DE1105173B - Process for the production of crosslinkable macromolecular compounds - Google Patents

Description

It is known that the physical and chemical properties of macromolecular compounds can be changed if substances are polymerized into the manufacture of these substances that are not polymerizable Double bonds still contain other reactive groups. Such polymers are Can be crosslinked by reaction of the functional groups with one another or with other polyfunctional substances, so that they have particularly desirable properties for certain applications. There are naturally suitable not all functional groups associated with a polymerizable double bond. The one react in an undesirable way already during the polymerization, for the implementation of the other must very much vigorous conditions, e.g. B. very high temperatures can be selected. In many cases, however, this is not the case he wishes.

It is also known that copolymers of acrylonitrile with lower percentages contain halogen Allyl ethers can be reacted with amines, preferably secondary amines, by incorporating amino groups to achieve better dyeability of the polyacrylonitrile fibers obtained from these polymers. The tertiary ammonium halides are obtained with secondary amines. Primary amines and ammonia effect at the same time a gelation which is very disturbing in spinning approaches and which is presumably due to a certain degree of crosslinking is based. However, this crosslinking reaction does not go so far that it can be used industrially.

It has now been found that agents which split off hydrogen halide can be used even at room temperature crosslinkable macromolecular compounds obtained when a mixture of 0.5 to 50 percent by weight of a Esters of a polymerizable, α, β-ethylenically unsaturated Carboxylic acid or dicarboxylic acid with a dihydric or higher alcohol, which is in the α-position to a free hydroxyl group carries a chlorine atom, and 99.5 to 50 percent by weight of other unsaturated polymerizable Copolymerized compounds.

As a ^ -ethylenically unsaturated carboxylic or dicarboxylic acids, the chlorohydrin esters of which are to be polymerized are, in particular, acrylic acid and methacrylic acid or fumaric and maleic acids in question. These acids can also be substituted, e.g. B. by halogen or Hydroxyl groups. As dihydric or higher alcohols, which are in the α-position to a free hydroxyl group have a halogen atom and those with α, / 3-unsaturated polymerizable carboxylic acids are esterified, for example 3 - chloropropanediol - (1,2), (2,3) - dichlorobutanediol- (1,4), 3-chlorobutanetriol- (1,2,4), (1,4) -dichlorobutanediol- (2,3), 3-chloro-2-methylpropanediol- (i, 2) and 3-chloro-2-chloromethylpropanediol- (1,2) in question.

As components for the copolymerization, all of the above-mentioned chlorohydrin esters come from the copolymeric process for the production

of crosslinkable macromolecular

links

Applicant:

Aniline & Soda Factory in Baden

Corporation,

Ludwigshafen / Rhine

Dr. Hansjürgen Kessler, Mannheim-Feudenheim,
Dr. Ernst Penning, Dr. Hans Wilhelm,

Ludwigshafen / Rhine,

and Dr. Hans Reinhard, Mannheim,

have been named as inventors

sable connections, e.g. B. α, / 3-unsaturated carboxylic acids and dicarboxylic acids and their esters, with the exception of the chlorohydrin esters, amides already mentioned, substituted amides and nitriles, as well as vinyl esters, unsaturated polymerizable aldehydes, ketones and Alcohols and their esters and ethers, monounsaturated polymerizable hydrocarbons and diene hydrocarbons, Vinyl ethers, vinyl halides, vinyl cyanides, aliphatic N-vinyl and aromatic N- or C-vinyl compounds, such as styrene or its homologues and substitution products, are possible. Such connections are for example acrylic acid, methacrylic acid, maleic acid, acrylic acid methyl ester, ethyl ester, butyl ester, Acrylic acid amide and the corresponding derivatives of methacrylic acid, acrylonitrile, vinyl acetate, vinyl propionate, Acrolein, methyl allyl ketone, isopropenyl ketone, allyl and methallyl alcohol, allyl methyl ether, allyl ethyl ether, Allyl acetate, propionate, ethylene, propylene and butadiene, vinyl methyl ether, vinyl ethyl ether, vinyl chloride, Vinylidene chloride, vinylidenecyanide, N-vinylpyrrolidone, N-vinylcarbazole, styrene, methylstyrene and dimethylstyrene.

The new crosslinkable macromolecular compounds should be about 0.5 to 50% of the polymerizable Esters of α, / 9-unsaturated mono- or dicarboxylic acids and the said halogen-containing alcohols, while the remainder from 99.5 to 50% of the mentioned and similar monomers, which of course are also used in a mixture with one another can be.

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The copolymers can be run according to the usual procedure in such a way that the temperature is kept at about 80.degree. C. in the block, in solution, emulsion, suspension or is. The mixture is kept at a temperature of 80 ° C. for a further 15 hours with stirring by precipitation polymerization using the, with conventional catalysts being prepared in 3 hours. Suitable long distances a total of four times 0.5 parts of potassium catalysts are, for. B. inorganic and organic 5 persulfate are added. Then the emul peroxides, azo compounds or redox systems. sion ^x _{steamed for 2} hours at 90 ° C.

The copolymers produced according to the invention are impregnated with this emulsion and a cotton can already fabric with hydrogen halide-releasing agents, which is previously crosslinked in 1% sodium hydroxide solution at room temperature. Among halogen- and squeezed has, and lets it again afterwards wasserstoffabspaltenden agents are particularly metal io 10 minutes to l ° / _o aqueous sodium hydroxide solution are, we obtain hydroxides, metal alkoxides and metal oxides to comparable after drying when heated (5 minutes, 140 ° C). A decisive advantage of the new process, a solvent-resistant coating, which consists of trichlorine, is that the crosslinking is only 0.3% when the halogen ethylene is added (2 hours, 25 ° C) and in 0.5% hydrogen-releasing compounds even with normal Sodium hydroxide solution (1 hour, 100 ° C) only 6 ⁰ J ₀ washout temperature takes place. It is of great importance to suffer losses
tion, if z. B. Fibers with the macromolecular, _. "
reactive compounds are equipped, as eispie

Here the harmful 142 parts of water that is otherwise common at high temperatures are mixed with 10 parts of a 20% strength

There is practically no need. Of course, the aqueous solution of sperm oil alcohol, which ethoxylates,

Crosslinking, if desired, sulfated at higher temperatures and neutralized with sodium hydroxide solution, and

ratures are made. In any case, you have. 0.2 parts of potassium persulfate are added. In one half

However, the possibility of selecting the temperature so, this solution will be 10 parts of butyl acrylate

that damage to the respective substrate, emulsified on the and with stirring under nitrogen to 80 ° C

these reactive macromolecular compounds are heated. In the other half of the aqueous emulsion

should be applied, should be largely avoided. 25 10 parts of acrylic acid ^ -hydroxy-ß-chloropropyl ester,

For many purposes, the new reactive, 15 parts of acrylonitrile, 1 part of acrylic acid, 14 parts of meth-

macromolecular compounds with other reactive methyl acrylate and 50 parts butyl acrylate

and compounds capable of polymers, polycondensates emulsified with 10 ° / ₀ sodium hydroxide solution is neutralized, and

seeded or natural macromolecular compounds this emulsion is left with stirring after polymer

be mixed, preferably such in consideration of the beginning of the sation in the course of about 2 hours so in the

come, which also contain reactive groups, run in the reaction vessel that the temperature is 80 ° C

z. B. amide groups, dialkylaminomethylene amide groups, remains. After 4 hours, another 0.1 part of potassium

Methylolamide groups, etherified methylolamide groups, persulfate added and after a further 4 hours

Epoxy groups, hydroxyl and carboxyl groups, amino ¹ J _{steamed for 2} hours at 90 ° C,

groups, aminomethylol groups and their ethers- 35 If this emulsion is used to impregnate a cotton

products. tissue that is previously immersed in l ° / _o aqueous sodium hydroxide solution added and

The new macromolecular, reactive compound has been squeezed off, and then leaves it again 10 times are ideal for finishing grooves in 1% sodium hydroxide solution, so you get after textiles, for the production of varnishes, coatings, foils drying when heated ( 5 minutes, 140 ° C) and films, as additives to press materials and laminates, as a solvent-resistant coating, in trichloro binder for nonwovens and for all other purposes, ethylene (2 hours, 25 ° C) only 1.3 ° / ₀ and in 0.5 ° / ₀ iger for the macromolecular, reactive compounds caustic soda (1 hour, 100 ° C) only 4.5% washout are used. Suffers losses.

The parts mentioned in the examples are by weight. . ,.

share. 45 Example 4

. 148 parts of water are mixed with 2 parts of the potassium salt ⁶¹³ P ^{1 e of} a sulfated oxethylation product of a fatty alcohol 90 parts of butyl acrylate, 90 parts of methacrylic acid mixture (C ₁₆ to C ₁₈ ) and 0.2 parts of potassium persulfate methyl ester and 20 parts of acrylic acid ^ -hydroxy- S-chlorine added. The solution is divided and one half with propyl ester is mixed with 270 parts of benzene. Mix 10 parts of butyl acrylate and then add 2 parts of azodiisobutyronitrile to a stirred vessel under nitrogen within 30 minutes, and the solution is heated to 80 ° C. for 6 hours while stirring and stirring. The other half of the aqueous reflux is heated. If the resulting solution is mixed with 10 parts of acrylic acid ^ -hydroxy-S-chlorine polymer with 1.5 parts of sodium methylate in propyl ester, 15 parts of styrene, 1 part of acrylic acid, 14 parts of methanol and 2 parts of ethylenediamine, a film is poured 55 methyl methacrylate and 50 parts of acrylic acid and heated after drying to 140 ° C. for 10 minutes, butyl ester added, neutralized with 10% sodium hydroxide solution, this is in contrast to a film of this mixed, vigorously stirred and with continued stirring to the polymer, which is added without the addition of alkali 140 ° C, first half of the emulsion was dried over within 2 hours, no longer soluble in toluene. give that the temperature in the reaction vessel is kept at about -ο ■ ■ 1 ο ^6o 80 ° C. At this temperature, the mixture is stirred for a further _{4 hours} , after 0.1 part of 540 parts of potassium butyl acrylate and 180 parts of acrylic acid persulfate have been added. The emulsion is then steamed for a further 4 hours 30 minutes at 90 ° C after nitrile and 80 parts of acrylic acid ^ -hydroxy-S-chloropropyl-
ester are mixed with 80 parts of a 20% aqueous solu- impregnated with this emulsion to a Baumwollsung of a sodium salt of a C ₁₂ to C ₁₅ -Paraffinsulfon- 65 fabric, which one acid previously added to l ° / _o aqueous sodium hydroxide solution and 1 part of potassium persulfate in 1120 parts of water and squeezed out, and then leaves it mixed again. ^λ Γ οη this mixture 400 parts of less than 10 minutes in 1% sodium hydroxide solution are so after drying on heating to stirring and passing receives from nitrogen to 80 ° C heated (5 minutes, 140 ^D C) up to about 15 to Polymerization takes about 20 minutes to form a solvent-resistant coating that integrates in trichloro. Thereafter, the remainder of 70 ethylene (2 hours, 25 ° C.) is left in only 0.2% and 0.5% in the course of 2 ¹ _{2 hours}

Sodium hydroxide solution (1 hour, 100 ° C) suffers only 2.5% washout losses.

Example 5

A. 74 parts of water are mixed with 1 part of the sodium salt of a sulfated oxyethylation product of a C _{13 to} C ₁₄ fatty alcohol mixture, 0.1 part of potassium persulfate and 10 parts of butyl acrylate and stirred in a stirred vessel under nitrogen. This emulsion is heated to 80 ° C. over a period of ¹ _{1/2 hours, the polymerization beginning.}

B. 74 parts of water are mixed with 1 part of emulsifier (as under A), 0.1 part of potassium persulfate, 10 parts of 2-hydroxy-3-chloropropyl methacrylate, 15 parts of styrene, 1 part of acrylic acid, 14 parts of methyl methacrylate and 50 parts of butyl acrylate , neutralized with 10 ° / ₀ sodium hydroxide solution, and the mixture is allowed within 2 hours to the initially polymerized emulsion A run. The temperature is kept at 80 ° C. during this process. This temperature is also maintained during the further course of the polymerization, which lasts 8 hours after the addition has ended, with another 0.1 part of potassium persulfate being added after 4 hours.

Is impregnated with this emulsion, a cotton fabric, which have been previously added to l ° / _o aqueous sodium hydroxide solution and squeezed, and leaves it after a further 10 minutes to l% sodium hydroxide solution are, is obtained after drying when heated (5 minutes, 140 ° C) a solvent-resistant coating that suffers only 3.0% in trichlorethylene (2 hours, 25 ° C) and only 1.5% in 0.5% sodium hydroxide solution (1 hour, 100 ° C).

Example 6

A. 71 parts of water are mixed with 5 parts of a 20% strength aqueous solution of sperm oil alcohol which has been ethoxylated, sulphated and neutralized with sodium hydroxide solution, 0.1 part of potassium persulphate and 10 parts of butyl acrylate and mixed under nitrogen in a stirred vessel with stirring for ₂ hours heated to 80 ° C.

B. 71 parts of water are mixed with 5 parts of the same emulsifier solution as under A, 10 parts of bis-2-hydroxy-3-chloropropyl fumarate, 15 parts of styrene, 1 part of acrylic acid, 14 parts of methyl methacrylate and 50 parts of butyl acrylate are added, and it is added 0.1 part of potassium persulfate is added, and the mixture is neutralized with 10% sodium hydroxide solution. This mixture is added with vigorous stirring within 2 hours to the emulsion A so that the temperature at about 80 ° C is maintained. The polymerization batch is subsequently stirred at 80 ° C. for 8 hours, with subsequent stirring Add 0.1 part of potassium persulfate for 4 hours.

A cotton fabric is impregnated with this emulsion and placed in 1% sodium hydroxide solution beforehand and has squeezed it off, and then leaves it to lie in 1% sodium hydroxide solution for another 10 minutes, this is how it is obtained after drying when heated (5 minutes, 140 ° C) a solvent-resistant coating in trichlorethylene (2 hours, 25 ° C) only 7% and in 0.5% sodium hydroxide solution (1 hour, 100 ° C) only 2.3% washout losses suffers.

Claims (1)

Claim: Process for the preparation of macromolecular compounds which can be crosslinked with hydrogen halide agents at room temperature or elevated temperature, characterized in that a mixture of 0.5 to 50 percent by weight of an ester of a polymerizable α, / 9-ethylenically unsaturated carboxylic acid or dicarboxylic acid with a di- or higher-valent alcohol which bears a chlorine atom in the α-position to a free hydroxyl group, and 99.5 to 50 percent by weight of other unsaturated polymerizable compounds are copolymerized. © 109'577 / 440 4.61