DE2048312A1 - Polymers containing lactam-groups - used for prodn of moulded bodies, coatings and adhesives - Google Patents

Abstract

Polymers are derived wholly or partly from monomer units of formula: (where R is H or methyl, and R1 is a cycloaliphatic lactam group. A cpd. of formula: is a suitable monomer. (Co)polymerisation is in presence of radical initiators. Suitable comonomers include ethylene, butadiene, styrenes, (meth)acrylates, (meth)acrylamides, vinyl esters and vinyl ethers.

Description

Polymers Containing Lactam Groups The invention relates to polymers containing lactam groups which are wholly or partly composed of monomer units of the general formula in which R is hydrogen or a methyl group and R1 is a lactam group.

R1 preferably consists of a lactam residue of the formulas n = 1 to 9.

It is known that one can use vinyl compounds that do not contain amino groups contain, can easily homo- or copolymerize.

Vinyl compounds with amino or ammonium groups, e.g. 3.

Allylamine or butene- (1) -amine (3), on the other hand, can be among the usual Conditions are practically not polymerized to high molecular weight substances. Even Secondary oder.tertiäre amines cause difficulties in the polymerization because they can act as regulators or activators for radical initiation.

It has now been found that new polymers containing lactam groups are obtained if derivatives of the general formula are used in which R is hydrogen or a methyl group and R1 is an imido radical, optionally polymerized together with other olefinically unsaturated monomers, in the presence of initiators which form radicals and then optionally the radical R1 is modified by customary reactions. According to the process of the invention it is now possible to produce high molecular weight substances which contain lactam groups. Such polymers are color-affine due to the lactam groups and other reactions such. B. Splitting and networking accessible.

Suitable unsaturated amine derivatives are, for example Such derivatives can be prepared, for example, by reacting hydroxyethyl derivatives with acrylic or methacrylic esters. The preparation of the new unsaturated derivatives is not the subject of this invention.

Suitable olefinically unsaturated monomers, optionally with The imido derivatives can be copolymerized are, for example, olefins, such as Ethylene, 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 or methacrylic acid amide and substituted amides, such as N-methylolacrylamide, N-methylol methacrylamide or ethers thereof, such as N-methylol acrylamide 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. from the above-mentioned compounds can also have two or more at the same time the imido derivatives are copolymerized.

For the production of copolymers, the proportion of unsaturated Amine derivative in the monomer mixture vary within wide limits, for example between 1 and 99, in particular between 10 and 90 Vo.

The usual free radicals are used to initiate the polymerization Initiators used. Suitable initiators are, for example, hydrogen peroxide, organic peroxides 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-dimethylvaleronitrile, 2,2'-azo-bis-isobutyronitrile and the like Azonitriles, for example in J. Hine "Reactivity and Mechanism in Organic Chemie, Verlag Georg Thieme, Stuttgart (1960), page 412, are listed, as well as Redox catalyst systems, such as the potassium or ammonium persulfate and ascorbic acid systems, Sodium hydrosulphite 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-dicarbon compounds are used as chelating agents used. Manganese (III) acetyl carbonate and cobalt (III) acetoacetic ester may be mentioned as examples.

The initiators are generally used in an amount from 0.05 to 5 percent by weight, based on the amount of monomer, used. The optimal amount and the optimally effective initiator can easily be determined through experiments.

The polymerization can be carried out in bulk.

However, it is advantageous to work in the presence of solution, or Thinners. For example, alcohols such as methanol, ethanol, Propanol or butanol; Ketones such as methyl ethyl or methyl propyl ketone; Ether how Tetrahydrofuran or dioxane; aliphatic, cycloaliphatic or aromatic hydrocarbons, such as heptane, hexane, cyclohexane or benzene, formamide and dimethylformamide are also very suitable, water is advantageously used as a diluent.

Those common for a variety of other monomers or mixtures of monomers Suspension, solution, or emulsion polymerization processes are also available for the suitable for new processes.

Also with regard to any auxiliaries used, such as buffer substances, Dispersants, protective colloids and the like differs from the new process not from known ones. The polymerization can take place in a wide range of temperatures between about 0 and 150, preferably between 50 and 120 ° C., can be carried out. In general, atmospheric pressure is used, but lower or lower pressure can also be used higher pressures, for example up to 3000 atmospheres, can be used. Especially with Using lower boiling comonomers is using higher pressures indicated to have a sufficient concentration of the comonomer in the reaction mixture to effect.

The copolymerization of the unsaturated lactam derivatives with ethylene or butadiene is advantageously carried out in emulsion by mixing with one another copolymerizable monomers in an aqueous soap emulsion containing an initiator, contains a buffer system and optionally a protective colloid, introduces and at increased pressure, up to about 2000 atmospheres, polymerized. Copolymerization with acrylic esters is useful in aromatic or aliphatic hydrocarbons among the for the polymerization of acrylic esters known conditions carried out.

The polymers can be used, for example, for the production of moldings, Coatings or adhesives, also mixed with other plastics, z. B. with polyethylene, polypropylene or with copolymers of vinyl acetate and ethylene can be used. Such products have an affinity for color. Because of their surface-active and The polymers produced according to the invention are antistatic properties among other things also suitable for the finishing of paper and textiles and allow for Part of cross-linking reactions. Those obtained by the radical polymerization Homopolymers have intrinsic viscosities (t) in the range of 0.4 to 2.0 dl / g (25 OC), Lit. W. R. Sorenson, T. W. Camphell, "Preparative Methods of Polymer Chemistry Intersc. Pub., N.Y. p. 44 (1968).

The copolymers obtained by the process according to the invention are statistically structured products, the intrinsic viscosities of these polymers are in the same range as those of the homopolymers.

The parts and percentages given in the examples are based on weight. The K values were each determined in 1 percent in dimethylformamide according to the instructions of H. Fikentscher, Cellulosechemie 13, 58, (1932). EXAMPLE 1 Cli C0i 2 10.0 parts CH2 = CH-COOCH2-CH2-N / lu / CH2 Nitrogen atmosphere and CH2 are heated to 60 ° C for 4 hours with 0.1 part of azobisisobutyronitrile while stirring.

After precipitation with methanol, washing out with methanol and drying, 9.3 parts of a polymer with a K value of 76.5 (0.5 ig in dimethylformamide) are obtained which has a glass temperature TG of +45 ° C. and has a refractive index nD of 1.5006, the N content is 9.0 ffi (theoretical 9.04) Examples 2 to 12 acrylic acid esters and are mixed in certain proportions, mixed with 0.1 percent by weight of azobisisobutyronitrile and heated to 70 C for 2 hours in the presence of 100 ml of alcohol. The copolymers were dried by drying in a rotary evaporator and then in a vacuum drying cabinet for 10 hours at 60 ° C./12 Torr. The results obtained are shown in the table below.

No. Acrylic acid imido conversion E value% N Share of the imi-ethyl ester derivative * do-derivative in the amount in parts of copolymers in% by weight 2 9.9 0.1 90.0 86.0 0.05 0, 8 3 9.5 0.5 84.0 85.5 0.3 4.5 4 9.0 1.0 86.0 91.0 0.6 9.0 5 8.5 1.5 86.0 89 , 0 0.9 14.0 6 8.0 2.0 86.0 87.0 1.4 19.6 7 7.0 3.0 89.0 89.0 1.9 28.0 8 6.0 4.0 93.0 88.0 2.5 57.5 9 5.0 5.0 97.0 88.5 3.2 48.0 10 4.0 6.0 98.0 89.0 3.7 56.0 11 2.5 7.5 97.0 88.0 4.8 72.5 12 1.0 9.0 100.0 79.5 5.8 87.5 Example 13 30 parts are mixed with 2 parts of sodium pyrophosphate, 1.5 parts of potassium persulfate, 2 parts of the sodium salt of a sulfonated fatty alcohol having 10 to 15 carbon atoms and 1000 parts of water. Sufficient ethylene is injected onto this mixture for 8 hours at 90 oC with stirring so that the pressure of the ethylene in the gas space is 285 atmospheres. After the reaction time of 8 hours, the dispersion has a dry content of 19.5 percent by weight. The E value of the copolymer is 36 (1% in decahydronaphthalene). The proportion of incorporated lactam is 4.9 percent by weight.

Example 14 The procedure is as in Example 13, but there are 30 parts to use. In addition, 170 parts of styrene are metered in instead of ethylene. After a polymerization time of 8 hours, a dispersion with a dry content of 16.5 percent by weight is obtained. The K value of the copolymer is 52 (1 ig in toluene).

The proportion of incorporated lactam is 15 percent by weight.

Example 15 The procedure described in Example 13 is followed, but used and replaced ethylene with 80 parts of butadiene. A dispersion with a dry content of 25.3 percent by weight is obtained at 90 ° C. within 8 hours and at a butadiene pressure of 6 atmospheres during the reaction time.

The E value of the copolymer, with a proportion of 19.2 percent by weight of built-in imide is 86.

Example 16 The procedure is as described in Example 9, but the acrylic ester is replaced by vinylthioethanol CH2 = CH-S-CH2-CH2-OH, a conversion is made of 89%, a K value of 69 and a proportion of 47 percent by weight of polymerized Lactam, corresponding to an N content of 3.2%, is achieved.

Claims (3)

Claims 1. Polymers which are wholly or partly composed of monomer units of the general formula are constructed in which R is hydrogen or a methyl group and R1 is a cycloaliphatic lactam group. 2. Polymers according to claim 1, characterized in that these in addition to Monomer units of the formula I nor monomer units from other olefinically unsaturated ones Contain monomers. 3. A process for the preparation of the polymer according to claim 1 or 2, characterized in that compounds of the general formula in which R and R1 have the meaning given in claim 1, subjected to the polymerization in the presence of initiators which form free radicals, optionally in a mixture with other polymerizable monomers.