DE2042268A1 - Polymers contg isocyanato-vinylene - and/or n-tert-butyl-n- chloroformylvinylene- groups - Google Patents

Abstract

Polymers have K-values 30-140, contg. units of formulae (I) and/or (II): in which R is H or methyl. Products contain reactive NCO and/or groups and have therefore excellent dye affinity and surface-active characteristics making them suitable for use as paper or textile dressings. Also used in mfre. of mouldings, coatings, adhesives.

Description

Isoczanato-vinylene and / or N-tert-butyl-N-chloroformylrinylene groups Polymers The invention relates to new isocyanato-vinylene and / or N-tert-butyl-N-chloroformyl-vinylene groups Homo- or copolymers and processes for producing the products from, if appropriate substituted butadienyl isocyanates and / or N-tert-butyl-N-butadienyl-carbamic acid chlorides and optionally other olefinically unsaturated monomers.

It is known that polymers containing isocyanato groups can be obtained by polymerization or copolymerization of inyl isocyanate and / or isopropenyl isocyanate and optionally other olefinically unsaturated monomers can produce.

The invention was based on the object of producing polymers in a simple manner to produce as substituents in addition to isocyanate and / or N-tert-butyl-N-chloroformyl groups contain olefinically unsaturated units in the side chain.

The invention relates to polymers with K values of 30 to 140 which contain units of the formulas I and / or II in which R denotes a hydrogen atom or a methyl group.

Due to the vinylene, isocyanate and / or N-tert-butyl-N-chloroformyl groups these polymers are reactive and, if necessary, accessible to further reactions. the Polymers can, for example, be intermolecularly and intramolecularly crosslinked, graft polymerized or vulcanized.

It is also possible to remove the 14-tert-butyl-III-chloroformyl radicals Splitting off of tert. Convert butyl chloride into isocyanate groups.

The polymers according to the invention are obtained by homo- or copolymerization of a) compounds of the formulas III and / or IV in which R has the meaning given above, and optionally b) one or more other olefinically unsaturated monomers in the presence of initiators which form free radicals.

Suitable compounds containing isocyanate groups are 3-methylbutadienyl isocyanate and preferably butadienyl isocyanate.

Substances containing N-tert-butyl-N-chloroformyl groups include N-tert . Butyl-N-3-methyl-butadienyl-carbamic acid chloride and preferably N-tert. Bu tyl-N-butadienyl-carbamic acid chloride into consideration.

The N-tert-butyl-N-butadienylcarbamic acid chlorides used as starting materials of the formula IV can, for example, by reacting phosgene with corresponding Schiff's bases according to the method of German patent application P 19 01 542.0 can be obtained. The N-tert-butyl-N-butadienylcarbamic acid chlorides can, for example thermal - accordingly the procedure of the German patent application P 19 22 412.5 - split into tert-butyl chloride and dutadienyl iocyanate of the formula III will.

The monomers of the formulas III and IV can each be used on their own are polymerized. Of course, it is also possible to use mixtures of different to copolymerize these compounds. In addition, they are of copolymerization accessible with other olefinically unsaturated monomers.

Suitable olefinically unsaturated monomers, optionally with the butadienyl isocyanates mentioned and / or N-tert-butyl-N-butadynyl-carbamic acid chlorides of the formulas 117 and IV can be copolymerized are, for example, olefins, such as ethylene, propylene, butadiene, isoprene; Styrene and substituted styrenes, such as X-methylstyrene, 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 amide and substituted amides, such as N-methylolacrylamide 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 ethers 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 with the mentioned butadienyl isocyanates and N-tert. Butyl-N-butadienyl-carbamic acid chlorides are copolymerized.

The proportion of butadienyl isocyanates can be used for the production of copolymers and / or N-tert-butyl-N-butadienyl-carbamic acid chlorides in the monomer mixture in vary widely, for example between 1 and 99, in particular between 5 and 80, preferably between 8 and 60 wt., 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, organic hydroperoxide, t-butyl pe @ enzoate, dicumyl peroxide, p-methane hydroperoxide, cumene hydroperoxide, succinic acid peroxide, also aliphatic azo compounds which decompose into radicals under polymerization conditions, such as 2,21-azo-bis-2,4-dimethyl-valronitrile, 2,21-azo-bis-isobutyronitrile and analogues Azonitriles, for example in d. Hine "Reactivity and Mechanism in Organic Chemic ", Verlag Gerog Thieme, Stuttgart (1960), @eite 412, are listed, as well as Usual redox catalyst systems, such as the potassium or ammonium persulfate systems and ascorbic acid, sodium hydrosulfite or iron-11 salts.

The chelates of transition metals known as radical formers are also suitable, especially those in which the metal is of an unusual value, such as chelates of manganese (III), cobalt (III), copper (II) and cerium (IV). In general use 1,3-dicarbonyl compounds as chelating agents. As examples are called manganese (III) acetylacetonate and cobalt (II) acetoacetate.

The initiators are generally used in an amount from 0.5 to 5 % By weight, preferably 0.1 to 1.0% by weight, based on the amount of monomers. The optimal amount and the optimally effective initiator can be determined by experiments easy to determine.

The polymerization can be carried out in bulk. Advantage however, one works in the presence of solvents or thinners. Suitable are for example ketones such as methyl ethyl or methyl propyl ketone, ethers such as diethyl ether, Tetrahydrofuran or dioxane; aliphatic, cycloaliphatic or aromatic hydrocarbons, such as hexane, heptane, cyclohexane, benzene or toluene, dimethylformamide is also very suitable.

The usual for a variety of other monomers or monomer mixtures Suspension or solution polymerization processes are also suitable for each process suitable. Also with regard to any auxiliaries used, such as dispersants, Protective colloid and the like, the new process does not differ from known ones.

The polymerization can take place in a wide temperature range, for example between 0 and 150 ° C, preferably between 50 and 120 ° C with reaction times of 1 to 20 Hours, preferably 2 to 10 hours. One works in general at atmospheric pressure, but higher pressures can also be used. In particular in the case of copolymerizations with low-boiling comonomers, the use of higher Printing indicated a sufficient concentration of the comonomer in the reaction mixture to effect.

The copolymerization of butalienyl isocyanates and / or N-tert-butyl-N-butadienyl-carbamic acid chlorides with ethylene or butadiene is advantageously carried out in aliphatics or aromatics, by adding the monomers copolymerizable with one another in the solvent that contains an initiator, introduced and at elevated pressure, with ethylene as comonomers polymerized to about 2000 atmospheres.

The copolymerization with acrylic esters is expedient in aromatic or aliphatic hydrocarbons among those used for polymerization of acrylic esters known conditions.

The polymers according to the invention, which have K values from 30 to 140, preferably from 50 to 110, are due to their content of reactive -NCO and / or Groups easily stainable. They are used, for example, for the production of moldings, impact-resistant compounds, coatings or adhesives, also mixed with other plastics, e.g. B. with polyethylene, polypropylene or mt copolymers of vinyl acetate and ethylene, used. Because of their surface-active properties, the polymers are also suitable for finishing paper and textiles, among other things.

Copolymers are also of particular technical interest of butadienyl isocyanates and / or N-tert-buty-N-butadienylcarbamic acid chlorides with acrylic esters. These products are soluble, highly molecular, and can be mixed with pigments and can be with conventional crosslinking agents at relatively low temperatures crosslink, Such polymers are excellent as paints or for the production of Foams can be used.

The parts and percentages given in the examples are mutually exclusive on the weight, Unless a different solvent is mentioned, the K values were 1% in each case in dimethylformamide according to the instructions of H. Fikantscher, Cellulosechemie 13, 58 (1932) determined.

Example 1 The ethyl acrylate and the butallenyl isocyanate are mixed in certain proportions, with; in each case 0.1 percent by weight of azo-bis-isobutyric acid nitrile and heated to 70 ° C for two hours.

The copolymers are precipitated with methanol, washed with methanol and dried in a vacuum drying cabinet for 10 hours at 60 ° C. and 12 mm. The results obtained are summarized in the following table. No. Acylic acid butadienyl conversion K value N proportion ethyl ester isocyanate of the iso- [Parts] [parts] [%] [%] cyanates in copo- lymeren in% by weight a 9.9 0.1 100 74 approx.0.1 approx.0.7 b 9.5 0.5 100 75 0.7 4.75 c 9.0 1.0 96 72 1.4 9.5 d 8.5 # 1.5 95 73 2.1 14.3 e 8.0 # 2.0 95 76 2.8 19 f 7.0 # 3.0 90 81.5 4.2 28.5 g 6.0 j 4.0 75 79 5.7 approx. 39 h 5.0 5.0 68 82 7.2 49 i 4.0 # 6.0 51 79 8.6 58.5 j 2.5 7.5 45 84 10.5 71 k 1.0 9.0 1 35 96 13.2 about 90 Example 2 A solution of 50 parts of toluene, 50 parts of a copolymer of ethyl acrylate and butadienyl isocyanate according to Example 1c and one part of p-phenylenediamine is applied to a metal sheet and crosslinked at 100 ° C. for 30 minutes.

The resulting lacquer coating is clear and insoluble in acetone or toluene.

Example 3 4 parts of acrylonitrile and 6 parts of butadienyl isocyanate are used in the presence of 0.01 part of azo-bis-isobutyronitrile for two hours at 70 ° polymerized. The polymer has a K value of 66 and contains 58 percent by weight of polymerized isocyanate. The conversion is 89%.

Example 4 To a solution of 150 parts of toluene and 10 parts of N-tert-butyl-N-butadienyl-cabamic acid chloride and 1 part of azobis-isobutyronitrile is stirred for 8 hours at 90 ° C so much Butadiene pressed on so that the butadiene pressure in the gas space is 6 atmospheres. The polymer has a solids content of 27 percent by weight after this reaction time K value of 94 and contains 16.5% by weight carbamic acid chloride.

Example 5a The procedure is analogous to that of Example 4, but if the butadiene is replaced by ethylene, a reaction time of 8 is obtained Hours, a reaction temperature of 90 ° O and an ethylene pressure in the gas space of 235 atü a solution with a solids content of 21 wt. The K value of the copolymer, which contains a proportion of 12.8% by weight carbamic acid chloride is 52.5 (1 Xig in decahydronaphthalene).

Example Sb A solution of 100 parts of toluene and 100 parts of a copolymer according to Example 5a and 0.5 part of p-toluenesulfonic acid is used to split off the tert-butyl chloride Boiled under reflux for 5 hours. The product that deals with styrene, butadiene and acrylonitrile graft polymerizes, has a hydrogenation number of 31.

Example 6a A solution of 150 parts of toluene, 10 parts of N-tert-butyl-N-butadienyl-carbamic acid chloride, 270 parts of styrene and 3 parts of azo-bis-isobutyronitrile are stirred for 8 hours heated to 90 ° C. 280 parts of a copolymer with a K value of 63 (0.5 ig in toluene) and a carbamic acid chloride content of 3.5 percent by weight.

Example 6b A solution of 100 parts of toluene and 100 parts of a copolymer according to Example 6a and 0.5 part of p-xoluenesulfonic acid is used to split off the tert-butyl chloride Boiled under reflux for 5 hours.

Mixtures of 10 parts of the polymer solution and 1 part 4,4'-dihydroxydiphenyl-propane-2,2 or 1 part of p-phenylenediamine are applied to sheet metal and 45 minutes at 130 oC networked. The coatings obtained are insoluble in toluene and acetone.

Example 7 6 parts of butadienyl isocyanate in the presence of 0.01 Part of azo-bis-isobutyronitrile polymerized at 70 0 for two hours. 5.5 is obtained Parts of homopolymer with a K value of 62.

Example 8 The procedure is analogous to the information in Example 7, but instead of butadienyl isocyanate, 3-methyl-butadienyl isocyanate is used 5.2 parts of a homopolymer with a K value of 59.5.

Example 9 If the reaction takes place according to Example 7, but instead of butadienyl isocyanate N-tert-butyl-N-butadienyl-carbamic acid chloride used, 4.7 parts of homopolymer with a K value of 46 are obtained in this way.

Example 10 The procedure is as described in Example 7, but instead of butadienyl isocyanate, N-tert-butyl-N-3-methylbutadienyl carbamic acid chloride used, 4.8 parts of a homopolymer with a K value of 49 are obtained.

Claims (4)

Claims 1. Polymerization products with K values from 30 to 140 containing units of the formulas I and / or II in which R denotes a hydrogen atom or a methyl group. 2. Polymerization products with K values from 30 to 140 consisting of units of the formulas I or II in which R has the meaning given above. 3. Homopolymers or copolymers with K values of 30 to 140 obtained by polymerizing a) butadienyl isocyanates and / or N-tert-butyl-y-butadienyl carbamic acid chlorides of the formulas III and 17 in which R has the meaning given above, and optionally b) one or more other olefinically unsaturated monomers. 4. A process for the preparation of isocyanato-vinylene and / or N-tert-butyl-N-chloroformyl-vinylene group-containing homo- or copolymers, characterized in that butadienyl isocyanates and / or N-tert-butyl-N-butadienyl -carbamido acid chlorides of the formulas III and / or IV in which R has the meaning given above, optionally polymerized together with other olefinically unsaturated monomers in the presence of initiators which form free radicals.