, and the cured products exhibit improved physico-mechanical and chemical properties.

Another significant improvement in the properties of the unsaturated hydrocarbon resins is provided by the present invention, which relates to synthetic resins based on copolymers of unsaturated polymers with monomers and a process for their preparation.

SUMMARY OF THE INVENTION The resins are prepared by radical polymerization of 5 to 98 wt. parts of unsaturated hydrocarbon copolymers having an average molecular weight of 500 to 5,000 and an iodine number of 30 to 150 g J / 100 g with 2 to 95 wt. parts of unsaturated compounds from the group consisting of alkyl esters of acrylic and methacrylic acids having 2 to 8 carbon atoms in the alkyl group, styrene and derivatives thereof. A mixture of 5 to 98 wt. parts by weight of the above specified unsaturated hydrocarbon copolymers; and 2 to 95 wt. parts of said unsaturated compounds are subjected to a reaction at a temperature of 60 to 160 ° C in the presence of radical polymerization initiators and optionally organic solvents or water, and optionally with the addition of additives from the group of accelerators, polymerization regulators, emulsifiers and protective colloids of at least 98.5%.

The synthetic resins of the present invention have some advantages over known modified unsaturated hydrocarbon copolymers. In particular, a large number of unsaturated copolymerization or addition of capable substances, either singly or in admixture with each other, can be used for modification. The nature and quantity of these monomers and the production technology used can vary widely the properties of the unsaturated hydrocarbon copolymers starting. The obtained synthetic resins or their solutions or dispersions are either permanently thermoplastic or curable and, in particular, cured products are characterized by increased elasticity and toughness, impact and abrasion resistance, adhesion to various substrates, chemical, water, weathering and corrosion resistance.

The synthetic resins of this invention are the reaction products of unsaturated hydrocarbon copolymers with olefinically unsaturated monomers. The starting unsaturated hydrocarbon copolymers are known technical resins, most often obtained by cationic polymerization of unsaturated hydrocarbons, which are by-products of thermal cracking (petroleum cracking) of olefins and diolefins, and form a varied mixture of low-boiling linear and cyclic olefins (butenes, pentenes, hexenes, hepenes , cyclohexenes) and diolefins (butadiene, pentadiene, hexadiene, cyclopentadiene, dicyclopentadiene, cyclohexadiene), high boiling unsaturated aromatic compounds (styrene, α-methylstyrene, wooltoluenes, allylbenzene, indene, methylindenes) and other unsaturated hydrocarbons are present. fractions which are then subjected to polymerization catalysed by Friedel-Craits catalysts or Lewis acids Liquid and solid hydrocarbon copolymers having an average molecular weight of 500 to 5 are suitable for reaction with the monomers of the present invention. 000 and iodine number 30 to 150 g J / 100 g.

The modifying component consists of olefinically unsaturated monomer compounds, of which alkyl esters of acrylic and methacrylic acid (methyl acrylate, ethyl crylate, butyl acrylate, 2-ethylhexyl acrylate and their corresponding methacrylate and styrene or their derivatives (n-methylstyrene, vinyltoluenes, p-chlorobenzene) ).

The reaction of said unsaturated hydrocarbon copolymers with olefinically unsaturated monomers takes place in the presence of initiators (dibenzoyl peroxide, dicumyl peroxide, cumene hydroperoxide, tert-butyl peroperoxide, tert-butyl perbenzoate, methyl ethyl ketone peroxide, cyclohexanone peroxide, bis (hydrogen peroxide), peroxide, optionally accelerators (amines, metal salts, sulfur reducing compounds), polymerization regulators, thioalcohols, namely laurylmercaptan, carbon tetrachloride and bromide), emulsifiers (polymethyleneoxidated alkylphenol), and cyclic alcohols, carboxylic acids, amides and amines, aminooxide (1), acyclic acid salts , alkylsulphates, alkylsulphonates, alkylarenesulphonates, alkylphosphates) and protective colloids (polyvinyl alcohol, methylcelluloses, hydroxyethylcelluloses, carboxymethylcelluloses) In addition to the monomers mentioned above, the reaction medium also comprises water softened, demineralized and conventional organic solvents (aromatic and chlorinated hydrocarbons, esters, ethers, ether esters and ketones).

The production of synthetic resins according to the invention is essentially carried out according to generally known polymerization processes. Thus, the modification of the unsaturated hydrocarbon copolymers with monomers takes place mainly as block, solution, solution precipitation, emulsion and suspension polymerizations. The rustless process is carried out in a stirred reactor equipped with a jacket for heating and cooling, a reflux condenser, possibly also an azcotropic adapter and a viscosity measuring device. In a continuous process, the reaction mixture passes through a series of reactors arranged in series or in a cascade or tubular reactor. The feedstocks are gradually or simultaneously introduced into the reactor. In particular, it is one or more types of unsaturated hydrocarbon copolymers and monomers. In addition, initiators, optionally accelerators, polymerization regulators, emulsifiers, protective colloids and, according to the selected preparation method, organic solvents or water are also added. The reaction mixture is subjected to a reaction at 80-130 ° C with efficient stirring, which is terminated at a conversion rate of at least 98.5%. In the case of solution copolymerization, the course of this reaction is generally monitored by the dry matter content of the copolymer solution which gradually increases with the amount of reacted monomers. In a block or emulsion copolymerization process, the most suitable conversion control is the chromatographic determination of the amount of residual monomers in the reaction mixture. Types of synthetic resins containing carboxyl or anhydride groups can be neutralized with ammonia or amines to form water-soluble or dispersible products. According to the technology used, both liquid and solid synthetic resins or their solutions are obtained in non-reactive No. ⁵ reactive solvents and aqueous or aqueous dispersions.

The synthetic resins prepared according to the invention are mainly processed into paints (solvent, water-dilute and powdered), printing and marking inks, adhesives, sealants, paper sizing, additives for rubber mixtures and plastics. The curable resins and their compositions are cured in use at room temperature, by heating or irradiation, in the presence of initiators, catalysts or hardener addition.

The invention is illustrated by the following examples.

The following hydrocarbon copolymers were used to prepare the synthetic resins of the invention:

Hydrocarbon copolymer A:

mol. weight 500 styrene content 12 wt.

Indene content 9% by weight

iodine number 31 g J / IOQ g softening temperature 123 ^C C

Hydrocarbon copolymer B:

crayfish. weight styrene content indene content iodine é number softening temperature

000 wt. 29% wt. 33 g Jz / 100 g 155 ° C

Hydrocarbon copolymer C:

mel. weight styrene content indene content · iodine number softening point

000

0.5 wt. 15 wt. 28 g) 2/100 g of 142 ° C

Example 1

Ke 15Π wt. After heating to 60 DEG C., 37.5% by weight of a 33% solution of hydrocarbon copolymer A in a toluene-isopropanol solvent mixture (3: 1 ratio by weight) are added dropwise. % of butyl acrylate and 12.5 wt. % of ethyl acrylate with 3 wt. parts of α, α-azo-bis-bis-isobutyronitrile). After completion of the dropwise addition, the system is held at 60 ° C until the dry matter reaches about 50% by weight. The resin obtained has a viscosity of 150 mPa. at 20 ° C to give a glossy, clear film.

Example 2

To 133 wt. After heating to 110 [deg.] C., a mixture of 17 wt.% of a 25% solution of hydrocarbon copolymer B in a solvent mixture of xylene-butanol (3: 1 ratio by weight) is added dropwise. parts of butyl acrylate, 33 wt. parts by weight of ethyl acrylate; parts of styrene together with 1 wt. % of di-tert-butyl peroxide. At the end of the DC drop, the system heats up to 160 degrees Celsius until the dry matter reaches 50% by weight. The resin has a viscosity of 200 mPa. at 20 ° C and provides a glossy, hard film.

Example 3

To 150 wt. After heating to 110 [deg.] C., a mixture of 17% by weight of a 33% solution of hydrocarbon copolymer C in a solvent mixture of 21206 del xylene-butanol (3: 1 wt.) is added dropwise. parts of butyl acrylate, 17 wt. parts by weight of ethyl acrylate and 17 wt. parts of methyl methacrylate together with 1 wt. % of di-tert-butyl peroxide. The system is heated to 120 ° C at the end of the drip until the dry matter reaches 50% by weight. The resin has a viscosity of 250 mPa. at 20 ° C and provides a hard, glossy film.

Example 4

Ke 190 wt. 4 parts by weight of the molten hydrocarbon copolymer A are added dropwise at 130 degrees Celsius. parts of butyl acrylate, 4 wt. parts of ethyl acrylate and 2 wt. parts of methyl methacrylate together with 2 wt. parts of dibenzoyl peroxide. After completion of the dropwise addition, the system was held at 130 ° C until the content of free monomers, measured by gas chromatography, was below 1% by weight based on the weight of the copolymer. The product is then dissolved in 200 wt.

parts of toluene. The 50% solution has a viscosity of 120 mPa at 20 ° C. and provides a clear, glossy film.

Example 5

To 120 wt. parts of demineralized water containing 3 wt. parts by weight of sodium persulfate and 1.5 wt. 160 parts by weight of an ammonium metabisulphite was added dropwise at 90 DEG C. for 2 hours. parts of vinyltoluene, 20 wt. parts by weight of 2-ethylhexyl acrylate, 10 wt. parts of the hydrocarbon copolymer B together with 2 wt. parts by weight of sodium dodecyl sulfate (Texapone K 12) and 8 wt. parts of ethoxylated nonylphenols (Antharox 88). After completion of the dropwise addition, the system is maintained at a temperature of 90 ° C until the content of free monomers, as measured by gas chromatography, is below 1% by weight, based on the weight of the copolymer. The aqueous dispersion obtained has a viscosity of 80 mPa. s at 20 ° C to provide glossy, clear and hard films.

Claims (2)

SUBJECT Synthetic resins based on copolymers of unsaturated polymers with monomers, obtainable by free-radical polymerization of 5 to 98 wt. parts of unsaturated hydrocarbon copolymers having an average weight of 500 to 5,000 and an iodine number of 30 to 150 g J / 100 g with 2 to 95 wt. parts of unsaturated compounds from the group consisting of alkyl esters of C 2 -C 8 -alkyl and methacrylic acid, styrene and derivatives thereof. 2. A process according to claim 1, wherein the mixture is from 5 to 98 wt. parts of unsaturated hydrocarbon copolymers of average molecular weight Weight of 500 to 5000 g and an iodine number of 30 to 150 g of J2 / 100 g and 2 to 95 wt. parts of unsaturated compounds from the group consisting of alkyl esters of C 2 -C 8 alkyl acrylic and methacrylic acid, styrene and its derivatives are subjected to a temperature of 60 to 160 ° C in the presence of radical polymerization initiators and optionally organic solvents or water and optionally with the addition additives from the group of accelerators, polymerization regulators, emulsifiers and protective colloids, the reaction being completed after reaching a degree of conversion of the reactants of at least 98.5%.