DE1191963B - Process for the production of copolymers - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

C08f

German class: 39 c -25/01

Number: 1191 963

File number: F 35214IV d / 39 c

Filing date: October 26, 1961

Opening day: April 29, 1965

It is known that 2-allyloxy-4,6-diaminotriazine-1,3.5 to be used as a component for copolymers. Allyl alcohol and derivatives of allyl alcohol are as components in the polymerization relatively inert reactants when the polymerization z. B. is carried out in an aqueous dispersion using the usual polymerization catalysts. The scope of allyl compounds as monomers in polymerizations are So limits are set from the start.

It is also known. Compounds of the general formula I

R-C = CH-R '

N N I

I Il

H ₂ N - CC - NHR ₂

to be used as monomers for polymerizations and copolymerizations. In formula I, R a methyl group or hydrogen, R 'hydrogen or the phenyl radical and R2 hydrogen, an alkyl, Aryl or aralkyl radical. Polymers and copolymers obtained from these monomers are as starting materials for the production of resins of the melamine-formaldehyde resin type have been used, but they show in a post-crosslinking with aldehydes compared to the trifunctional Melamine has the disadvantage that it only has two crosslinkable functions per monomer unit contain.

In the Swiss patent 336 087 the preparation of compounds of the general formula

Il

o = C - C - N - A - C

Process for the production of copolymers

Applicant:

Paint factories Bayer Aktiengesellschaft,

Leverkusen

Named as inventor:
Dr. Carlhans Süling, Leverkusen;
Dr. Dr. hc Dr. eh Dr. hc Dr. hc
Dr. eh Otto Bayer, Burscheid;
Dr. Egon Kuniz, Leverkusen

This polymerization process is not described in detail in the cited patent. the As can be seen from the comparative experiments, this copolymerization was unsatisfactory Yields and polymers which are unable to form continuous clear films.

There has now been a process for the preparation of copolymers by free radical polymerization organic compounds containing polymerizable carbon-carbon double bonds found together with derivatives of 2,4-diaminos-triazine, which is characterized by that 1 to 50 percent by weight, calculated on the total monomers, of derivatives of 2,4-diaminos-triazine the formula

N = C

CH ₃

-C = CH ₂

H ₂ N - C

I!

C -NHR

N-C

described, in which R is hydrogen or an alkyl, Alkenyl, aralkyl or cycloalkyl radical and A is an alkylene group with 1 to 8 carbon atoms, and stated that these compounds can be copolymerized with monovinyl compounds.

can be used, in which R is a hydrogen atom, an alkyl radical, a carboxamide group-containing Aryl radical, B a hydrogen atom or a lower alkyl radical, A the group

Ϊ
NH-C -

their aromatic hydrocarbon ring in o-, in

509 567 / Ϊ53

bonded to the triazine ring in the m- or p-position and can carry one or more alkyl or alkoxy substituents.

Examples which may be mentioned as compounds according to the above formula II:

2- (3-aminomethacryloylphenyl) -4,6-diamino-

triazine-1,3,5,
2- (4-aminomethacryloylphenyl) -4,6-diamino-

triazine-1,3,5,
2- (3-aminomethacryloyl-4-methoxyphenyl) -

4,6-diaminotriazine-1,3,5,
2- (3-aminoacryloyl-4-ethoxyphenyl) -4,6-di-

aminotriazine-1,3,5,
2- (3-aminomethacryloyl-4-methylphenyl) -

4,6-diaminotriazine-1,3,5.

It must be described as surprising that compounds of the general formula II with the conventional catalyst systems can be brought to the polymerization without difficulty. While from methacrylamide via methacrylic acid butylamide to methacrylic acid anilide the polymerizability decreases considerably, makes the compounds of general formula II the further decrease in reactivity to be expected due to an increase in molecular weight not noticeable.

The compounds of the general formula II are new as such, but can be used in analogy to an known processes are obtained, for example by nitrobenzonitrile with dicyandiamide in In the presence of a basic catalyst, the nitrophenyldiaminotriazine obtained is converted to corresponding aminophenyl compound is reduced and the amines thus obtained with methacrylic acid chloride to be converted to the corresponding methacryloylaminophenyl compounds.

However, the preparation of the monomers is not the subject of the invention.

The polymerization of the monomers can be carried out analogously to methods known per se in aqueous Emulsion, suspension, solution or substance.

Suitable polymerization catalysts are those customarily used for the polymerization of free radicals polymerizable monomers used polymerization initiators, such as inorganic ones as well organic peroxy compounds or nitrogen-containing compounds that tend to decompose free radicals. Organic peroxides, such as diacyl peroxides, alkyl hydroperoxides, dialkyl peroxides, Hydrogen peroxide or organic peracids, called. Are of practical interest in addition, especially redox systems, for example those that act as oxidative components Alkali metal or ammonium persulfate, perborate, percarbonate. Chlorates or as a reducing agent in acidic medium effective sulfur compounds of the low valency level of sulfur or in alkaline medium effective reducing agents such as alkanolamines, Oxäthylenpolyamine, etc. contain. Azodiisobutyric acid dinitrile are particularly suitable as nitrogen-containing compounds which tend to decompose free radicals as well as diazoamino compounds mentioned.

These compounds are used in the amounts usually considered here, i. H. from of the order of about 0.5 to 5%, calculated on the total weight of the monomers used, used.

Copolymers should be 1 to 50 percent by weight, preferably 1.5 to 30 percent by weight on total monomers, the compounds of the general Formula II included. In principle, radicals are suitable as copolymerization components polymerizable compounds with at least one polymerizable carbon - carbon double bond, especially vinyl and / or vinylidene monomers. As suitable comonomer components are mentioned by way of example: vinyl aromatics, such as styrene, nucleus or side-chain alkylated styrenes, Nuclear halogenated styrenes, styrenesulfonic acids; Vinyl ester, such as vinyl acetate, vinyl propionate, vinyl butyrate; Vinyl heterocycles such as vinyl pyrrolidone, vinyl pyridine; Vinyl or vinylidene halides, such as vinyl chloride, vinylidene chloride and vinylidenecyanide; links the acrylic acid series, such as acrylic acid, methacrylic acid, acrylamide, methacrylic acid amide, acrylonitrile as well as the esters of acrylic acid or methacrylic acid, especially those with 1 to 12 carbon atoms containing alcohol component; aliphatic conjugated diolefins, preferably those with 4 to 6 carbon atoms, such as. B. butadiene, isoprene, chloroprene. It is of course possible to use one or more monomers of the type mentioned above.

Deserve particular interest in this context containing ternary acrylonitrile copolymers

a) at least 80% acrylonitrile in accordance with the order of magnitude,

b) an ester of acrylic acid or methacrylic acid ^ and their substitution products as well

c) monomer components according to formula II.

In addition, of the same interest are quaternary polymers that exceed those above named monomer components as a fourth component monomers such as styrenesulfonic acid. Vinyl esters, methacryloylaminodisulfimide, methacryloylaminosulfanilic acid or vinylpyridine, may contain.

The polymerization or copolymerization of the aforementioned monomer components can under conditions known per se for the polymerization of the vinyl or vinylidene monomers mentioned be made. As polymeriza-

so tion temperatures come in the case of emulsions or. Suspension polymerization temperatures between 10 and 100 ° C., preferably 35 and 95 ^° C., are possible. The polymerizations in solution are preferably carried out at temperatures from 40 ^° C. to the boiling point of the solvent in question. In the bulk polymerizations, it is often advantageous to carry out the polymerization at temperatures of 100 to 180 C ^c. In many cases it is advantageous, with the exclusion of oxygen or under the atmosphere of an inert gas, such as. B. nitrogen, or solvent vapors to work.

The copolymers which can be prepared by the process according to the invention have the ability with a wide variety of aldehydes, especially formaldehyde, easily and particularly extensively crosslinkable to be. With the technically interesting use of the monomers of the formula II for the production

of acrylonitrile copolymers has been shown in particular that the dye absorbency of Shaped structures made from copolymers of this type, in particular with a high content of acrylonitrile is not or hardly noticeably impaired, but that these formed structures are beyond that A post-treatment with formaldehyde can be subjected, creating a particular improvement the mechanical quality or the wearing behavior (in the case of textiles) is achieved.

The polymers which can be prepared by the above process are valuable components for Cast resin combinations.

They are also suitable as coating agents. In addition, shaped objects such as films, threads and fibers can be produced from these copolymers.

The parts mentioned in the following examples are parts by weight, unless otherwise stated.

example 1

7 parts of 2- (3-methacryloylaminophenyl) -4, 6-diaminotriazine-1,3,5 are dissolved in 308 parts of boiled water in a polymerization vessel. It is acidified with 4.3 parts of n-HaSOa. After thorough flushing with nitrogen, 0.14 part of potassium persulfate and 0.19 part of sodium pyrosulfite are added. The polymerization medium is now ^{heated to 55 °} C., and a mixture of 133 parts of acrylonitrile and 6.3 parts of methyl acrylate, a solution acidified with 6.4 parts of n-HaSQi, is left uniformly over the course of 3 hours

1.0 part of potassium persulfate in 429 parts of water and a solution of 1.37 parts of sodium pyrosulfite in 435 parts of water are run in. After completion of the polymerization mixture inlet is maintained for 1 hour at 55 ³ C. The precipitated polymer is isolated and dried at 60C. Yield: 129 parts; Polymer: K value 86.

Example 2

In an enamel vessel with a stirrer, 10 parts of 2- (3-acryloylaminophenyl) -4,6-diaminotriazine-1,3.5 suspended in 385 parts of water. After the atmospheric oxygen by thorough flushing Was displaced from the polymerization vessel with nitrogen, is achieved by adding phosphoric acid adjusted to a pH of 2.5, then entered 15 parts of acrylonitrile and then with 0.10 parts Potassium persulfate and 0.20 parts of sodium pyrosulfite are added. The reaction mixture is 15 minutes stirred, then 110 parts of acrylonitrile, 10 parts of vinyl acetate, one with Phosphoric acid adjusted to pH 2.5 solution of

., 1 part of potassium persulfate in 470 parts of water and a solution of 1.42 parts of sodium pyrosulfite and 1 part of sodium styrenesulfonate in 440 parts Running in water. The batch is kept at 45 ° C. during the reaction. After 5 hours it will The polymer was filtered off and dried. A white polymer is obtained in a yield of 95% the theory that easily dissolves in dimethylformamide and cast into films or spun fibers leaves.

Example 3

The procedure is as in Example 1, except that instead of the methyl acrylate used there Methacrylic acid ethyl ester is used. After drying, a white in dimethylformamide is obtained soluble powder with a K value of 84.

_s example 4

After purging with nitrogen, a polymerization vessel is filled with 327 parts of water, which is adjusted to a pH of 2.7 with nitric acid, 12 parts of acrylonitrile, 0.5 part of vinyl acetate, 6.2 parts of 2 - (3 - methacryloylaminophenyl) -4.6 - diaminotriazine - 1,3,5, 0.1 part of potassium chlorate and 0.4 part of sodium pyrosulfite charged. After 15 minutes, the mixture is left for 4 to 5 hours evenly from separate vessels

a) a mixture of 128 parts of acrylonitrile, 5.3 parts of vinyl acetate and 5.7 parts of vinyl pyridine,

b) a solution of 0.5 parts of potassium chlorate in 520 parts of water and

c) a solution of 3 parts of sodium pyrosulfite in 480 parts of water

run up. During the feed, 10% nitric acid is added to ensure that the The pH of the reaction mixture is always between 2.5 and 3. After filtering and drying a white powder with a K value of 89 is obtained. Films made from this polymer contain acidic dyes easy to color.

Comparative experiments

After purging with nitrogen at 55 ^° C., 100 parts by weight of water and 0.2 parts by weight of η-sulfuric acid are placed in a polymerization vessel.

} s Within 3 hours, solutions I. II, III and IV are then added to the reaction medium according to the following experiments and the temperature is kept at 55 ° C. After the solutions have been combined, the batch is stirred for 1 hour, the precipitated polymer is filtered off and the polymer dried ^{at 50 3 C.} The polymer obtained is a white powder which is soluble in dimethylformamide. In the tests according to the method of the invention, break-resistant films can be drawn from these solutions, but not in the comparative tests.

1. Method according to the invention

Solution I:

so 150 parts by weight of water, 0.85 parts by weight

Potassium persulfate, 18 parts by weight of n-sulfuric acid;
Solution II;

150 parts by weight of water, 0.8 parts by weight of wet trium pyrosulfite;
Solution III:

400 parts by weight of water, 5 parts by weight of 2 - (3 - methacryloylaminophenyl) - 4,6 - diaminotriazine-1,3,5;
f, o solution IV:

95 parts by weight of acrylonitrile.
Yield: 89 parts by weight; clear, break-proof films.

2. According to Swiss patent specification 336 078

,, s solution I:

150 parts by weight of water, 0.85 parts by weight of potassium persulfate, 18 parts by weight of n-sulfuric acid;

Solution II:

150 parts by weight of water, 0.8 parts by weight of Na-

trium pyrosulfite;
Solution III:

400 parts by weight of water, 5 parts by weight of N-Cy-

clohexyl - methacryloylamino - acetoguanamine; Solution IV:

95 parts by weight of acrylonitrile.
Yield: 51 parts by weight; no movies.

3. Method according to the invention

Solution I:

150 parts by weight of water, 0.85 parts by weight of potassium persulfate, 18 parts by weight of n-sulfuric acid;

Solution II:

150 parts by weight of water, 0.8 parts by weight of sodium pyrosulfite;

Solution III:

400 parts by weight of water, 10 parts by weight of 2 - (3 - methacryloylaminophenyl) - 4,6-diaminotriazine-1,3,5;

Solution IV:

90 parts by weight of acrylonitrile.

Yield: 66 parts by weight. ^ s

4. According to Swiss patent specification 336 078

Solution I:

150 parts by weight of water, 0.85 parts by weight of potassium persulfate, 18 parts by weight of n-sulfuric acid;

Solution II:

150 parts by weight of water. 0.8 part by weight of sodium pyrosulfite;

Solution III:

400 parts by weight of water, 10 parts by weight of N-cyclohexyl-methacryloylamino-acetoguanamine;

Solution IV:

90 parts by weight of acrylonitrile.

Yield: 32 parts by weight.

5. Method according to the invention

Solution I:

150 parts by weight of water, 0.45 parts by weight of potassium persulfate, 0.7 parts by weight of n-sulfuric acid;

Solution II:

150 parts by weight of water, 0.6 parts by weight of sodium pyrosulfite;

Solution III:

400 parts by weight of water, 5 parts by weight of 2 - (3 - methacryloylaminophenyl) - 4.6 - diaminotriazine-1,3,5, 2 parts by weight of concentrated hydrochloric acid;

Solution IV:

95 parts by weight of acrylonitrile.

Yield: 77 parts by weight; clear, break-proof films.

6. According to Swiss patent specification 336 078

Solution I:

150 parts by weight of water, 0.45 parts by weight of potassium persulfate, 0.7 parts by weight of n-sulfuric acid:

Solution ii:

150 parts by weight of water, 0.6 parts by weight of sodium pyrosulfite;

Solution III:

400 parts by weight of water, 5 parts by weight of N - cyclohexyl - methacryloylamino - acetoguanamine, 2 parts by weight of concentrated hydrochloric acid;

Solution IV:

95 parts by weight of acrylonitrile.

Yield: 36 parts by weight; no movie.

7. Method according to the invention

Solution I:

150 parts by weight of water. 0.45 part by weight of potassium persulfate. 0.7 part by weight of n-sulfuric acid;

Solution II:

150 parts by weight of water. 0.6 part by weight of sodium pyrosulfite;

Solution III:

400 parts by weight of water. 10 parts by weight of 2 - (3 - methacryloylaminophenyl) - 4,6 - diaminotriazine-1,3,5, 2 parts by weight of concentrated hydrochloric acid;

Solution IV:

95 parts by weight of acrylonitrile.

Yield: 65 parts by weight; clear, break-proof films.

8. According to Swiss patent specification 336 078

Solution I:

150 parts by weight of water. 0.45 parts by weight;, ü potassium persulfate 0.7 parts by weight n-sulfur

acid;
Solution II:

150 parts by weight of water, 0.6 parts by weight of sodium pyrosulfite;
is solution III:

400 parts by weight of water. 10 parts by weight of N-cyclohexyl-methacryloylamino-acetoguanamine. 2 parts by weight of concentrated hydrochloric acid; Solution IV:
95 parts by weight of acrylonitrile.

Yield: 38 parts by weight; no movie.

Claims (1)

Claim: Process for the preparation of copolymers by polymerizing radically polymerizable Organic compounds containing carbon-carbon double bonds together with derivatives of 2,4-diamino-s-triazine, characterized in that up to 50 percent by weight, calculated on the total monomers, of derivatives of 2,4-diaminos-triazine of the formula AC = CH ₂ N
C-NHR can be used, in which R is a hydrogen atom, an alkyl radical, a carboxamide group-containing Aryl radical. B is a hydrogen atom or 9 10 a lower alkyl radical, A the group in the m- or p-position on the triazine ring O is bonded and one or more alkyl or Can carry alkoxy substituents, means. 5 Considered publications: their aromatic hydrocarbon ring in o-, Swiss patent specification No. 336 078. 509 567/353 4.65 ® Bundesdruckerei Berlin