DE2006834A1 - Vinyl sulphide polymers - Google Patents

Abstract

Vinyl sulphide polymers with a K value of 30-100 contain units of formula (I), (II) and/or (III). (where R is H, CH3 or CH=CH2; and X is halogen, pref. Cl). The polymers are reactive as a result of the hydroxy, halohydrin and/or epoxide groups in units (I), (II) and/or (III). Used alone or mixed with other resins for the prodn. of mouldings, coatings or adhesives. Esp. useful for finishing paper and textile.

Description

Vinyl sulfide polymers containing dihydroxy, halohydrin and / or epoxy groups The invention relates to dihydroxy, halohydrin and / or epoxy groups Vinyl sulfide polymers and processes for the preparation of the products from, if appropriate substituted 2,3-dihydroxy-propyl-vinylsulfidens 2- (chloro-ß-hydroxy-propoxy) -ethyl-vinylsulfiden and / or 2- (ß, γ-epoxy-propoxy) -ethyl-vinylsulfiden and optionally others Ethylenically unsaturated monomers It is known that vinyl compounds that contain no hydroxyl groups, can easily homo- or copolymerize.

Acrylic compounds containing chlorohydrin or epoxy groups are also used polymerizable.

In contrast, vinyl compounds, the hydroxy, chlorohydrin or epoxy groups anthalten, such as allyl alcohol, buten-1-ol-3, 3-chloro-2-hydroxy-propyl-allyl-ether or 2,3-epoxy-propylallyl-ether, under the usual free-radical reaction conditions are practically not polymerized to high molecular weight substances. Based on these Such compounds become properties, e.g. as regulators in free-radical polymerizations used.

It has been found that polymers with K values of 30 to 100 contain the units of the general formulas I, II and / or III in which R is hydrogen, a methyl or vinyl group and X is halogen, preferably chlorine, have advantageous properties. Such polymers are reactive because of the hydroxyl, halohydrin and / or epoxy groups and are optionally accessible to further reactions. The polymers according to the invention are obtained by homopolymerization or copolymerization of a) compounds of the general formula in which R and X have the meaning given above, and optionally b) one or more other olefinically unsaturated monomers in the presence of radical-forming initiators.

Suitable unsaturated monomers are, for example, 2,3-dihydroxypropyl vinyl sulfide, 2,3-Dihydroxypropy1-isopropenyl sulfide, 2,3-Dihydroxy-propyl-butadienyl-2-sulfide, 2- (r-Chloross-hydroxy-propoxy) -ethyl-vinyl-sulfide, 2- (t-chloro-ß-hydroxyprogoxy) -ethyl-isopropenyl-sulfide, 2- (r-chloro-ß-hydroxy-propoxy) -ethyl-butadienyl-2-sulfide, 2- (ß,> -epoxy-propoxy) -ethyl-vinylsulfide, 2- (ß, -Epoxy-propoxy) -ethyl-i 90 propenyl-sulfide, 2- (ß, γ-epoxy-propoxy) -ethyl-butadienyl-2-sulfide.

Monomers of the formula IV can, for example, by reacting acetylene, Propyne or butenine can be produced with 2,3-dihydroxypropyl-mercaptan-1. the containing halohydrin and opoxide groups Monomers of the formulas V and VI are expediently obtained from optionally substituted 2-hydroxy-ethylvinyl sulfides and epichlorohydrin and optionally subsequent ring closure to the epoxide in alkaline Medium.

Suitable olefinically unsaturated monomers, optionally with These sulfides can be copolymerized are, for example, olefins, such as Ethylene, butadiene, isoprene; Styrene and substituted styrenes, such as methyl styrene, p-chlorostyrene and p-methylstyrene; Acrylic esters and methacrylic esters, especially those with 1 to 18, preferably 1 to 8 carbon atoms in the alcohol radical, for example Acrylic or methacrylic esters of methanol, ethanol, butanol or ethylcyclohexanol; Acrylic and methacrylic acid amides and substituted amides, such as N-methylol acrylamide and N-methylol methacrylamide or their ethers, such as N-methylolacrylamide butyl ether, N-methylol methacrylamide methyl ether; Acrylic and methacrylonitrile; Vinyl esters such as vinyl acetate, vinyl propionate; Vinyl ether, such as methyl, ethyl or alkyl vinyl ether with alkyl radicals with 3 to 6 carbon atoms, also fumaric, maleic or itaconic acid, esters of these acids and maleic anhydride. Two or more of the abovementioned compounds can also be used at the same time are copolymerized with the thioether derivatives.

For the production of copolymers, the proportion of unsaturated Sulphides in the monomer mixture vary within wide limits, for example between 1 and 99, preferably between 10 and 90, in particular between 20 and 65 percent by weight, based on the total weight of the monomers.

The usual free radicals are used to initiate the polymerization Initiators used. Suitable initiators are, for example, hydrogen peroxide, organic hydroperoxides and peroxides, such as caproyl peroxide, lauroyl peroxide, t-butyl perbenzoate, Dicumyl peroxide, p »menthane hydroperoxide, cumene hydroperoxide, succinic acid peroxide, also aliphatic azo compounds which decompose into radicals under polymerization conditions, such as 2,2'-azo-bis-2,4-dimethyl-vaBlunitril, 2,2'-azo-bis-isobutyronitrile and the like Azonitriles, for example in J. Hine "Reactivity and Mechanism in Organic Chemistry, publisher Georg Time, Stuttgart (1960), page 412 are, as well as customary redox catalyst systems, such as the potassium or ammonium persulfate systems and ascorbic acid, sodium hydrosulfite or ferrous salts.

The chelates of known as radical formers are also suitable Transition metals, especially those in which the metal is in an unusual Valence is present, such as chelates of manganese (III), cobalt (III), copper (II) and Cerium (IV). In general, 1,3-dicarbonyl compounds are used as chelating agents. Examples are manganese (III) acetylacetonate and cobalt (III) acetoacetic ester.

The initiators are generally used in an amount from 0.05 to 5 percent by weight, preferably 0.1 to 1 percent by weight, based on the amount of monomers, used. The optimal amount and the optimally effective initiator let through Easily identify attempts.

The polymerization can be carried out in bulk. Advantageous however, one works in the presence of solvents or diluents. Suitable for the polymerization of vinyl sulfides containing epoxy and halohydrin groups are, for example, solvents which are inert under the reaction conditions. Particularly Ethers such as tetrahydrofuran or dioxane and aliphatic, cycloaliphatic ones have proven useful or aromatic hydrocarbons such as heptane, hexane, cyclohexane or benzene. Zers are suitable for the polymerization of vinyl sulfides containing dihydroxy groups polar solvents for example alcohols such as methanol, ethanol, propanol or Butanol; Ketones, such as methyl, ethyl or methyl propyl ketone and acid amides, such as Pormamide and dimethylformamide.

Those common for a variety of other monomers or mixtures of monomers Suspension, solution or emulsion polymerization processes are also for the new Procedure suitable. Also with regard to the aids that may be used, such as A distinction is made between buffer substances, dispersants, protective colloids and the like the new procedure is not familiar from it.

The polymerization takes place in a temperature range approximately between 0 and 1500C, preferably between 50 and 12000 with reaction times of 1 to 20 Hours, preferably 2 to 8 hours performed. One works in general at atmospheric pressure, but higher pressures, for example up to 3000 atü can be applied. In particular when using low-boiling comonomers the use of higher pressures is indicated to ensure sufficient concentration to effect the comonomer in the reaction mixture.

The copolymerization of those containing dihydroxy, halohydrin and / or epoxy groups Monomers with ethylene or butadiene is advantageously carried out in emulsion by one with one another.

of the copolymerizable monomers into an aqueous, preferably emulsifier-containing one Emulsion containing an initiator, a buffer system and optionally a protective colloid contains, brings in and at increased pressure, with * ethylene as a comonomer about up to 3000 atü, polymerized. The copolymerization with acrylic ester is expedient in aromatic or aliphatic hydrocarbons among those for the polymerization of acrylic esters known conditions.

The polymers according to the invention, the K values from 30 to 100, preferably from 40 to 70, have an affinity for color.

They can be used, for example, for the production of moldings, coatings or adhesives, also mixed with other plastics, e.g. with polyethylene, Polypropylene or with copolymers of vinyl acetate and ethylene are used will. Because of their surface-active and antistatic properties, the Polymers prepared according to the invention, inter alia, also for the finishing of paper and textiles. They can also be used to produce reactive paints.

The parts and percentages given in the examples relate to the weight.

The K values were in each case 1 percent in dimethylformamide according to the Regulation by H. Fikentscher, Cellulosechemie 13, 58, (1932) determined, example 1,100 parts of 2,3-dihydroxypropyl vinyl sulfide are added under a nitrogen atmosphere and stirring with 0.1 part of azobisisobutyronitrile heated to 60 ° C. for 4 hours.

There are after precipitation with methanol, washing with methanol and Drying 40.3 parts of a polymer with a K value of 52.5 (1 percent in dimethylformamide) obtained, which has a glass transition temperature TG of -480C and a refractive index n0 of 1.6205 Has.

Examples 2 to 12 ethyl acrylate and 2,3-dihydroxypropyl vinyl sulfide are mixed in certain proportions, each with 0.1% by weight of azobisisobutyronitrile added and heated to 7000 for 2 hours. The copolymers are precipitated with methanol, washed with methanol and dried in a vacuum drying cabinet for 10 hours at 600C / 12 Torr. The results obtained are shown in Table 1.

Table 1 Copolymers of ethyl acrylate and 2,3-dihydroxypropyl vinyl sulfide No. Acrylic acid 2,3-dihydroxy conversion K value portion of the 2,3-ethyl ester propyl vinyl % Dihydroxypropyl sulfide vinyl sulfide in the copolymer in total 56 amount in one 2 9.9 0.1 36 56.8 0.4 3 9.5 0.5 44.9 54.7 4.2 4 9.0 1.0 46.2 53.4 10.3 5 8.5 1 , 5 46.6 50.9 11.1 6 8.0 2.0 56.3 51.5 14.5 7 7.0 3.0 79.8 49.7 23.5 8 6.0 4.0 83.5 48, 4th 32.1 9 5.0 5.0 97.8 46.9 48.0 10 4.0 6.0 100 47.8 55.0 11 2.5 7.5 100 45.5 73.0 12 1.0 9.0 100 42.0 89.7 Example 13 To a mixture of 30 parts 2,3-dihydroxypropyl isopropenyl sulfide, 2 parts sodium pyrophosphate, 4.5 parts Potassium persulfate, 2 parts of the sodium salt of a sulfonated fatty alcohol with 10 to 15 carbon atoms and 1000 parts of water are stirred for 8 hours at 90 ° C so much ethylene pressed that the pressure of the ethylene in the gas space 285 atm amounts to. After a reaction time of 8 hours, the dispersion has a dry content of 20% by weight. The K value of the copolymer is 44 (1 percent in decahydronaphthalene) and the proportion of built-in sulfide 10.3% by weight.

Example 14 The procedure is as described in Example 13, but 2,3-Dihydroxy-propyl-isopropenyl-sulfide by 2,3-Dihydroxy-propylbutadienyl -? - sulfide and ethylene replaced by butadiene, it is obtained at 90 ° C within hours and a butadiene pressure of 6 atm during the reaction time with a dispersion a dry content of 26.0% by weight. The K value of the copolymer, with a portion of 17.5% by weight of sulfide is 62.5.

Example 15 If you work in the same way as in example 9 = however If the acrylic ester is replaced by acrylonitrile, the conversion is 7949, a K value of 60 and a proportion of 53.2% by weight of polymerized sulfide, accordingly achieved an S content of approx. 16%.

Example 16 100 parts of 2- (S-chloro-β-hydroxy-propoxy) -ethyl-vinyl-sulfide are added under a nitrogen atmosphere and stirring with 0.1 part azobisisobutyronitrile Heated to 600C for 4 hours.

After precipitation with methanol, washing with methanol and Drying 40.3 parts of a polymer with a K value of 59 (1 percent in dimethylformamide) obtained, which has a glass transition temperature TG of -49 ° C and a refractive index of nD20 of 1.6201.

Example 17 A mixture of 100 parts of 2- (β, -epoxypropoxy) -ethyl vinyl sulfide and 100 parts of acrylic acid n-butyl ester are analogous to the information in Example 16 polymerized.

200 parts of a copolymer are obtained, the glass transition temperature of which is at -58 ° C. The elemental analysis shows after a vacuum treatment of the product (5 hours at 60 ° C and 0.1 Torr) to remove volatiles, a sulfur value of 2.5%, which corresponds to a sulfide content of 50% by weight in the copolymer.

Examples 18 to 21 A mixture of 100 parts of styrene and 100 parts Vinyl sulfide is polymerized analogously to the information in Example 16.

The copolymers are in a toluene-dimethylformamide mixture dissolved in a weight ratio of 1: 1 and precipitated with n-hexane.

Details of the type of monomers and copolymers are given in the table 2 summarized.

Table 2 Copolymers of vinyl sulfides containing chlorohydrin or epoxy groups and styrene No. chlorohydrin and epoxy conversion K value% S Proportion of vinyl sulfides containing sulphides in% fide in the copolysulfide merizate 18 CH, IC-S-CH, -CH, -O-CH, -CH-CH, 98 62 3.25 49 ffi 3 9, CH2 = gS-CH2-CH2-0-CH2-CH-CH2 97 54 2.7 50% H) \ 0 / 20 CH2 = CH-S-CH2-CH2-0-CH2-CH -CH297 56 3.0 48% OH Cl 21 aH2 = CH-8-CH2-CH2-0-CH2-CH-CH2 96 55 2.4 49% 0 10983411434

Claims (4)

Claims 1. Polymers with K values from 30 to 100, containing units of the general formulas I, II and / or III in which: R is hydrogen, a methyl or vinyl group and X is halogen, preferably chlorine. 2, polymers with K values from 30 to 100, consisting of units of the general formulas I, II or III, in which R and X have the meaning given above. 3. Homopolymers or copolymers with K values of 30 to 100 obtained from a) vinyl sulfides containing dihydroxy, halohydrin and / or epoxy groups of the general formulas IV, V and / or VI in which R and X have the meaning given above, and optionally b) one or more other olefinically unsaturated monomers. 4. Process for the preparation of dihydroxy-, halohydrin- and / or epolid-containing homo- or copolymers, characterized in that vinyl sulfides of the general formulas VV and / or VI in which R and X have the meaning given above, if necessary polymerized together with other olefinically unsaturated monoins in the presence of initiators which form free radicals.