DE1720841C3 - Process for the preparation of alkoxy or aryloxyethylated polymers of heterocyclic N-vinyl monomers - Google Patents

Description

The invention relates to a process for the preparation of alkoxy- and aryloxyethylated polymers of heterocyclic compounds N-vinyl monomers, which have very interesting solubility characteristics in a wide range of polar to non-polar solvents.

The inventive method for the preparation of alkoxy or aryloxyethylated polymers of heterocyclic N-vinyl monomer is now characterized in that 1 mol of a heterocyclic N-vinyl monomers that have a carbonyl function in the heterocyclic ring in the vicinity: tum nitrogen atom or a monomer mixture of 5 to 99 mole percent of such a heterocyclic N-vinyl monomer and 1 to 95 mole percent of a monoethylenically unsaturated monomer along with 0.05 to 10 moles of a vinyl ether in an inert organic solvent in the presence of 0.025 to 0.2 moles of one organic peroxide per mole of vinyl ether heated to a temperature of 80 to 200 ° C.

The new process makes it possible to control the solubility of the polymers produced or to be determined beforehand.

The process enables simultaneous copolymerization and alkoxy or aryloxy ethylation heterocyclic N-vinyl monomers carried out with a vinyl ether

According to the invention, simultaneous terpolymerization and alkoxy or aryloxyethylation can also be used a mixture take place, which is a heterocyclic N-vinyl monomer, a monoethylenically unsaturated polymerizable monomer and a vinyl ether or a mixture of two different heterocyclic N-vinyl monomer and a vinyl ether. Here, too, there is a systematic control of the Solubility of the oxyethylated terpolymer obtained is possible.

In particular, heterocyclic N-vinyl monomers are easily polymerized and alkoxy- or aryloxylated by adding 1 mole of a heterocyclic N-vinyl monomer with 0.05 to 10 moles of vinyl ether in an organic solvent compatible with the N-vinyl monomer and the vinyl ether in the presence of 0.025 to about 0.2 moles of hydrogen peroxide or a Tertiäralkylperoxyds as a catalyst per mole of vinyl ether about 3 to about 48 hours at a temperature of 80 to 200 ⁰ C are reacted, the resulting solution of the alkoxy or aryloxyäthyuerten polymer can either be used as such or, if appropriate, the solvent can also be removed by vacuum distillation or by another method known per se.

The heterocyclic N-vinyl monomers used according to the invention can be polymerized and alkoxy- or aryloxyethylated, are those in the heterocyclic Remainder have a carbonyl group in the vicinity of the nitrogen, for example

N-vinyl succinimide, N-vinyl diglycolylimide,
N-vinyl glutarimide, N-vinyl-3-morpholinone,
N-vinyl-5-methyl-3-morpholinone,
N-vinyl-S-ethyl-a-morpholinone,
N-vinyl oxazolidone and 5-, 6- and 7-membered N-vinyl lactams of the following general formula

(CH ₂ ), -

C = O

R ₁ N

CH = CH ₂

in which R and Ri are hydrogen, the methyl or ethyl radical, π is an integer from 1 to 3
Examples of usable N-vinyl lactams are:

N-vinyl pyrrolidone;

N-vinyl-5-methylpyrrolidone;

N-vinyl-5-ethylpyrrolidone;

N-vinyl-5,5-dimethylpyrrolidone;

N-vinyl-5,5-diethylpyrrolidone and

N-vinyl-5-methyl-5-ethylpyrrolidone;

N-vinylpiperidone;

N-vinyl-6-methylpiperidone;

N-vinyl-6-ethylpiperidone;

N-vinyl-6,6-dimethylpiperidone;

N-vinyl-6,6-diethylpiperidone and

N-vinyl-6-methyl-o-ethylpiperidone;

N-vinyl caprolactem;

N-vinyl-7-methylcaprolactam;

N-VinyI-7,7-dimethylcaprolactam;

N-vinyl-7-ethylcaprolactam;

N-vinyl-7,7-diethyl caprolactam; such as

N-vinyl-7-methyl-7-ethylcaprolactam.
The average molecular weight m of the polymers obtained can be determined by measuring the K value.

The viscosity coefficient K, which is described in more detail in the reference Modem Plastics, 23, No. 3, pp. 157 to 161, 212, 214, 216 and 218 (1945), is calculated using the following formula:

log // rcl

75 K _o i

and K = KKX) K _n

where c is the concentration of polymer in grams per ml of solution and r \ rci is the viscosity of the solution in

Relation to the solvent means.
Polymerizable as monoethylenically unsaturated

Monomers can e.g. B. can be used:
Vinyl esters, such as vinyl acetate, vinyl propionate,
Vinyl butyrate, vinyl isobutyrate, vinyl lactate,

Vinyl caproat, vinyl caprylate,

Vinyl oleate and vinyl stearate;

Vinyl phenyl acetate, vinyl phenyl butyrate, vinyl a-naphthoate, acrylonitrile;

Vinyl ketones, vinyl cyclohexane; s

Styrene, 2-vinylpyridine, 4-vinylpyridine, Acrylic acid, acrylate ester of the formula

CH ₂ = CHCOOR ₂

in which R _{2 is} an aryl radical, a straight-chain or branched alkyl radical or an alkoxyalkyl radical in which the number of carbon atoms in the alkyl group is at least 3, The following are examples of such acrylic esters:

Methyl, ethyl, propyl, isopropyl, ι s

Butyl, isobutyl, s.-butyl,

2-ethyl-1-butyl-, amyl-, 3-pentyl-, 2-methyl-1-pentyl-, 4-methyl-2-pentyl-,

Hexy! -, 2-ethylhexyl-, heptyJ-,

2-heptyl, octyl, 2-octyl, nonyl, ₂₀

5-Ethy! -2-nonyl-, decyl-,

2-methyl-7-ethyl-4-undecyl-,

Dodecyl, tetradecyl, hexadecyl, octadecyl, 2-methoxyethyl,

2-ethoxyethyl and 2-butoxyethyl acrylate; 2 «,

Phenyl acrylate, o-tolyl acrylate or tetrahydrofurfuryl acrylate

Corresponding methacrylic acid derivatives and amide derivatives of acrylic or methacrylic acid can also be used used as 10

Methacrylic acid, methyl methacrylate, cyclohexyl methacrylate, isobutyl methacrylate, Isoamyl methacrylate,

jS-methoxyethyl methacrylate and

oc- (o-chlorophenyl) ethyl methacrylate; is

ß- phenoxyethyl methacrylate,

«-Phenylethyl methacrylate, phenyl methacrylate, o-cresyl methacrylate,

p-cyclohexylphenyl methacrylate,

2-nitro-2-methylpropyl methacrylate, 40

Diethylaminoethyl methacrylate,

Ethylidene acetate methacrylate,

Glycidyl methacrylate;

also esters of haloacrylic acids, such as

Methyl 2-chloro-acrylate, 45

Ethyl chloroacrylate, phenyl-ft-chloroacrylate,

α-ethyl acrylic acid; Methacrylonitrile; N-alkyl and N-aryl substituted acrylamides, such as N-methylacrylamide, N-ethylacrylamide,

N-propyl acrylamide, N-n-butyl acrylamide, 50

N -n- dodecylacrylamide,

N-n-octadecylacrylamide,

N, N-dimethylacrylamide,

N, N-diethylacrylamide,

N.N-di-n-butyl acrylamide, 5 «,

N.N-di-isobutyl acrylamide.

N-cyclohexyl acrylamide,

Ν, Ν-dicyclohexyl acrylamide,

N-phenylacrylamide,

Np-nitrophenylacrylamide, d ₀

N - ^ - Nuphthylacrylamid,

Ν-Λ-naphthylacrylamide,

N-methyl-N-phenylacrylamide,

Ν, Ν-diphenylacrylamide,

N-benzyl acrylamide, 65

Ν, Ν-di-benzyl acrylamide.

It has been found that the monoethylenically unsaturated monomer used is not critical

It is important that this is within the abovementioned ratios with the heterocyclic N-vinyl monomers copolymerize and easily be alkoxy- or aryloxyethylated simultaneously.

If insolubility in water is desired, it is recommended that the above heterocyclic N-vinyl monomers in an amount of at least 5 mole percent based on the number of moles of the monoethylene unsaturated monomers, there is mixtures present in this range of amounts of heterocyclic N-vinyl monomers contain enough active protons in the heterocyclic rings for reaction with the vinyl ether, whereby alkoxy- and aryloxyethylated polymers are formed, which in water are insoluble.

The vinyl ethers, i.e. H. the vinyl alkyl ethers and vinyl aryl ethers, as simultaneous alkoxy and aryloxyethylating agents can be used in the process of the invention and with the above-mentioned heterocyclic N-vinyl monomers or terpolymerizable Monomers or monoethylenically unsaturated polymerizable monomers are copolymerizable have the following general formula:

CH ₂ = CHORs

in which Rj denotes a straight-chain or branched alkyl radical having 1 to 30 carbon atoms, e.g. B. the

Methyl, ethyl, propyl, isopropyl,

η-butyl-, sec-butyl-, t-butyl-,

2-ethylbutyl-, 1,3-dimethylbutyl-,

n-amyl, isoamyl,

1 -Methyl-2-methylpropyl-,

Diisopropylmethyl, hexyl,

2-ethylhexyl-, octyl-, 1 -methylheptyl-,

Nonyl-, n-decyl-, 1-methyl-4-ethyloctyl-,

n-Tetradecyl-, n-Hexadecyl-, n-Octadecyl-,

Oleyl, eicosyl, ceryl and myricyl radicals;
R3 also denotes an aryl radical, e.g. B. the phenyl, o-, m- and p-cresyl, the «-naphthyl- and j3-naphthyl radical. The alkyl radical can also be substituted by an alkoxy radical or by one or more chlorine atoms, for example by the methoxy or ethoxy radical. The aryl radical can be in the form of an aralkyl group or a chloroaryl group, for example as an o-ethylphenyl, benzyl, p-chlorophenyl, 2,4-dichlorophenyl or 2,4,6-trichlorophenyl radical. The alkyl radical can be in the form of a cycloalkyl group, for example as a cyclohexyl, p-butylcyclohexyl radical.

The following are examples of such vinyl alkyl and vinyl aryl ethers:

Vinyl methyl ether, vinyl ethyl ether,

Vinyl propyl ether, vinyl butyl ether,

Vinyl isobutyl ether, vinyl amyl ether,

Vinyl 2-methoxyethyl ether,

Vinyl 2-chloro-ethyl ether,

Vinyl octyl ether, vinyl octadecyl ether,

Vinyl eicosyl ether, vinyl ceria ether,

Vinyl myricyl ether

(the latter made by vinylating eicosyl alcohol and other high-boiling alcohols such as made from Chinese wax Ceryl alcohol or myricyl alcohol made from carnauba wax, using acetylene),

Vinyl 2-methoxyethyl ether,

Vinyl-2-chloro-ethyl ether,

Vinyl cyclohexyl ether,

Vinyl phenyl ether,

Vinyl-o-cresyi ether,

Vinyl o-ethylphenyl ether,

Vinyl p-chlorophenyl ether and

Vinyl a-naphthyl ether.

Many of these vinyl ethers are commercially available substances; the others can be easily referred to in themselves Establish procedures that are described in the literature.

It stress in to that no limitation with respect to ο ι the size or configuration of the alkyl and aryl groups in vinyl ether or concerning the nature will be made of the substituents of the alkyl or aryl groups in the alkoxy and aryloxy ethylation by the method of the present invention. These groups and their substituents do not take part in the reaction.

Instead of the vinyl alkyl listed above and also VinylaryJäther VinyJätber substituted aliphatic alcohols of formula

in the R ₄

CH ₂ = CHORUS ₄

-CH ₂ CH ₂ OCH ₃

-CH ₂ CH ₂ OC ₂ H ₅

- (CH ₂ CH ₂ O) ₂ CH ₃

- (CH ₂ CH ₂ O) ₂ C ₂ H ₅

CH ₂ OCH ₃ -CH ₂ CH ₂ Cl

means that vinyl ethers prepared from amino alcohols, for example vinyl ethers of ethanolamine, diethanolamine, ß-morpholinoethanol and vinylthioethers (vinyl sulfides) are also used, with another type of very useful polymeric products being obtained. _4S

Instead of using 0.05 to 10 moles of a single specific vinyl ether, a Mixture of 2 or more different vinyl ethers can be used.

As already stated, the simultaneous alkoxy or aryloxy ethylation reaction becomes a common one Solvent used. Various alcohols such as Methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, Butanol, secondary butanol, amyl alcohol, hexanol, 2-ethyl-1-hexanol, ethylene glycol, 1,2-butanediol and 1,4-butanediol in question. Other inert Solvents such as diethylene glycol or ethylene glycol monomethyl ether can be used. The chemical The nature of the organic solvent is not critical as long as it is ensured that it is compatible with the Starting materials (or the polymers formed during the polymerization) are a solution forms and is insensitive to alkoxy or aryloxy ethylation.

The amount of inert organic solvent used is not critical. Loads of Solvent that meets the specified conditions can be used. It was found that out for practical reasons, about 1 to 10 parts of organic solvent per part by weight of starting materials (Parts by volume or parts by weight) are sufficient to obtain a usable solution.

Any known organic tertiary alkyl peroxide or Hy droperoxyd can be used, for example

Di-tert-butyl peroxide,

tert-butyl perbenzoate,

Di-terL-butyl perphthalate,

tert-butyl-pentamethylethyl peroxide,

terL-butyl-triphenylmethyl peroxide,

bis- (triphenylmethy]) - peroxide,

2,5-dimethylhexyl-2,5-dihydroperoxide,

2,5-dimethyl-2,5-di (tert-butyIperoxy) -hexane,

2,5-dimethylhexyl-2,5-di (peroxybenzoate) _T

tertiary butyl hydroperoxide:

para-methane hydroperoxide.

If low-boiling vinyl ethers, for example those which boil below 70 ⁰ C, is used in this reaction must be carried out in pressure vessels. In such cases, the organic peroxide catalyst and the heterocyclic N-vinyl monomer, alone or as a mixture, dissolved in an inert organic solvent, are placed in a corrosion-free steel shaking bomb. The low-boiling vinyl ether is then added to the bomb, which is sealed and heated to a temperature of about 80 to 200 ° C. for 3 to 48 hours. The resulting pressure in the bomb can range from 3.5 to 70 atmospheres. After cooling to the usual temperature, the contents of the bomb are freed from solvents or volatile substances by vacuum distillation or other customary measures.

However, if it is desired that the alkoxy or aryloxyethylated product in solution is a high-boiling point aliphatic hydrocarbon is obtained, the reaction mixture is subjected to vacuum distillation subjected and the removed inert organic solvent at the same time by a saturated replaces aliphatic hydrocarbon, which has a higher boiling point than the organic solvent owns. When the organic solvent is removed there is a solution of the alkoxy or aryloxyethylated Polymers originated in the aliphatic hydrocarbon. Saturated aliphatic hydrocarbons, the have a higher boiling point than the organic solvent used, are available in large Number available; it therefore means no difficulty in finding such a suitable hydrocarbon to be selected in the preparation of the solution of the alkoxy or aryloxyethylated polymers. The consumption of vinyl ether can be 75 to 100% in the reaction process described above.

If 1 mol of a heterocyclic N-vinyl monomer is copolymerized at the same time with 0.05 to 10 mol of vinyl ether in a solution of an inert organic solvent and in the presence of 0.025 to 0.2 mol of an organic peroxide per mol of vinyl ether at 80 to 200 ⁰ C and alkoxy or aryloxyethyl is obtained, a copolymer is obtained in which some or all of the heterocyclic N-vinyl radicals contain one or more alkoxyethyl or aryloxyethyl groups.

For example, for N-Vinvl-2-PvrmliHr> n

and a vinyl ether, the resulting copolymer following formula:

CH, - CH

in which A denotes hydrogen, an alkoxyethyl or aryloxyethyl radical and at least one A represents the said alkoxyethyl or aryloxyethyl radical; R3 has the same meaning as above, Z denotes 100 mol percent N-vinyl-2-pyrrolidone used and we have a numerical value of at least 1.

c
j - CH Λ A. I.
-H C- ( ) N .... I.
C. CH, - ■ - Λ

With this VurUhrensweise one can instead of the Use of one mole of a heterocyclic N-vinyl monomer 1 mole of a mixture of two different heterocyclic N-monomer or 1 mole of a mixture consisting of 5 to 99 mole percent of one heterocyclic N-vinyl monomer and 1 to 95 mole percent of a monoethylenically unsaturated polymerizable Monomer consists, at the same time with 0.05 to 10 mol of a vinyl ether in solution in an inert

ίο terpolymerize organic solvents in the presence of 0.025 to 0.2 mol of an organic peroxide per mol of vinyl ether at 80 to 200 ⁰ C within a period of 3 to 48 hours and alkoxy or aryloxyethylate.

The resulting from this simultaneous reaction alkoxy- or aryloxyethylated terpolymer can with Use of a mole of a comonomer mixture of N-vinyl-2-pyrrolidone and ethyl acrylate and of 0.05 to 10 moles of vinyl ether are described as follows will:

CH, CH-A

OH

C = O

N
I.

'-CH,

C) -A

CO-CHCH,
C-CH,

CH, -CH

where A is hydrogen or an alkoxyethyl or aryloxyethyl radical and at least 1 A is said alkoxyethyl or aryloxyethyl radical; Ra has the same meaning as above, .sr in the terpolymer 5 to 99 mol percent, y 1 to 95 mol percent, ν has a numerical value of at least 1. The exact value of w is in the alkoxy- or aryloxyethylated copolymer or terpolymer that made in this way difficult to determine. It should be noted that since the molar ratio of vinyl ether to heterocyclic N-vinyl monomer, or a mixture of such monomer with other comonomer, is 0.05 to 10, a difficult and time consuming effort would be required to obtain the exact amount of vinyl ether to determine who actually copolymerizes or terpolymerizes in each case; the same applies to the exact amount that is actually consumed in the alkoxy or aryloxyethylation of the active sites.

From the results of systematic studies carried out by means of fractional solution, thermal degradation, vapor phase chromatography, infrared spectroscopy and nuclear magnetic resonance spectroscopy, it was concluded that the alkoxy- and aryloxyethylated copolymers and terpolymers by simultaneous copolymerization or terpolymerization and alkoxy- and aryloxyethyl-heterocyclic monomerization optionally with the addition of other polymerizable monomers, the value of w in the copolymeric or terpolymeric structures being at least 1, can be obtained.

If it is desired that the alkoxy or aryloxyethylated copolymer or terpolymer is obtained in a solution of a high-boiling aliphatic hydrocarbon liquid in a mineral or lubricating oil, the simultaneous copolymerization or terpolymerization and alkoxy or aryloxyethylation with vinyl ether is one of the further options Carry out the above-mentioned more volatile solvent, then, when the reaction is approximately complete, the reaction mixture is subjected to vacuum distillation, the more volatile solvent and dif other volatile components are replaced by the high-boiling liquid hydrocarbons just mentioned in the same way.

The alkoxy and aryloxyethylated polymers produced according to the invention have numerous new « and advantageous uses. So they have properties that when applied to dit cause human skin to soften and relieve tension, for example The compounds prepared according to the invention are therefore excellent additives for soaps and cosmetics

So see preparations that serve for cleaning, conditioning and beautifying, whereby in addition to the above-mentioned effects, a smoothing of the skin is brought about.

These homopolymers and copolymers can be ai

Place or next to petroleum hydrocarbons, d. h mineral oils, petroleum jelly and paraffin waxes are used. They are not only soluble in these petroleum hydrocarbons, but also in other oily, fatty or oily materials, such as ii

Fatty acid, stearic acid, myristic acid, oleic acid, fernei in glyceryl monostearate (-glycosterol), Lanolii (Wool fat), beeswax and other animal and vegetable waxes, higher alcohols, such as hexa noL myristic alcohol ethylene glycol methyl ethyl ketor

Ethylene glycol ether and butyrolactone, which are too nice unity preparations and analogous preparations of this type are used. The compound produced according to the invention «

can be easily emulsified by the reagents customary in the cosmetics industry. As a result of their solubility, their emulsifiability and because of their compatibility with other components of cosmetic preparations, the new compounds reduce to a large extent or eluminate the drying tendency of the mineral oils and petrolatum which are present in such compositions. The new compounds, as additives in cosmetic substances which contain paraffin wax, also avoid clogging of the pores. Whether the cosmetic preparations petroleum hydrocarbons, animal oils, lanolin and / or other oily or ointment-like components include, or not, the presence of the additives of the invention gives these preparations, the ι s property in the treatment of skin or skin-like structure of this smooth To give texture, at the same time a softening of the skin and possibly a relief of tension and the like is achieved. _J0

The amount of product produced according to the invention that is added in order to achieve the effects indicated above varies between about 1 to about 50 percent by weight, based on the total weight of the finished cosmetic composition. The new compounds can following products are added at each stage of production: cold creams, cleansing cream, Erweichungscreme, finishing cream, halbflüssife emollients, hand cleaners, lubricating cream, night cream, absorption sub \ a location cream, Handcreme- and lotions, foot cream, baby cream, baby skin oils, Special cream, such as astringent creams, bleaching creams, acne creams. Barrier creams (creams for industrial use), vanishing creams, base creams, shaving creams, shaving preparations, post-shave lotions and sprays, medicinal creams, anti-odor and anti-fumes, such as anti-odor creams and lotions, anti-odor creams and lotions, anti-odor agents to be rolled up, red-paste or sunburn preparations Lotions, red creams, massage oils, face masks, hair removal agents and hair removal creams, makeup agents in paste or lotion form, face powders, eye makeup agents, ie shadow and eyebrow creams, fingernail creams and cleansers, hair bleaching 1 · -. agents and coloring agents, epidermis softeners, hair conditioning agents, hair curlers, hair dressings, hair brillantines, hair oils, hair sprays, creams and shampoos, nail polish removers, lip pens, perfume pens, facial soaps, synthetic soaps, antiseptic soaps (tincture of green hand soap), insect protective soap , water-free hand cleansers, dentifrices, shampoos for pets or bath talk.

Cosmetics and toilet preparations which the invention- 5s Made-to-measure products are smoother in texture and lighter on the skin and on it Environment (hair and nails).

After these agents have acted on the skin, for example the scalp, it remains soft and supple, this softening effect also remaining when the agents themselves are removed again by washing with soap and water. When applied to the hair, a film of these preparations is deposited on the hair. which makes it soft, smooth, shiny and lively looking; these effects persist even after washing the hair with soap and water. it also improves the ability of the hair to treat. After the fingernail or toenail compositions have been applied, they become smooth, with the neighboring skin also becoming soft and supple.

The compounds prepared according to the invention are also available as pigment distributors: open and as Dye receptors effective. In the case of hair preparations, the presence of the present invention improves Products of the softness, the water repellency and the workability of the hair, in hair conditioning agents the new products can be added to creams, foams or gels, the resulting preparations then being mixed with nitrogen, Argon or the usual ciuor-chloro-hydrocarbons are pressure treated.

Due to their solubility in hydrocarbons and mineral oils, the products are particularly suitable for Use as a hot melt alone or in combination with paraffin waxes as a coating agent for the various fiber materials suitable. Extruded Films made from these compounds can be used either alone or together with waxes and resins in paper or other fibrous materials are incorporated.

The compounds made according to the invention are available with a variety of resins, waxes and compatible with polymeric substances at normal or elevated temperatures. You are as Binding materials or penetrants in hard and soft cardboard can be used.

Furthermore, the products made according to the invention are useful as protective agents for wires and Cable in the form of outer sheaths or sheaths.

Films or coatings made from the polymers are also suitable as lining material for metal or fiber drums for transporting products that are prone to moisture, dust or corrosion. The newer. Connections can also be used as electrical finishing material, for example as insulating means for electrical cables, as dip lacquer for electrical capacitors, as insulating coating means, as sealing means, for example in the production of moisture-proof coils, resistors and paper capacitors; The new compounds are also useful as sealants, as adhesives and distributors of insecticidal compositions, as waterproof sealants, as adhesives, as paper coating agents and as dispersants for inks and dye pastes, also as leather treatment agents !, al: dyeing aids, as agents for waterproofing textiles and as a textile forming agent.

Emulsions of the compounds of the invention are particularly useful in impregnating paper .

If you dissolve the compounds in amounts of up to 3 percent by weight in light mineral oil, the result is an effective penetrant that loosens rusty and frozen nuts and bolts

The products according to the invention further sini particularly in the dye removal, al i igment dispersants and protective colloids, as before nT ^{8e de Scnutzüber} trains, as paper additives to -Überzüge, as a binder for pressed Detergenzier as binders for tablets and as Dyes: Coloring ferment in tablet coating. suitable

Uie connections are still usable i dispersion resins and various polymer types

"V

They are particularly useful as sludge dispersants in lubricating oils and as binders for paper, plastics and textiles; They are very useful as reprecipitation inhibitors in detergents, as detergent hydrotropes and softeners, rather, in dry cleaning detergents, as foam stabilizers for shampoos, as stabilizers for detergents of higher and lower density, as foam stabilizers when drilling into oil or gas sources, as latex stabilizers, as stabilizers of hydraulic ι ο emulsion liquids, as emulsifiers in emulsion polymerization reactions, as emulsifiers for agricultural protective agents, such as insecticides, fungicides, herbicides as inhibitors for clay hydration sludge, as corrosion inhibitors, as inhibitors for ι s machine rust by oil, as complex-forming agents Liquid-liquid extracts, as dye receptors for polypropylene, as dye fixatives, as pigment dispersants in pigment printing, as fluidizers for paper coating suspensions, as pitch dispersants, as adhesives Instead of starch, casein, synthetic lances, as an antistatic agent for polystyrene and other plastics, as an adhesive for polyolefins and other plastics, as a flexibility- generating agent κ, for phenolic and other thermosetting resins, as a dispersant and gloss improver for floor waxes and polishes , as a thickening agent in non-aqueous systems, as a membrane for staining procedures and filtrations, as adhesion promoters for \ o paper or paperboard to polyamides.

The new compounds can also be used as additives for waxes to lower the melt viscosity, to improve the flexibility, the gloss and also the hardness. The new compounds are also useful as color ink acceptors for surface printing of high-density polyethylene vessels, as absorbents for tobacco tar in cigarette filters, as absorbents for toxic gases and vapors, as thickeners for petroleum oils and 4 "oil-based paints, as coatings for adhesive tapes and as ingredients for hot melt adhesive, as the melting point distribution for natural and synthetic resins such as an amplifier means for Leimreduktionsmittel with respect to the hydrophobic character of polar resins. ₄ ς

The compounds are also excellent dye receptors for polyolefin fibers, in particular for those made of polyethylene, polypropylene and polybutylene. They also lend rayon fibers to both Viscose as acetate fibers increased strength and good dyeing properties. The connections are further excellent sizing agent for glass fibers as they have an adhesiveness due to the heterocyclic nature N-vinyl units and a further lubricity due to the presence of alkoxy ss or have aryloxyethylated groups.

The compounds prepared according to the invention further improve the gloss of waxes and polishing agents. They are better soil suspending agents than the corresponding unreacted synthetic detergent products. For example, the new compounds are particularly useful as soil dispersants in dry cleaning agents, and they are also useful as antistatic agents for synthetic fibers; in the textile industry they are valuable in t * the manufacture of antistatic agents. Lubricants, waxes and coloring agents to maintain the degree of coloring. The compounds are also useful as adhesives, flocculants and gelling agents.

The compounds prepared according to the invention give petroleum products such as kerosene, fuel oils, Jet fuels and other combustible hydrocarbon liquids have dispersing and detergent properties. Thus, the new compounds easily disperse resins and in the products just mentioned resinous substances such as asphaltenes.

The compounds are also useful as mold removal lubricants, as anti-stick and anti-blocking agents, and also as anti-static agents for films and textile fibers and as flattening, softening and sizing agents for textiles. You are with Petroleum resins compatible, such a mixture can advantageously be used for waterproofing, as Coating material of pipelines and used as a concrete hardening agent, with the deposit a water-tight membrane takes place with certainty.

In the case of carbon paper, the compounds produced according to the invention serve as a means of transport for the color and prevent the color ink from completely sinking into the paper.

The compounds prepared according to the invention form with elemental iodine, with iodine monochloride and Iodine monobromide halogen adducts. These iodine adducts are made by making the compounds carefully heated until they melt, stirring constantly and elemental iodine or a solution of elemental iodine in alcohol or carbon tetrachloride or a mixture of these Adding solutions. About 2.5 to 25.0 weight percent iodine can be added to the molten product incorporate. The resulting iodine adduct is in mineral oil of one pharmaceutical grade and others soluble in oily materials. The iodine adduct can be used in powders, ointments, suppositories and toilet compositions (cosmetic substances and soaps) can be incorporated into antiseptic germicidal compositions which at the same time soften and smooth human skin.

The compounds made in accordance with the present invention are also excellent V.I. improvers for Lubricating oils and useful additives for mineral oils used as hydraulic fluids. the Compounds prepared according to the invention are also valuable additives for automotive polishes, as they improve the gloss and act as rust inhibitors in coating varnishes and finish paints against metal works.

example 1

In a 1 liter shake bomb made of stainless steel: which had been purged with nitrogen, the one from the dei Enter the existing solution in the following ingredients and seal the bomb on it:

N-vinyl pyrrolidone
Isopropanol
Vinyl isobutyl ether
Di-tert-butyl peroxide

200.0 g (1.8 moles)

300.0 g (solvent) 70, Og (OJMoI) 10.0 g (0.068 mol)

The bomb was at 130 to 140 degrees for H hours heated and shaken, then cooled and ventilated. A sample was taken and un analyzed, which was found to be no N-Viny

pyrrolidone and vinyl isobutyl ether was no longer present in the polymeric solution. The contents of the bomb was then placed in a beaker, by adding water to a solids content of 10% diluted (the addition of water resulted in a white emulsion) and dried by spraying. Man thus obtained a dry, white powdery product which was 97.5% solids and 9.8% nitrogen content, which corresponds to 77.8% of polymerized N-vinylpyrrolidone residues. The product obtained is insoluble in water, but can be distributed in it, it is also insoluble in Hydrocarbons, but soluble in amides and alcohols, ketones and halogenated hydrocarbons. Its average molecular weight is 17,000.

Example 2

A 1 liter four-necked flask fitted with a stirrer, thermometer, reflux condenser, and nitrogen sparge became thorough purged with nitrogen and then charged with the following compounds:

N-vinyl pyrrolidone

Ethyl acrylate

Methyl isobutyl carbinol

Di-tert-butyl peroxide

Vinyl cetyl ether

90.0 g (0.81 mole) 60.0 15 (0.6 mole)

200.0 15 10.0 (j

335.0 15 (1.25 moles)

The resulting mixture was heated, initially at a temperature of 100 ° C a vigorous re-condensation was carried out, which, however, subsided in the progression of the reaction and temperature elevation, left for 3 hours at 125 to 14O ⁰ C, then additional 10.0 g of the peroxide were added and the Reaction continues. (A total of 20.0 g of peroxide were added = 137 mol). After a total reaction time of 16 hours, the flask contents were cooled and analyzed. There was no residue of N-vinylpyrrolidone or ethyl acrylate. 0.9 percent by weight of vinyl cetyl ether was found in the solution, which corresponds to only 6.3 g of unreacted vinyl ether.

The contents were then subjected to the Vakuurnverdampfung, wherein at the end of 30 minutes ruled a temperature 135-150 ⁰ C and a pressure of 1.0 mm Hg. The product remaining in the reaction vessel consisted of 443 g of an amber-colored, clear and viscous liquid; The: se, while tie was still hot, input into a vessel containing 440 g 100 sec-solvent, an oil solution was obtained, which is valuable as a sludge dispersant in lubricating oils

N-vinyl pyrrolidone Vinyl acetate Vinyl isooctyl ether

Ethanol

Di-tert-butyl peroxide

III, 0 g (1.0 mol) 28.15 g (O333 mol)

156JDg (1.0 mole)

200g 14.0g (0.0% mole).

The bomb was heated to 125 to HOC for 16 hours while shaking; it was then cooled, vented, the contents of the bomb placed in a 1 liter reaction flask and analyzed. N-vinylpyrroliuon, vinyl acetate and vinyl isooctyl ether could no longer be determined. The volatile constituents were then evaporated first at atmospheric pressure and then in vacuo, at the end of this operation a temperature of 140 to 160 ° C. and a pressure of 0.5 mm Hg prevailing for 45 minutes. The remaining residue was removed from the flask at a temperature of 100 ^° C. and consisted of 265 g of a product which, after cooling to room temperature, changed into a clear, flexible solid. The analysis showed that this product contains 4.92% nitrogen, which corresponds to 39% polymerized N-vinylpyrrolidone residues. It is soluble in all aliphatic and aromatic hydrocarbons, in halogenated hydrocarbons, ketones, esters and alcohols.

Example 4

Into a 1 liter stainless steel shake bomb that had previously been purged with nitrogen, the following components were entered and then the bomb was sealed:

35

_so

55

Example 3

The following components were placed in a 1 liter stainless steel shake bomb which had been purged with nitrogen, and the bomb was then sealed:

60 N-vinyl pyrrolidone
Vinyl phenyl ether
Isopropanol
Di-tert-butyl peroxide

150.0 g (1.35 moles)
50.0 g (0.41 mol)
300 g (solvent)
9.0 g (0.061 mole).

The bomb was then ^{heated to 125 to 135 °} C. for 12 hours and shaken in the process. This was followed by cooling, ventilation and a sample taken for analysis for residual monomer. It was found that no trace of N-vinylpyrrolidone and only 1.5 percent by weight of vinylphenyl ether were present in the solution, which corresponds to only 7.6 g of vinyl ether. The contents of the bomb were transferred to a stainless steel trough and placed in a vacuum oven. The latter was held at a temperature of 120 to 130 ° C. for 16 hours at a pressure of 10 to 15 mm Hg. The yellowish-colored solid product obtained in this way consisted of 95.0% solid components and weighed 197 g. It is insoluble in hydrocarbons and water, but soluble in amides, ketones and alcohols. Its nitrogen content was determined to be 9.8%, which corresponds to 77.8% of polymerized N-vinylpyrrolidone residues

It is clear to the average person skilled in the art that in the simultaneous copolymerization and terpolymerization according to the present invention, alkoxy- and aryloxyethylated tetra-, penta- and hexapolymers are obtained if one mole of a mixture of 3, 4, 5 or 6 different polymerizable monomers, In these cases, the respective proportional amounts from which the monomer mixture of the simultaneous polymerization to alkoxy or aryloxyethylation is composed are unimportant as long as the mixture of monomers is at least 5 mol percent of heterocyclic! N-Vinylmono mer, which has a carbonyl functionality, contains

The polymerizable monomers of such mixtures can also be other than those described above

being. In other words, if the mixture of monomers contains at least 5 mole percent of heterocyclic} Contains N-vinyl monomer and the mixture is soluble in an inert organic solvent, so a polymerization and alkoxy or aryloxy

Ethylation of the mixture according to the present invention take place, with a variety of polymeric Products can be obtained that have varying solubility characteristics in polar and non-polar Own solvents.

Claims (1)

Claim: Process for the preparation of alkoxy- or aryloxyethylated polymers of heterocyclic N-vinyl monomers, characterized in that 1 mol of a heterocyclic N-vinyl monomer which has a carbonyl function in the heterocyclic ring in the vicinity of the nitrogen atom, or a monomer mixture of 5 to 99 mol percent of such a heterocyclic N-vinyl monomer and 1 to 95 mole percent of a monoethylenically unsaturated monomer together with 0.05 to 10 moles of a vinyl ether in an inert organic solvent in the presence of 0.025 to 0.2 moles of an organic peroxide per mole of vinyl ether to a temperature of 80 heated to 200 ^{0 C.}