DE1570655B2 - Process for the simultaneous polymerization and alkylation of heterocyclic compounds - Google Patents

Description

/ \
R ₁ -CH C = O

CH = CH ₂

/ \
R ₁ -CH C = O

CO-CR ₁ = CH ₂

/ \
R ₁ -CH C = O

(Cnti ₂ n0) _m - COCR ₁ = CH ₂

/ \
R ₁ -CH C = O

C _y H ₂ y ■ NR ₂ CO CR ₁ = CH ₂

(I)

(Π)

(III)

(IV) the polymerized, the use of ethylene as the α-olefin being excluded.

2. Use of the products prepared according to claim 1 as an additive in propellant and Fuels and lubricating oils.

in which R is an ethylene, trimethylene or tetramethylene group and R _{1 is} a hydrogen atom or a methyl group, m is an integer with a value of 1 to 4 and η is an integer with a value of 1 to 4, if m denotes Has the value 1, and is from 2 to 4, when m has the value 2 to 4, R ₂ denotes a hydrogen atom, an alkyl radical having 1 to 12 carbon atoms or a phenyl group and y has the value 2 or 3, or

(c) a mixture of two of the compounds mentioned, or

(d) a mixture of 5 to 99 percent by weight of one of the compounds mentioned and 1 to 95 percent by weight of a non-heterocyclic, polymerizable, monoolefinically unsaturated Monomers with 0.05 to 12 moles of either an α-olefin or a chlorofluoroethylene or Fluoroethylene with 2 carbon atoms in solution in an organic solvent in Presence of 0.025 to 0.30 moles of an organic peroxide per mole of -olefin and temperatures from 80 to 200 ° C for 3 to 60 hours. It is known that homopolymers can be heterocyclic N-vinyl lactams, N-vinyloxazolidones, N-vinylmorpholinones and their copolymers with other monomers containing a polymerizable vinyl group easily by conventional methods getting produced. Homopolymers of such heterocyclic N-vinyl monomers and their Copolymers with 1 to 95 percent by weight of a monomer with a polymerizable vinyl group are usually in a wide variety of solvents, such as alcohols, ether alcohols, amines and other polar organic solvents, soluble but insoluble in aliphatic Hydrocarbons such as hexane, heptane, cyclohexane, methylcyclohexane, white spirit, mineral oil and

Lubricating oil. j

The industry is now calling for homopolymers and

Copolymers of heterocyclic N-vinyllactams, N-vinyloxazolidones and N-vinylmorpholinones, the Have properties given them by the presence of their heterocyclic rings v / earths, but which have particular solubility properties that are intended by the particular End use depend. So are z. B.

Polyvinylpyrrolidone and copolymers of vinylpyrrolidone and vinyl acetate are very effective hair care products, however, their solubility in water is undesirable for certain purposes. Also should such products have a lower degree of hygroscopicity and improved moisture resistance exhibit. In another case, the effectiveness of polyvinylpyrrolidone as a dispersant can be used cannot be made usable because it is in the medium, e.g. B. a lubricating oil in which it acts as a dispersant is intended to serve, is insoluble. The same goes for B. for polyvinylimidazole, polyvinyloxazolidones and Polyvinyl morpholinones. In another case, the one polymer through the heterocyclic The adhesive properties conferred on the ring are partially impaired by its poor moisture resistance. Furthermore, the complex-forming abilities of such homopolymers and copolymers can as color receptors in difficult-to-color polymers such as polyethylene and polypropylene, cannot be made useful because of the insolubility of the polymers in these polymers.

According to an older, not previously published proposal is a process for the production of copolymers of ethylene with N-vinyl lactams and optionally vinyl acetate under increased pressure in Presence of radical-forming compounds known as catalysts, which is characterized is that one is in an organic solvent or in a mixture of organic solvents polymerized, whereby the liquid phase can contain up to 50 percent by weight of water and ethylene, if necessary under increased pressure, at least 5 percent by weight must dissolve. Preferably

this process is carried out at pressures of 20 to 2500 atm.

The invention relates to a process for the simultaneous polymerization and alkylation of heterocyclic polymerizable compounds, characterized in that 1 mol

(a) a monomeric heterocyclic N-vinyl compound or

(b) a compound of the general formula

/ \
R ₁ - CH C = O

(I)

R.
R ₁ -CH C = O

CO - CR ₁ = CH ₂

/ \
R ₁ -CH C = O

N
(C "H ₂ " O) _m - COCR ₁ = CH ₂

/ \
R ₁ -CH C = O

(Π)

(ΠΙ)

(IV)

35

40

NR ₂ CO CR ₁ = CH ₂

in which R is an ethylene, trimethylene or tetramethylene group and R _{1 is} a hydrogen atom or a methyl group, m is an integer with a value of 1 to 4 and η is an integer with a value of 1 to 4, if m denotes Has the value 1, and from 2 to 4, when m has the value 2 to 4, R _{2 is} a hydrogen atom, an alkyl radical with

1 to 12 carbon atoms or a phenyl group and y is 2 or 3, or

(c) a mixture of two of the compounds mentioned, or

(d) a mixture of 5 to 99 percent by weight of one of the compounds mentioned and 1 to 95 percent by weight of a non-heterocyclic, polymerizable, monoolefinically unsaturated monomer with 0.05 to 12 mol of either an α-olefin or a chlorofluoroethylene or fluoroethylene with

2 carbon atoms in solution in an organic solvent in the presence of 0.025 to 0.30 mol of an organic peroxide per mole of α-olefin and temperatures of 80 to 200 ° C for 3 to Polymerized for 60 hours, the use of ethylene as an α-olefin is excluded.

The resulting solution of the alkylated polymer prepared according to the invention can be used as such can be used or the organic solvent can be removed by vacuum distillation. The degree of alkylation is determined by the amount of α-olefin consumed and can be from only 1 to 90 percent by weight of the alkylated polymer. The solubility in polar solvents decreases, and the solubility in non-polar solvents increases with higher Degree of alkylation. In other words, homopolymers and copolymers can be obtained, in which some or all of the heterocyclic rings have one or more alkyl groups with at least 3 carbon atoms up to as many carbon atoms as in that used in the reaction a-olefin are included. The average molecular weight of such homopolymers and copolymers varies between 50,000 and 350,000.

Examples of the monomeric heterocyclic N-vinyl compounds (a) are N-vinyloxazolidone, N-vinylsuccinimide, N-vinylpiperidine, N- vinyldigly kolylimide, N-vinylglutarimide and N-vinyl-3-morpholinone.

Examples of compounds of the general formula I are N-vinyl-2-pyrrolidone, N-vinyl-5-methyl-2-pyrrolidone, N-vinyl-2-piperidone, N-vinyl-6- methyl-2-piperidone, N -Vmyl-e-caprolactam and N-vinyl-7-methylcaprolactam. Comparable compounds can be obtained from the corresponding thiolactams, and these can also be used in the process according to the invention.

Examples of compounds of the general formula II are N-methacryloylpyrrolidone, -piperidone and caprolactam; N-methacryloyl-5-methylpyrrolidone, N-methacryloyl-6-methylpiperidone and N-methacryloyl - 7 - methylcaprolactam; N -acryloyl-5-methylpyrrolidone, N-acryloyl-6-methylpiperidone and N-acryloyl-V-methylcaprolactam.

Examples of compounds of the general formula III are N-acryloxymethylpyrrolidone, -piperidone and caprolactam; N-methacryloxyethoxy-ethylpyrrolidone, piperidone and caprolactam; N-methacryloxypropyl pyrrolidone, piperidone and caprolactam; N-methacryloxy-methylpyrrolidone, -piperidone and -caprolactam; N-methacryloxy-ethylpyrrolidone, -piperidone and caprolactam; N-methacryloxy-methyl-5-methylpyrrolidone, -6-methylpiperidone and -7-methyl-caprolactam.

Examples of compounds of the general formula IV are N-methacrylamidomethyl, N-methacrylamidoethyl, N-methacrylamidopropyl and N - (N-phenylaerylamidopropyl) -pyrrolidone, -piperidone and -caprolactams. These connections can easily be made by Acryloyl or methacryloyl chloride or bromide with an N- (aminoalkyl) lactam in which the Alkyl has 1 to 12 carbon atoms, in the presence of a base as hydrogen halide acceptor implements.

The simultaneous polymerization and alkylation of a mixture of comonomers containing 5 to 99 percent by weight of one of the aforementioned heterocyclic polymerizable compounds and 1 to 95 percent by weight of a non-heterocyclic, polymerizable, monoolefinically unsaturated monomer is carried out in the same way as for the heterocyclic compounds alone or for a mixture of two such monomers. The various, non-heterocyclic, polymerizing

available, monoolefinically unsaturated monomers, which copolymerized with the heterocyclic compounds are z. B. vinyl acetate, vinyl methoxyacetate, vinyl diethyl acetate, vinyl trimethyl acetate, Vinyl propionate, vinyl isobutyrate, vinyl butyrate, vinyl lactate, vinyl caproate, vinyl caprylate, vinyl stearate, Acrylic and methacrylic acid derivatives, such as methyl methacrylate, cyclohexyl methacrylate, isobutyl methacrylate, Isoamyl methacrylate, p-methoxyethyl methacrylate and a- (o-chlorophenyl) ethyl methacrylate, ß-phenoxyethyl methacrylate, ß-phenylethyl methacrylate, Phenyl methacrylate, o-cresyl methacrylate, p-cyclohexylphenyl methacrylate, 2 - nitro - 2 - methylpropyl methacrylate, diethylaminoethyl methacrylate, ethylidene acetate methacrylate and glycidyl methacrylate, including esters of haloacrylic acids such as methyl-a-chloroacrylate, Ethyl-a-chloroacrylate, phenyla-chloroacrylate, α-ethyl acrylic acid, methyl acrylate, propyl acrylate, acrylic acid, methacrylic acid, acrylonitrile, Methacrylonitrile, acrylamide, methacrylamide, as well as N-alkyl- and N-aryl-substituted acrylamides. According to the invention is the type of non-heterocyclic, polymerizable, monoolefinically unsaturated Monomers are not critical as long as such a monomer is in every proportion with the heterocyclic polymerizable compound can enter into copolymerization.

It is noteworthy that a mixture of comonomers containing only 5 percent by weight of those mentioned heterocyclic polymerizable compound and 95 percent by weight of a non-heterocyclic, polymerizable monoolefinically unsaturated monomers contains sufficient nitrogen-containing heterocyclic rings for alkylation during simultaneous polymerization and alkylation having.

Instead of such a mixture, it is also possible to use a mixture of two different heterocyclic polymerizable compounds. The latter mixture can contain 5 to 99 percent by weight of any of the aforementioned heterocyclic compounds and 1 to 95 percent by weight of another heterocyclic compound. Such a comonomer mixture contains sufficient nitrogen-containing heterocyclic rings for a higher degree of alkylation during the simultaneous polymerization and alkylation.

In the alkylation of monomers of the aforementioned heterocyclic polymerizable compounds alone or in admixture during the simultaneous polymerization and alkylation any α-olefin with a molecular weight up to 2500 can be used, the use of Ethylene as «-olefin is excluded. This means that olefins such as propene, 1-butene, 1-pentene, 2-ethyl-l-butene, 2-methyl-l-pentene, 1-hexene, 5-methyl-1-hexene, 2-methyl-l-pentene, 3-ethyl-l-pentene, 1-heptene, 1-octene, 1-nonene, 2-ethyl-l-hexene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 1-docoses, 1-tetracoses, 1-pentacoses and polybutenes with a molecular weight of 400 to 2500 can be used.

Instead of a single one of the aforementioned -olefins, a technical alkylating agent can also be used Mixture of linear olefins, as produced by petroleum wax cracking or polymerisation of lower olefins obtained can be used. The technical product contains a mixture of linear olefins. One such mixture can be linear olefins having 6 to 8 carbon atoms, 8 to 10 carbon atoms, 10 to ^ carbon atoms, 12 to 16 carbon

Ξ atoms, 16 to 20 carbon atoms and 20 to Contains 42 carbon atoms. So contains z. B. the product of linear heptene with 92% monoolefins 89% α-heptene, 6% α-hexene and 5% α-octene, based on monoolefins. Through careful distillation of the technical product are essentially individual -olefins obtained as alkylating agents can be used.

Although linear olefins are preferred because of their ready availability, the present invention found that the numerous isomers of α-olefins range from 1-pentene to 1-pentacoses as well Polybutenes can also be used in the alkylation. The only condition in one such a case is that the isomer contains a double bond in the α-position.

Instead of a-olefin as an alkylating agent can also chlorofluoroethylene, such as dichlorovinylidene fluoride, chlorovinylidene fluoride, chlorotrifluoroethylene, Tetrafluoroethylene or vinylidene fluoride, for the production of new valuable polymers with a nitrogen-containing heterocyclic ring containing a fluorine or chlorofluoroethane group is used will.

When carrying out the simultaneous polymerization and alkylation, an organic solvent should be used be used that the α-olefins, fluoroethylene, chlorofluoroethylene, the heterocyclic polymerizable compound alone, a mixture of two different heterocyclic polymerizable Compounds or a mixture of a heterocyclic polymerizable compound and dissolves a non-heterocyclic, polymerizable, monoolefinically unsaturated monomer. Examples suitable solvents are alcohols such as methanol, ethanol, propanol, isopropanol, butanol, sec-butanol, amyl alcohol, hexanol, 2-ethyl-1-hexanol, Ethylene glycol, 1,2-butanediol and 1,4-butanediol. Other solvents such as Diacetone alcohol, diethylene glycol, ethylene glycol monomethyl ether acetate or methylene chloride are used will. The type of organic solvent is not critical, as long as it is it is liquid, with the heterocyclic monomers and polymers, the non-heterocyclic, polymerizable, monoolefinically unsaturated monomers and copolymers, the α-olefin and the fluorine and chlorofluoroethylene forms a solution and is less subject to alkylation than the abovementioned monomers and polymers.

The amount of organic solvent used is also not critical. It is sufficient that a solution of the monomer, the mixture of monomers and the α-Olefins or the fluorine or chlorofluoroethylene supplies. However, for the sake of convenience found that per part by weight of monomer or a mixture of monomers 2 to 10 parts (parts by volume or parts by weight) of the organic solvent to achieve a workable solution sufficient.

According to the invention, the usual peroxide initiators for the polymerization and alkylation can be used organic peroxides are used, such as tert.

Butyl perbenzoate, dibenzoyl peroxide, benzoyl hydroperoxide, tert-butyl hydroperoxide, tert-butyl perphthalic acid, p-chlorobenzoyl peroxide, tert-butyl peracetate, Di-tert-butyl peroxide or cumene peroxide.

Where homo- and copolymers with a low degree of alkylation are required and where a low molecular weight -olefin is used, the simultaneous polymerization and alkylation can be carried out in the presence of any of the aforementioned alcohols.

Where the alkylated homo- or copolymers in an aliphatic, liquid hydrocarbon with 6 or more carbon atoms, a mineral oil or lubricating oil based on paraffin should be soluble, the simultaneous polymerization and alkylation is preferably carried out in the presence of a higher-boiling one aliphatic alcohol such as hexanol. After the desired degree of alkylation has been reached the reaction mixture subjected to vacuum distillation, and the removed, higher-boiling alcohol is made up of a saturated aliphatic hydrocarbon with a higher boiling point than that of alcohol. After removal of the alcohol, a solution of the alkylated polymer is obtained obtained in the aliphatic hydrocarbon.

If low-boiling α-olefins with 3 to 6 carbon atoms or the fluoro- and chlorofluoroethylene are used as the alkylating agent, the organic peroxide, preferably di-tert-butyl peroxide, and the solution of the heterocyclic polymerizable compound or a mixture of the monomers are placed in a shaking autoclave corrosion-resistant steel. Then the low-boiling α-olefin or fluorine or chlorofluoroethylene is placed in the autoclave and heated to temperatures of 110 to 140 ° C. for 5 to 28 hours. The pressure developed in the autoclave can be between 7 and 70 kg / cm ² . After cooling to room temperature, the contents of the autoclave are placed in a vacuum distillation device to remove the solvent and the remaining product is recovered as a solid.

The examples illustrate the invention. Unless otherwise stated, parts are by weight is.

example 1

Into a 1 liter four-necked flask equipped with a stirrer, thermometer, nitrogen inlet and reflux condenser the following compounds were given:

N-vinyl-2-pyrrolidone .... 111g (1.0 mol)

a-eicosen 140 g (0.5 mol)

Methyl isobutyl carbinol ... 200 g

Di-tert-butyl peroxide 7.3 g (0.05 mol)

The flask was then purged with nitrogen and heated. After reaching a reaction temperature An exothermic reaction set in at about 120.degree. C., but the temperature rose to 120-135.degree held. After 16 hours of reaction, the experiment was terminated and the product was analyzed. No free N-vinyl-2-pyrrolidone could be found, and it was still 2.73% a-eicosene available, which corresponds to 12.5 kg. After the solvent was completely removed, the product was at Room temperature a waxy solid.

Example 2

Into a 1 liter four-necked flask equipped with a stirrer, thermometer, nitrogen inlet and reflux condenser the following compounds were added and the flask was then filled with nitrogen flushed and heated:

N-vinyl-2-pyrrolidone .... 83.2 g (0.75 mol)

α-dodecene 126 g (0.75 mol)

n-butanol 150 g

Di-tert-butyl peroxide 11g (0.075 mol)

The contents of the flask were increased to 120 to 12 hours Heated to 125 ° C., whereupon a second addition of 5.5 g (0.037 mol) of peroxide was made and the reaction continued Was continued for 12 hours (total amount of peroxide = 16.5 g or 0.11 mol). The solution was analysed. It contained no residual N-vinyl-2-pyrrolidone and only 2.26 percent by weight of a-dode-

ao cen, which corresponds to 8.5 g of olefin. Then the contents of the flask were placed in a 1 liter flask and the solvent is distilled off under reduced pressure. The product obtained was a colorless, flexible, highly hydrophobic solid.

* ⁵ Example 3

Into a 1 liter four-necked flask equipped with a stirrer, thermometer, nitrogen inlet and reflux condenser the following compounds were given:

N-vinyl-2-pyrrolidone .... 37 g (0.33 mol)

α-dodecene 336 g (2.0 mol)

n-butanol 200 g

Di-tert-butyl peroxide 14.6 g (0.1 mol)

The contents of the flask were first purged with nitrogen and then refluxed for 24 hours (120 to 125 ° C). A further 14.6 g (0.1 mol) of di-tert-butyl peroxide were then added, and that The mixture was heated for an additional 24 hours (total amount of peroxide 29.2 g or 0.2 mol). The content was cooled and analyzed. It contained no residual N-vinyl-2-pyrrolidone and only 4.65% α-dodecene, which corresponds to 28 g of the α-olefin. After removing all volatile materials in a high vacuum a colorless, viscous product was left which was soluble in most organic solvents is.

Example 4

Into a 1 liter four-necked flask equipped with a stirrer, thermometer, nitrogen inlet and reflux condenser the following compounds were given:

N-vinyl-2-pyrrolidone .... 111g (1.0 mol)

α-eicosen 280 g (1.0 mol)

Methyl isobutyl carbinol ... 200 g

Di-tert-butyl peroxide 14.6 g (0.1 mol)

The contents of the flask were first flushed with nitrogen and then at 130 to 135 ° C. for 16 hours heated. An additional 7.3 grams (0.05 moles) of peroxide was then added and the reaction continued Continued for 8 hours (total amount of peroxide = 21.9 g or 0.15 mol). The solution was cooled and analyzed. The data showed a complete absence of N-vinyl-2-pyrrolidone and only 5.48% a-eicosene, which corresponds to 33.6 g of the olefin

409 535/425

9 10

speaks. The contents were vacuum distilled; according to N-vinyl-2-piperidone 125 g (1.0 mol)

Removal of the solvent, 391 g of an α-octadecene 252 g (1.0 mol)

paraffin-based lubricating oil with a viscosity of n-butanol 200 g

100 Saybolt seconds added. There were 780 g of di-tert-butyl peroxide 14.6 g (0.1 mol)

a clear, viscous liquid. After the 5th

The solution solidified when it was cooled to room temperature. The flask was thoroughly flushed with nitrogen.

to a waxy solid. rinsed and then refluxed for 30 hours

. . heats (120 ⁰ C vessel temperature), then cooled ^ice P ^ie and analyzed. The analysis showed the complete ab-in a 1 liter quota of only 3.5% .alpha.-octadecene provided with a stirrer, thermometer, nitrogen content of N-vinyl-2-piperidone and the property inlet and reflux condenser Solution, what neck flask were the following compounds ge 18g unreacted olefin corresponds,
give: After distilling off the solvent under N-vinyl-2-pyrrolidone .. 111 g (1.0 mol) (74 <V ₀ ) reduced pressure and replacement with 377 g paraf-vinyl acetate .... 39 g (0, 45 moles (26%) of ¹⁵ base lubricating oil became 750 g (50%>) of one

α-Hexadecene obtained 336 g (1.5 mol) of a very clear, oily solution.

Methyl isobutyl carbinol 200 g Examples

Di-tert-butyl peroxide .. 15 g (0.1 mol). . ", _M

In one with a stirrer, thermometer, nitrogen inlet

After thorough flushing with nitrogen, let the 1 liter four-necked tube fitted with a reflux condenser

the contents were heated. At a vessel temperature flask the following compounds were given: from about 105 ° C was vigorous reflux

of vinyl acetate (boiling point 72 to 73 ⁰ C) solid- N-vinyl-e-caprolactam ... 139g (1.0Mol)

posed. The temperature increased slowly with a-octadecene 214 g (0.85 mol)

decreasing reflux. The contents were 25 methyl isobutyl carbinol ... 200 g

16 hours heated to 120 to 135 ° C, then di-tert-butyl peroxide 13.1 g (0.09 mol)

a further 10.0 g of peroxide were added, and the reaction

continued for a further 8 hours (total amount of flask was blown thoroughly with nitrogen Peroxide = 25.0 g or 0.17 mol). The analysis rinsed and then earthed to 125 to 135 ° C for 24 hours Solution showed the complete absence of N-Vi heats. Analysis of the content showed the absence nyl-2-pyrrolidone, the presence of 0.07% vinyl of N-vinyl-6-caprolactam and the presence of acetate (corresponding to 0.5 g) and only 3.3% a-hexa- 4.54% a-octadecene, which is only 25.7 g of the non-umdecene, which corresponds to 23.5 g of the olefin. Corresponds to deposed olefin. After distilling off Removal of the solvent, the product was relative to the solvent under reduced pressure transparent solid that was added to the 353 g of paraffin-based lubricating oil in the front and called paraffinic lubricating oil was soluble. 705 g of a 50 percent oil solution were obtained.

Example 6 Example 9

In one with stirrer, thermometer, nitrogen inlet In one with stirrer, thermometer, nitrogen inlet 1 liter four-necked flask fitted with a reflux condenser and a 1 liter four-necked flask fitted with a reflux condenser the following compounds were flasked the following compounds were given: give:

N-vinyl-2-piperidone 70 g (0.56 mol)

N-vinyl-2-pyrrolidone .... 30 g (0.25 mol) ethyl methacrylate 30 g (0.26 mol)

Dimethylaminoethyl- 45 a-Eicosen 252 g (0.90 mol)

methacrylate 10 g (0.063 mole) methyl isobutyl carbinol ... 200 g

a-Eicosen 160 g (0.57 mol) di-tert-butyl peroxide 10 g (0.68 mol)

Methyl isobutyl carbinol ... 150 g

Di-tert-butyl peroxide 10 g (1st portion) The flask was thoroughly flushed with nitrogen.

50 rinsed and heated. After reaching a temperature

The flask was thoroughly nitrogen-transit temperature of 115 ° C, an exothermic reaction was purged and then observed 16 hours 125 to 130 ⁰ C. The temperature was raised to 125-135 ° C. Then a further 5.0 g of peroxide was held in place. After 8 hours a further 10 g of peroxide were added and the reaction was added for a further 16 hours of oxide (total of 20 g or 0.137 mol) and continued (total amount of peroxide = 15 g or 55) and heating was continued for a further 16 hours (total time 0.1 mol After cooling, the content was = 24 hours). The contents of the flask have been analyzed, analyzed. It contained no residual N-vinyl-2-pyr- It contained neither N-vinyl-2-piperidone nor ethylrolidone or dimethylaminoethyl methacrylate and only methacrylate and only 5.7% unreacted a-egg-6.58% (percent by weight) a- Eicosen, which corresponds to 24 g of the cosen, which corresponds to 32.8 g of the α-olefin. That corresponds to olefin. Removal of the solvent in the solvent was carried out under reduced pressure from high vacuum and replacement with 200 g of the pre-distilled and one was replaced with 352 g of paraffin-based lubricating oil called paraffin-based lubricating oil. The 50 percent solution in oil obtained was a clear, amber-colored solution. clear and weighed 700 g.

Example 7 _6g Example 10

In one with stirrer, thermometer, nitrogen inlet In one with stirrer, thermometer, nitrogen inlet 1 liter four-necked flask fitted with a reflux condenser and 1 liter four-necked flask fitted with a reflux condenser the following compounds were given: flasks were given the following compounds:

N-vinyl-2-pyrrolidone .... IHg (I ₅ OMoI)

α-decene 210 g (1.5 mol)

n-butanol 200 g

Dibenzoyl peroxide 25 g (0.1 mol)

The flask was purged with nitrogen and the contents heated to 95-100 ° C for 10 hours. Then the solution was analyzed. It contained no residual N-vinyl-2-pyrrolidone and only 23.5% a-decene, which corresponded to 128 g of unconverted a-decene. The contents were placed in a flask, the solvent distilled off under reduced pressure and the residue dried for 24 hours at 3 to 5 Torr and a bath temperature of 130 to 14O ⁰ C. The clear, colorless solid (188 g) was analyzed and contained 7.45% nitrogen, which corresponds to 59% converted N-vinyl-pyrrolidone in the product. The product was hydrophobic and soluble in many organic solvents.

Example 11

Into a 1 liter four-necked flask equipped with a stirrer, thermometer, nitrogen inlet and reflux condenser the following compounds were given:

N-vinyl-2-pyrrolidone ..
N-vinyl-3-morpholinone
Methyl isobutyl carbinol.

α-octadecene

tert-butyl hydroperoxide

55.5 g (0.5 mole)
63.5 g (0.5 mole)

200 g

315 g (1.25 moles)
11 g (0.12 mol)

The flask was purged thoroughly with nitrogen and heated to 130-140 ° C for 12 hours. Then an additional 11.0 grams of peroxide (22 grams total or 0.24 moles) was added and more were added Heated for 12 hours. When the contents were analyzed, no N-vinyl-2-pyrrolidone or N-vinyl-3-morpholinone were found found and found only 11.6% α-octadecene, which corresponds to 76 g of unreacted olefin. The contents were placed in a 2 liter flask and the solvent was reduced under reduced pressure Distilled off pressure and replaced by 434 g of paraffin-based lubricating oil. The finished 50 percent solution was a clear, amber colored liquid and weighed 860 g.

Example 12

Into a 1 liter four-necked flask equipped with a stirrer, thermometer, nitrogen inlet and reflux condenser After thorough purging with nitrogen, the following compounds were given:

N-vinyl-5-methyl-

2-pyrrolidone 125 g (1.0 mol)

Hexanol (mixture

isomeric hexanols) ... 200 g

α-octadecene 227 g (0.9 mol)

Di-tert-butyl peroxide ..... 15 g (0.1 mol)

The solution was heated to 120 to 140 ^° C. for 30 hours, then cooled and analyzed. It contained less than 0.1 percent by weight of monomer and only 2.4% of α-octadecene, which corresponds to 13.6 g or 94 percent consumption of the α-olefin introduced. Removal of the solvent under reduced pressure and replacement with 352 g of paraffinic lubricating oil gave 700 g of a clear (50 percent) solution.

Example 13

Into a 1 liter four-necked flask equipped with a stirrer, thermometer, nitrogen inlet and reflux condenser After thorough purging with nitrogen, the following compounds were given:

N-vinyl-2-oxazolidone .... 56.5 g (0.5 mol)

Methyl isobutyl carbinol ... 200 g

ίο a-eicosen 210 g (0.75 mol)

Di-tert-butyl peroxide 11.0 g (0.075 mol)

The mixture was then heated to 120 to 140 ° C. for 12 hours, whereupon a further 11.0 g of peroxide (total 22.0 g or 0.15 mol) were added. Thereafter, the reaction was continued. After total The contents were cooled down and analyzed for a reaction time of 28 hours. It contained 0.2 percent by weight N-vinyloxazolidone (= 0.98 g) and 3.44% a-eicosen (= 16.8 g), based on the weight of the solution. Thereafter, the solvent was distilled off under reduced pressure and at the same time were 495 g of paraffin-based lubricating oil were added. The finished solution was clear and weighed 760 g.

Example 14

Into a 1 liter four-necked flask equipped with a stirrer, thermometer, nitrogen inlet and reflux condenser the following compounds were given:

N-vinyl-3-morpholinone .. 63.5 g (0.5 mol)

n-butanol 150 g

α-hexadecene 224 g (1.0 mol)

Di-tert-butyl peroxide 15 g (0.1 mol)

The flask was flushed with nitrogen and heated for 16 hours under reflux (118-124 ⁰ C). Then an additional 7.0 grams of peroxide (total 22.0 grams or 0.15 mol) was added and the mixture was refluxed for an additional 20 hours (total 36 hours). The contents were cooled and analyzed. It contained 0.05% N-vinyl-3-morpholinone (= 0.23 g) and 4.7% α-hexadecene (= 21.6 g), based on the weight of the solution. The solvent was then distilled off at temperatures up to 140 ° C. and 0.05 to 1.0 torr. The residue obtained weighed 280 g, was clear, colorless and very viscous. This product was soluble in a wide variety of polar and non-polar organic solvents.

Example 15

Into a 1 liter four-necked flask equipped with a stirrer, thermometer, nitrogen inlet and reflux condenser the following compounds were given:

N-vinyl succinimide 62.5 g (0.5 mole)

Methyl isobutyl carbinol ... 150 g

a-eicosen 182 g (0.65 mol)

Di-tert-butyl peroxide 15 g (0.1 mol)

The flask was flushed through with nitrogen and ^{heated to 120 to 140 °} C. for 30 hours. Then the contents were cooled and analyzed. It contained only a trace of N-vinylsuccinimide and 3.66% (= 15.0 g) unreacted α-eicosen, based on the weight of the solution. Then 244.5 g of paraffinic lubricating oil was added and the solvent was distilled off under reduced pressure.

13 14

The 50 percent solution obtained was clear and weighed flasks were given the following compounds:

485 g (theory = 489.0 g). N-vinyl-2-pyrrolidone 55.5 g (0.5 mol)

Example 16 C ₄₂ α-olefin from the trimer

_T. . ".., ^,". , ". cation of a-tetradecene .. 294 g (0.5 mol)

, ο T4- fS ¹ IA * ' Tte ™ ⁰ ™ ¹ ? ¹ ' nitrogen in- 5 methyl isobutyl carbinol 120 g

ate and reflux cooler provided 1 liter four-necked di-tert-butyl peroxide 15 g (0.1 mol)

flasks were after thorough rinsing with

The following compounds were added to nitrogen: The flask was thoroughly flushed with nitrogen.

N-Methacryloyloxyäthyl- rinsed then heated under reflux for 24 hours,

pyrrolidone 46.0 g (0.23 mol) ^{cooled 10} nm and analyzed The analysis showed

η butanol 200 2 complete absence of N-vinyl-2-pyrrolidone

«-Eicosen. '.'. '. '.'. '.'. '.'. '.'. '.'. '. 140 g (0.5 moles) ™ <* ^die . Presence of 7.75% of _{the C 42 "olefin}

Di-tert-butyl peroxide 10 g of ^{the solution} S> ^wa »37.5 g of unreacted olefin

. is equivalent to.

The clear solution was left under for 20 hours after distilling off the solvent

Nut heated to 117 to 125 ° C, then further reduced pressure and replacement with 349 g of paraf-

5.0 g peroxide (a total of 15.0 g or 0.1 mol) tensile-based lubricating oil were 695 g of a clear,

give, and the mixture was obtained for a further 16 hours amber-colored oily solution, which is

heated to reflux. Then the contents turned to an amber color after cooling

cools and analyzes. Analysis showed that the wax completely solidified, but hardened on heating

Absence of methacrylate and only 3.0% (= 12.0 g) liquefied again.

unreacted a-eicosen. From the examples it can be seen that the solvent was distilled off under reduced pressure and replaced by simultaneous polymerization according to the invention and 186 g of paraffin-based lubricating oil. The final alkylation, the solubility of the homo-50 percent solution obtained, was clear and weighed 371 g. 25 and copolymers systematically through both. the type as well as the amount of B e 1 s ρ 1 e 1 17 olefin used can be regulated so that polymer 111g (1 mol) of N-vinyl-2-pyrrolidone were obtained in sate, which was still in polar solvents How dissolved 250 g of anhydrous ethanol. Then alcohols that are soluble, as well as polymers, which are added in 14.6 g (0.1 mol) of di-tert-butyl peroxide, 30 aliphatic hydrocarbons, mineral and and the solution was in a 1-liter shaker lubricating oils are soluble; In addition, you can give a polyclave made of corrosion-resistant steel. In merisate with intermediate solubility properties between the two autoclaves, 60.0 g (0.51 mol) of chlorine tri-see polar and non-polar solvents fluorinated ethylene, and the container was held. For example, polymers are heated ^{to 125 to 130 °} C. to a small extent for 24 hours. After the alkylation, still soluble in ethanol, so that you can cool the contents in a 1-liter four-liter with low-boiling fluorochloroalkanes to aerosol necked flasks and formulate for the removal of hairsprays; However, their sensitivity to moisture and their low-boiling components are diminished. Subjected to vacuum distillation. As a residue, these polymers can also be processed in adhesives with and 7.7% chlorine, which gives 27 percent by weight chlorine-superior properties, due to their dry solids obtained containing 13.3% fluorine 40 increased moisture resistance. The trifluoroethane, based on the weight of the product, polymers with a high degree of alkylation are tes, corresponds. soluble in liquid hydrocarbons. When they are dissolved in example 18 at a concentration of about 0.001 to 2% by weight, e.g. in kerosene, jet fuel or in a stirrer, thermometer, nitrogen-filled heating oil, they provide an effective let and reflux condenser. Liter four-neck protection against the separation of grease, pistons were given the following compounds: Resins and sludge They are very effective as N-vinyl-2-pyrrolidone .... 112.21 g (1.0 mole) £ j ^to improve the viscosity index and as a-octene. .... 112 2Ig (IOMoI) 50 dispersant in lubricating oils.

n butanol 2Οθ'ε trations of about 0.03 to 5 percent by weight in

D ~ i-tert-butyl peroxide. '.'. ''.'. 14.6 g (0.1 mol) of lubricating oils are dissolved, they disperse lubricating

^{r ö v} 'reindeer, resins and sludge, thereby preventing them

The flask was thoroughly filled with nitrogen by depositing it on engine parts. The gay and

rinsed, then heated under reflux for 30 hours, 55 mixed polymer alkylates of α-olefins with 8 to

then cooled and analyzed. Analysis showed 42 carbon atoms are a new class of

the complete absence of N-vinyl-2-pyrrolidone products, which is particularly suitable as a dispersant

and the presence of only 3 ° / o a-octene in the medium for motor oils, since they do not have any deposits

Solution, which releases 13.13 g of unreacted olefin, d. H. are ashless.

speaks. 60 polymers with a high degree of alkylation

After the solvent has been distilled off, hydrocarbon polymers such as poly-

reduced pressure and replacement with 450 g parafethylene and polypropylene, soluble and lend

Fin-based lubricating oil was 674 g of a polymer that was very difficult to color

get clear, oily solution. Dye receptivity.

...... _Q 65 When using «olefins with up to 4 carbon

Example material atoms in homo- or mixed polymerisation

In one with a stirrer, thermometer, nitrogen inlet, polymers are obtained that are more flexible and

Let and reflux condenser equipped 1 liter four-necked under moist conditions are less sticky than

15 16

Polyvinylpyrrolidone itself or vinylpyrrolidone- for paper, plastics and textiles. This poly-

Vinyl acetate copolymers. Flexibility is created from solutions in a large number of organisa-

increases, and the stickiness in high humidity nischer solvents or as emulsions smooth

decreases with higher degree of alkylation. continuous films, which makes them particularly suitable

The homo- and mixed polymer alkylates from 5 net are used as flame-retardant primers for

Chlorofluoroethylene and fluoroethylene with 2 carbon polyester laminates.

Atoms of matter have flame-resistant properties. The invention thus also relates to the use

They are particularly suitable for the production of the products produced according to the invention for

flame retardant adhesives, d. H. Binders specified purposes.

Claims (1)

Patent claims: 1. Process for the simultaneous polymerization and alkylation of heterocyclic polymerizable Compounds, characterized in that 1 mol (a) a monomeric heterocyclic N-vinyl compound or (b) a compound of the general formula