CH634338A5 - Liquid preparation containing copolymers containing halogen atoms and phosphonate groups - Google Patents

Abstract

The copolymers containing halogen atoms and phosphonate groups present in the liquid preparations and comprising components (a), (b) and (c) have good flame-inhibiting properties. Components (a), (b) and (c) are defined precisely in Claim 1. The copolymers are employed in the form of aqueous dispersions or in organic solvents for coating and impregnating non-textile substrates.

Description

634 338

2nd

PATENT CLAIMS 1. Liquid, water or organic solvent-containing preparation of copolymers containing halogen atoms and phosphonate groups

(a) 50 to 70% by weight of (meth) acrylic acid esters of the formula Ï •

in which Rx represents -CH2- or -CH2-CH2-, R2 represents hydrogen or a methyl or ethyl group, R3 represents a hydrogen atom or a methyl group and X represents bromine or chlorine atoms;

5 (b) 20 to 40% by weight of phosphonates of formula II

H H

I I

R2-C -C -RJ-OC-C = CH2

II II I XX o R3

(I),

10th

h in which Rt represents -CH2- or -CH2-CH2-, R2 represents hydrogen or a methyl or ethyl group, R3 represents a hydrogen atom or a methyl group and X represents bromine or chlorine atoms;

(b) 20 to 40% by weight of phosphonates of the formula II

H

R.

ch2-c

I.

c = o

I.

NH

o = pr

CH0 | ? OR,

"OR,

15

20th

CH = C

r.

-ch2-c c = o

NH

ch.

: or,

o = p;

"or n

r

3rd

ch = c c = 0

NH

(ii)

ch.

o = p;

: or,

"or,

C = 0

I.

NH

(ii)

ch.

0 = P

n or,

or,

25 in which R3 represents a hydrogen atom or a methyl group, R4 stands for alkyl radicals containing 1 to 4 carbon atoms and n stands for integers from 0 to 5 and

(c) 10 to 30% by weight of other monoolefinically unsaturated monomers which, when polymerized, give water-insoluble, hard polymers,

polymerized in an aqueous emulsion, the percentages by weight based on the total monomers.

6. Use of the liquid preparation according to claim 1 for coating and for coating and impregnating 35 non-textile substrates.

in which R3 represents a hydrogen atom or a methyl group, R4 stands for alkyl radicals containing 1 to 4 carbon atoms and n stands for integers from 0 to 5 and

(c) 10 to 30% by weight of other monoolefinically unsaturated monomers which, when polymerized, give rise to hard polymers which are insoluble in water,

the weight percentages refer to the total monomers.

2. Preparation according to claim 1, characterized in that it is in the form of an aqueous dispersion.

3. Preparation according to claim 1, characterized in that it is in the form of an organic solution.

4. Preparation according to claim 3, characterized in that it contains an organic solvent from the group containing 1 to 6 carbon atoms alkanols and cyclohexanol, 1 to 4

C-containing aliphatic ketones and cyclohexanone, 4 to 8 C-containing aliphatic ether, 4 to 6 C-containing esters of saturated aliphatic carboxylic acids and alkanols and liquid aliphatic and aromatic hydrocarbons.

5. A process for the preparation of aqueous dispersions of halogen atoms and phosphonate-containing copolymers according to claims 1 and 2 in the presence of radical-forming polymerization catalysts and dispersants, at temperatures from 20 to 100 ° C, characterized in that

(a) 50 to 70% by weight of (meth) acrylic acid ester of the formula I.

H H

I I

R2-C -C -RI-OC-C = CH2

I.

X X

(I),

o R3

From US Pat. Nos. 3,763,108 and 3,823,124 and 40 of DE-OS 2 217 746, N- (meth) -acrylamido-methylene-phosphonates and polymers from these monomers are known. The preparation of an aqueous dispersion of a copolymer of bis- (2-chloropropyl) -N-acrylamidomethylphosphonate, 45 methyl methacrylate and 2-ethylhexyl acrylate is also known from examples 3 of the US patents, with dodecyl mercaptan as regulator and potassium persulfate as polymerization catalyst for the emulsion copolymerization carried out at 75 to 80 ° C. The copoly-50 merisate obtained, which has halogen atoms and phosphonate groups, has pressure-sensitive adhesive properties and a film produced therefrom extinguishes when removed from a flame. The homo- and copolymerization of the optionally halogen atoms-containing phosphonates of these US patents can also be carried out in solution under reflux, in particular in butanol and / 55 or aromatic hydrocarbons using radical-forming polymerization catalysts and preferably with the addition of regulators such as dodecyl mercaptan, allyl acetate, cyclopentadiene or mercaptoacetic acid will. The known copolymers can be used to produce fio coatings which are said to have good chemical and solvent resistance and non-burning properties.

However, the flame-retardant properties of the polymers prepared from these known sulfonates leave a lot to be desired. A particular disadvantage of the copolymer known from Example 3 of US Pat. Nos. 3,763,108 and 3,823,124, which has halogen atoms and phosphonate groups, is, however, that there is no flame on synthetic fibers

can be reached with protection: the samples burn without extinguishing.

The flame-retardant properties of the homopolymers and copolymers, which are prepared by emulsion copolymerization of dibromopropyl acrylate or methacrylate in aqueous emulsion according to the information in Japanese Patent Application Laid-Open No. 4,720,238 and No. 7,236,236, also leave something to be desired left, even if, as is the case in the last-mentioned Japanese patent application, with alkylphosphoric esters, and the stability of aqueous dispersions of the copolymers which additionally contain the alkylphosphoric esters in emulsified form relatively low, so that a sediment forms when standing.

It has now been found that the copolymers containing halogen atoms and phosphonate groups contained in the liquid preparations

(a) 50 to 70% by weight of halogen atoms containing (meth) acrylic acid esters of the formula I.

20th

H H

I I

R2-C -C -RJ-OC-C = CH2

II II I XX O R3

(I).

25th

in the

R! for -CH2- or -CH2-CH2-,

R2 for hydrogen (H-) or for a methyl (CH3) or 30 ethyl (CH3-CH2 -) - group,

R3 represents a hydrogen atom (H-) or a methyl group (CH3-) and

X represents bromine (Br) or chlorine atom (C1-),

b) 20 to 40% by weight of N- (meth) acrylamido-methylene-phos-35 phonate of the formula II

r.

CH2-C

c = o nh ch.

0 = p.

or,

"or,

r.

ch = c

40

C = 0 NH

(ii)

ch.

0 = p n

; or,

or,

45

50

55

in the

R3 represents a hydrogen atom (H-) or a methyl group (CH3-),

R4 is alkyl radicals containing 1 to 4 carbon atoms and n is an integer from 0 to 5 and c) 10 to 30% by weight of other monoolefinically unsaturated monomers which, when polymerized, give rise to hard polymers which are insoluble in water, the weight percentages are based on the total weight of the monomers,

have particularly good flame-retardant properties.

Suitable halogen acrylates of formula I are especially the dibromoalkyl esters of acrylic and methacrylic acid, e.g. of the 2,3-

60

65

634 338

Dibromobutanol- (l), 3,4-dibromo-n-pentanol- (l), 2,3-dibromo-propanol- (l), 3,4-dibromo-n-hexanol- (l), 3,4- Dibromobutanol- (1) and 2,3-dibromopentanol.

The suitable N- (meth) acrylamido-methylene-phosphonate of the formula II can, however, be prepared in a manner analogous to that described in US Pat. Nos. 3,763,108 and 3,823,124 and DE-OS 2,217,746 in a solvent-free manner. In the processes specified there, the reaction products obtained are mixtures which, in addition to the monomeric N- (meth) -acrylamido-methylene-phosphonates, contain oligomers of these phosphonates which are composed of two to six monomeric N- (meth) -acrylicamido-methylene- Build up phosphonates. These oligomers arise from the monomeric N- (meth) -acrylamido-methylene-phosphonates in the production methods of the above-mentioned US Pat. Nos. And DE-OS (for example, if one works according to the information in the examples of these patents) by radical addition reaction and Phosphonates in which n represents integers from 0 to 5 are of particular interest as monomers (b) for the new copolymers contained in the liquid preparations. They can be separated off from the mixtures obtained in the preparation of the N- (meth) -acrylamido-methylenephosphonates in accordance with the literature references specified for this purpose, for example by fractional distillation. Of particular interest for the new copolymers contained in the liquid preparations are phosphonates of the formula II in which R3 represents a hydrogen atom and R4 represents a methyl or ethyl group.

The comonomers (c) which are used in particular in the preparation of the new copolymers contained in the liquid preparations by emulsion copolymerization in amounts of 10 to 30% by weight are the monoolefinically unsaturated monomers which, when polymerized, are insoluble in water , hard polymers, such as, in particular, acrylonitrile, methacrylonitrile, vinyl acetate, styrene, a-methylstyrene, methyl methacrylate, ethyl acrylate and methacrylate, tert-butyl acrylate and methacrylate, and in particular vinyl chloride and vinylidene chloride.

The copolymers containing new halogen atoms and phosphonate groups contained in the liquid preparations can be prepared in a conventional manner from the monomers of the type mentioned, generally using radical-forming catalysts in bulk, in solution, in aqueous emulsion or suspension, the emulsion polymerization and solution -Polymerization are of particular interest.

In the preparation of the new copolymers containing halogen atoms and phosphonate groups contained in the liquid preparations by polymerization in aqueous emulsion, the halogen acrylates of the formula I in amounts of 50 to 70% by weight, the phosphonates of the formula II in amounts of 20 to 40 % By weight and the other monoolefinically unsaturated monomers (c) are used in amounts of 10 to 30% by weight and the polymerization is carried out at temperatures from 20 to 100 ° C., preferably from 50 to 95 ° C., using the customary radical-forming polymerization catalysts and dispersing aids and, if appropriate, regulators. Radical-forming polymerization catalysts for emulsion polymerization include, in particular, water-soluble persulfates, such as ammonium persulfate, sodium persulfate and potassium persulfate, azobiscarboxylic acid nitriles, such as azobisbutyric acid dinitrile, and mixtures of persulfates of the type mentioned or hydrogen peroxide with reducing agents, such as sodium triumbinate acid or called so-called redox catalysts. The radical-forming catalysts of the type mentioned can be used in the amounts customary for this, which are usually between 0.05 and 2% by weight, based on the monomers, preferably in amounts of 0.5 to 1.2% by weight will.

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Dispersing agents which are likewise generally used in the amounts of 0.2 to 3% by weight, based on the monomers, which are customary, preferably in amounts of 0.5 to 1.2% by weight.

Dispersing aids which can likewise generally be used in the amounts customary per se of 0.2 to 3% by weight, preferably 0.3 to 1.0% by weight, are, for example, called anionic emulsifiers, such as sodium dialkyl sulfosuccinates, K or NH4 salts of saturated or unsaturated aliphatic carboxylic acids, Na salts of sulfated oils, Na salts of alkyl acryl sulfonic acids, N, K or NH4 salts of unsaturated acids, Na , K or NH4 alkyl sulfates (C12-C24 alcohols, sulfated), Na, K or NH4 salts of sulfonic acids. Examples of nonionic emulsifiers are fatty acid ethylene oxide condensates, oxyethylated alkylphenols, sorbitan esters, polyoxyethylene fat glycerides, glycerides of fats and oils and oxyethylated fatty alcohols. If necessary, protective colloids such as methyl cellulose and polyvinyl alcohols can also be used. Of particular interest as dispersing aids are Na, K and NH4 salts of sulfated oxyethylated C12-C24 fatty alcohols and oxyethylated fatty alcohols.

In the case of emulsion polymerization, the amount of the total monomers is usually between 30 and 60, preferably between 40 and 60,% by weight, based on the total amount of the polymerization batch, and the entire monomers can be charged in batches or with some of the monomers present and the remaining ones being fed in. preferably polymerize monomers emulsified in part of the aqueous phase (emulsion feed process). In the new process, the use of butenols, such as, in particular, butene- (l) -ol- (3) and n-dodecyl mercaptan in amounts of 0.5 to 5%, preferably 1.5 to 2.5%, has been found to be a regulator hastily proven to be particularly advantageous since this can be used to obtain aqueous dispersions which are particularly low-viscosity. The aqueous dispersions of the new copolymers are suitable for coating, coating and impregnating flat non-textile substrates. Additives customary for this purpose, for example color pigments, tackifying resins or fillers, can be added to the aqueous dispersions in the amounts customary for the particular application for the production of coatings and coatings. Using clay and / or titanium dioxide with the addition of small amounts of antimony trioxide, from the dispersions according to the invention, e.g. Paper coating slips for the flame-retardant coating of paper and cardboard can be obtained.

For the preparation of the new copolymers contained in the liquid preparations in solution, the customary organic solvents, in particular alkanols containing 1 to 6 carbon atoms, such as methanol, ethanol, n-propanol, isopropanol and butanols, and cyclohexanol, 1 to 4 carbon atoms Aliphatic ketones containing atoms, such as acetone, methyl ethyl ketone, diethyl ketone and methyl isobutyl ketone, and cyclohexanone and methyl cyclohexanone, aliphatic ethers containing 4 to 8 carbon atoms, such as especially diethyl ether, diisobutyl ether, tetrahydrofuran and dioxane, 4 to 6 -Atoms containing esters of saturated aliphatic carboxylic acids and alkanols, such as especially ethyl acetate, isopropyl acetate, n-butyl acetate, and also dimethylformamide or liquid aliphatic or aromatic hydrocarbons can be used. For solution polymerization, organic peroxides soluble in the solvents used, such as benzoyl peroxide, acetyl peroxide, lauroyl peroxide, 2,4-dichlorobenzoyl peroxide and / or azo compounds such as azodiisobutyric acid nitrile and / or peresters, such as 4-butyl perpivalate, are preferably used as catalysts in amounts of preferably 0.2 to 3% by weight, based on the amount of monomers, and the concentration of the monomers in the solvents is generally 10 to 40, preferably 20 to 30% by weight, based on the mixture, of monomers from monomers and solvents. When carrying out the solution polymerization, the procedure is generally carried out at from 50 to 5120.degree. C., preferably from 80 to 120.degree. C., and the monomers can be introduced in whole or in part and, if appropriate, in part in solution in accordance with the polymerization . Dioxane is of particular interest as a solvent, since it regulates at the same time and the resulting solvent has a low viscosity, which is favorable for further processing.

The solutions of the copolymers of the type mentioned can be used in particular for the production of coatings and impregnations, for example for flame-retardant finishing. If conventional polymer films are coated with it, optionally with the addition of tackifying resins, the copolymers contained in the liquid preparations can be used to produce pressure-sensitive adhesive tapes with flame-retardant properties.

2o The aqueous dispersions and organic solutions of the new copolymers can generally be applied per se to flat non-textile substrates, for example by spraying, brushing or padding, the application being preferred if a flame-retardant coating or finish is desired 20 to 40 wt .-% of new copolymer (solid), based on the substrate to be coated, is.

To test for the flame-retardant effect of the new copolymers 30 contained in the liquid preparations, substrates which have been treated with the copolymers are placed on asbestos and clamped vertically. It is then flamed with a 2 cm high propane gas flame, the flame being ignited in the middle of the width dimension of the sample, 4 cm above its lower edge. Ignition times are chosen between 30 and 60 seconds. In the samples, the ignition generally takes place after 10 to 15 seconds, but the flame often extinguishes before the ignition time has ended.

The formation of drops is greatly reduced in the case of samples made of synthetic fibers. The test specimens usually carbonize, while un-40 equipped comparison samples burn completely.

The parts and percentages given in the following examples relate to the weight.

example 1

45 7.5 parts of sodium pyrophosphate, 30 parts of sec-butenol and 3 parts of potassium persulfate are dissolved in 1500 parts of water and the solution is heated to 85 ° C. (initially). In addition, 90 parts of styrene, 75 parts of acrylic acid, 135 parts of a 45% aqueous N-methylol methacrylamide solution, 900 parts of 2,3-di-50 bromopropyl acrylate and 450 parts of oligomeric N-dimethylphos-phonomethylene acrylic acid amide (average molecular weight Mn = 300, measured with the Vapor pressure osmometer, produced according to Example 2 or US Pat. No. 3,763,108, but without solvent), using 100.5 parts of aqueous 55 solution of the Na salt of sulfated oxyethylated fatty alcohol (degree of ethylation 25) in 1240 parts of water. yaws. 7.5 parts of sodium pyrophosphate and 9 parts of potassium persulfate are added to the emulsion. The emulsion is then run to the template within 2 hours. The pH-60 value of the reaction mixture is kept at 6. After the monomer feed has ended, a solution of 3 parts of potassium persulfate in 150 parts of water is added over the course of 15 minutes and the mixture is polymerized at 90 ° C. (2 hours). A 35% aqueous dispersion of a bromine atom and a copolymer having five phosphonate groups is obtained.

Example 2

A solution of 7.5 heated to 85 ° C serves as a template

Parts of sodium pyrophosphate, 33 parts of sec-butenol and 3 parts of potassium persulfate in 1300 parts of water. 240 parts of methyl methacrylate, 75 parts of acrylic acid, 900 parts of 2,3-dibromopropyl alcohol are emulsified in 1080 parts of water, to which 100.5 parts of a 35% strength aqueous solution of a sulfated oxyethylated stearyl alcohol (degree of oxyethylation 20) have been added. acrylate and 450 parts of N-dimethylphosphonomethylene acrylic acid reamide (oligomer mixture, molecular weight 250, prepared analogously to Example 2 of US Pat. No. 3,763,108, but without solvent). 7.5 parts of sodium pyrophosphate and 9 parts of potassium persulfate are added to the emulsion obtained and they are allowed to run to the initial charge within 2 hours, the pH being maintained at 6. After the monomer feed has ended, a solution of 3 parts of potassium persulfate in 150 parts of water is added and the mixture is left to polymerize at 90.degree. A 40% aqueous dispersion is obtained.

Example 3

A solution of 5 parts of sodium pyrophosphate, 15.3 parts of sec-butenol and 2 parts of potassium persulfate in 100 parts of water, heated to 85 ° C., is used as the initial charge. 100 parts of n-butyl acrylate, 100 parts of 2,3-dibromopropyl acrylate, 20 parts of acrylic acid and 800 parts are added to 800 parts of water to which 100 parts of a 30% aqueous solution of the sodium salt of a sulfated, oxyethylated nonylphenol (degree of ethylation 25) are added N-dimethylphosphonomethylene acrylic acid reamide (molecular weight Mn 235, oligomer mixture, prepared analogously to Example 2 of US Pat. No. 3,763,108,

5 634 338

but without solvent) emulsified and 90 parts of a 45% aqueous solution of N-methylol methacrylamide added. 5 parts of sodium pyrophosphate and 6 parts of potassium persulfate are added to the emulsion obtained and 5 are added to the initial charge within 2 hours, the pH of the mixture being kept at 5 to 6. After the addition of the monomers has ended, a solution of 3 parts of potassium persulfate in 150 parts of water is added and the mixture is polymerized at 90.degree. A 35% aqueous polymer dispersion is obtained which is suitable for the flame-retardant impregnation of fabrics, knitted fabrics and nonwovens.

A paper (unsized, basis weight 65 g / m2) is impregnated with the dispersion, the order being 26%, based on the twill, and dried. The sample extinguishes 15 after an ignition time of 60 seconds.

Example 4

16 parts of sec-butenol and 0.8 part of 2,2'-azoisobutyronitrile 20 in 1640 parts of dimethylformamide are placed in a reaction vessel and heated to 95 ° C. 560 parts of 2,3-dibromopropyl acrylate, 160 parts of N-dimethylphosphonomethylene acrylic acid reamide and 80 parts of acrylonitrile are added to 1100 parts of dimethylformamide. This solution is allowed to run to the template with stirring for 2 hours. After the end of the feed, 7.2 parts of 2,2'-azoisobutyronitrile in 360 parts of dimethylformamide are run in and the mixture is polymerized for a further two hours. The polymer solution contains 20% polymer.

C.