DE2112008A1 - Composition for the manufacture of foam products in particular and their use - Google Patents

Description

Compound for the manufacture of foam products in particular

as well as their use

The invention relates to a composition for making foam products which has an aqueous medium with a pH in the range from about 6.5 to 11 and contains, as a component, a polymer latex, determined in parts by weight on a dry basis. As another ingredient, the composition has a reactive resin in an amount in the range of about 1 to 75 wt -.% Per 100 parts by weight of the polymer latex present at. The reactive resin is characterized in that it contains at least two substituent groups which are reactive with one another and which react with the polymer, or which contain groups which react or rearrange during processing to form groups, which latter react together and with

211200?

react with the polymer. The reactive groups include methylol groups attached to a nitrogen atom are; modified methylol groups which have been alkylated with an alcohol having 1 to 4 carbon atoms, if such groups are attached to a nitrogen atom; and methylol groups attached to the aromatic ring of a phenolic Group are affiliated.

The polymer latex includes at least ^one conjugated diene polymer or a copolymer which is produced from a conjugated diene with one or more ethylenically unsaturated, copolymerizable monomers, or mixtures of such homopolymers and copolymers. Such copolymers may be as much as 85 wt -.% Of ethylenically unsaturated monomers [CH "= C -) characters.

Examples of latices are those which contain polymers with unsaturated bonds, namely natural rubber, Butadiene-acrylonitrile copolymer, butadiene-styrene-acrylonitrile terpolymer -, butadiene-styrene copolymer -, polyisobutylene and Ethylene-propylene-diene terpolymer elastomers. Any a latex, which contains a polymer with unsaturated carbon -! - carbon bonds, is suitable for curing, regardless of whether it is foamed or not.

The latices are prepared either by copolymerizing the monomers in aqueous emulsions, which are surface-active Contain agents, catalysts, modifiers, etc.,

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ORIGINAL INSPECTED

under conditions used in emulsion polymerization technology are known, or by preparing an aqueous polymer dispersion, which is prepared by other methods was, for example, after block or solution polymerization.

Examples of reactive resins are condensates such as melamine-formaldehyde, urea-formaldehyde, methylated melamine-formaldehyde, methylated urea formaldehyde, butylated Melamine formaldehyde, butylated urea formaldehyde and phenol formaldehyde. The resins can advantageously be in the form of Compounds are used which are capable of forming the resins in situ. So, are the reactive resins, which are mixed with latices, those which are soluble in water or in water-miscible solvents.

The products made from the aqueous mass can be as much as about 1 to 75% by weight of the reactive Resin per 100 parts by weight of the latex solids, with the range of about 3 to 15 parts by weight being particularly advantageous is when flexible foams are desired. As is known to the person skilled in the art, fillers can be added to the mass in amounts of 0 to about 200 parts by weight per 100 parts of latex solids can be added, with a particularly preferred range of about Is 20 to 125 parts by weight of filler per 100 parts by weight of latex solids.

The storage stability of the latex and resin mixtures is 109839/1614

depends on the pH value. For example, if the pH is too high or too low, the resin will condense prematurely. Therefore, if the latex-resin mixture is held for an extended period of time a pH value of 6.5 to 9.5 should be maintained. However, if the mixture is to be used within a few hours of manufacturing time, it is a high pH not critical and can be as high as 11. Catalysts can be used for the condensation of the resins. Examples Usable catalysts are ammonia, ammonium salts of inorganic or organic acids such as ammonium phosphate, and amine salts such as aminopropanol hydrochloride, or hydroxylamine salts.

Fillers, plasticizers and antioxidants as well as other conventional products commonly used you can sit down.

The latex-resin mixtures prepared according to the invention are suitable for the production of film structures by methods which are commonly used for conventional latex compositions. You can handle them by brushing, Spraying, dipping, pouring, application by means of application rollers or a squeegee. The mass is used in particular for production of foam products. In general, the foam products of the invention have good aging properties when they Exposed to light or heat. They are also advantageous in that they use sulfur-containing substances is avoided and therefore, unpleasant odor will result

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Sulfur largely prevented. The foams of the invention have numerous applications and are particularly suitable for use as supports or pads for carpets and like floor coverings, and for use as cosmetic foams. '-

In general, the finished products should be ^{heated to temperatures of up to about 150 °} C., the length of time depending on the thickness of the finished product. Pur foam applications, where the foam is poured about 6.35 mm thick, the product is dried and cured in 20 to 30 minutes at 138 ° C, the time depending on the density of the wet foam.

example 1

A mass is produced which consists of a mixture of butadiene / acrylonitrile latex and melamine-formaldehyde resins, the mixture being formed mechanically in a mixer. The latex used is a butadiene / acrylonitrile latex 70/30, which is polymerized on a mixture of natural resin and fatty acid.

There will be a weight of about 675.6 (grams) of the latex which contains about 400 parts by weight (grams) of solids the following added:

22.8 g 30 / Sige aqueous solution of a phenolic An-109839 / 16U

oxidizing agent (bis-phenol sulfide) 45.2 g of 40% diammonium phosphate solution 32.4 g 8O # solution of mixed melamine-formaldehyde resins (the mixture contains dimethylol melamine, Trimethoxy-methylol-melamine and hexamethoxy-hexamethylol-melamine in a weight ratio of 1: 3: 2)

400 g aluminum hydrate filler 20 g 15 # solution of silicone surfactant

(Oxyalkylene-siloxane copolymer) 16.8 g of 30 # strength sodium lauryl sulfate solution 124.8 g of water to make up the finished preparation (about 1339 g) with a pesticide content of about 65 % and a pH of about 9.1.

About a quarter (334.7 g) of the above-mentioned preparation is foamed mechanically in a planetary mixer to a foam density of about 200 g per liter. The foam is then spread on a fabric with a thickness of 6.35 mm and the surface is heated by means of electrical heating elements (or infrared) in order ^{to generate a temperature of 218 °} C. on the surface of the foam and the foam to form a surface skin to harden in order to avoid cracking of the surface during the subsequent processing. After heating for 30 seconds, the foam is placed in a powered draft oven set at 149 ° C where the foam is dried for 25 minutes. The hardening of the foam is caused by the lack of adhesion of the cell wall

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and by the complete resistance of the cured foam to degradation upon washing in a detergent solution.

Example 2

This example illustrates the preparation of a blend of resin with a butadiene / styrene / acrylonitrile terpolymer latex, which is polymerized with a synthetic anionic detergent, as well as those made from the mixture Foam.

The latex is prepared in a bubble polymerization vessel by repeating the following latex preparation eight times by adding the following ingredients to a 907 g cookie:

57 cm ^ of water

10 cnr 5J solution of potassium persulphate

80 cm solution of the sodium salt of a linear Alkylarylsulfonate (surfactant) 8 cm 10 / fige sodium carbonate solution 15 em ^ l% solution of the salt of ethylene dinitrilo-

tetraacetic acid
150 g 1,3-butadiene

i * 4 g of styrene
12.5 cnr acrylonitrile
0.68 g of mixed tertiary mercaptan

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The placed in the bottle latex formulation is placed in a rotating constant temperature bath, with the temperature being held for 15 1/2 hours at 5O ° C, and at this time the Peststoffgehalt 47, J ^1% has been reached. About 30 cnr 2 # solution of acidic hydroxylamine sulfate is then injected to stop the polymerization. The pesticide content of the mixture of the eight repeated latices is 43.1 %, the latices being flowable and free from coagulum. The latex mixture is then steam distilled to remove unreacted monomers and then re-concentrated to a pesticide content of 58.7%.

When combining an initial latex-resin mixture for sponge testing, the following procedure is used: Procedure A

At 170, I ¹ g (100 g dry weight) of the latex are employed add:

5.7 g of a 53J6igen dispersion of a phenolic

Antioxidant (bis-phenol sulfide) 11.3 g 4O% diammonium phosphate solution 15.0 g 20% solution of a mixture of melamine resins (present in a ratio of 1: 3: 2 of dimethylol, trimethoxytrimethylol, and hexamethoxy-hexamethylol melamines)
100 g of alumina hydrate as a filler

5.0 g of a 15% solution of a silicone (oxyalkylene-siloxane copolymer) as a surfactant

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4.2 g 30% solution of sodium al ze s of lauryl

sulfate

19.2 grams of distilled water to make the full formulation which is 65% to about 70% total solids and has a pH of about 6.7.

The pH of the finished formulation is adjusted to 8.2 with 10% ammonium hydroxide solution and the preparation is then mechanically foamed as in Example 1, a foam density of about 193 g per liter being established. The foam is spread on a fabric surface, as in example "L" heated for 30 seconds at 28 ° C to form a surface skin, and then dried for 25 minutes at 149 ° C in forced air. The finished foam has a good structure and shows only slight sticking of the cell wall and slight shrinkage.

When combining a second latex-resin mixture, the following procedure is used: Procedure B

The second latex-resin mixture is prepared in the same way as in step A, with the exception that the resin is increased to 10 g (8 g on a dry basis). The preparation is foamed, as in step A, for 2 minutes, so that a foam density of 200 g per liter results. The finished one After the above-described heat treatment and drying in driven air, foam shows a fine structure and

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in addition, the sticking of the cell wall is greatly reduced, which indicates that an improved hardening has been achieved.

Example 3

This example illustrates the use of butadiene / styrene latex in practicing the invention.

ψ The butadiene / styrene latex is produced in bottles,

preparing four bottles by adding the following ingredients to each of them:

19 cnr distilled water 80 cm 53% potassium persulphate solution

80 cm lOJige solution of the sodium salt of a linear Alkylarylsulfonate (surfactant) 8 cm 10 solution of sodium carbonate 15 cm of a litigen solution of the sodium salt of

Ethylene dinitrilotetraacetic acid 150 g butadiene

55 cwr styrene
0, ^ 5 g of a mixed tertiary mercaptan.

The bottles are rotated in a polymerization bath, which is ^{kept at 50 °} C. for 22 1/2 hours, after which 20 cm ^ of a 2 # strength hydroxylamine sulfate solution is injected in order to stop the polymerization reaction. The four bottles of the formulation are then mixed together to make it

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a total solids content of M.9 %. The mixture is then steam stripped to remove unreacted monomers and then concentrated to > 4% total solids.

The latex produced as above is combined for foam sponge testing as follows. At 180.5 g (100 g on a dry basis) of the latex, the following is added:

3.0 g of a 53% dispersion of a phenolic

Antioxidant (bis-phenol sulfide) 18.8 g of an iOXy diammonium phosphate solution 0.5 g of a 50% solution of tetrapotassium pyrophosphate
g Georgia clay (No. 10 whipping chalk)

8.3 6 of a 15% solution of a silicone (oxyalkylene-siloxane copolymer) as a surfactant

8.1 g of an 80% solution of a mixture of MeIa-

mineral resins (present in a ratio of 1: 3: 2 of dimethylol, trimethoxy-trimethylol; and hexamethoxy-hexamethylol-melamine)

27.7 g of water to supplement the recipe, which has a solids content of 65 to 70 % .

The following operations are used in the manufacture and testing of the foam product:

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Operation A

About 3 ^ 9 j6 g of the preparation are adjusted to a pH of 8.5 with 30% ammonium hydroxide solution and then, as in Example 1, foamed mechanically for 3 minutes. The foam produced, which has a density of 222 g per liter, is spread on a fabric surface, heat-treated for 30 seconds at 218 ° C. as in Example 1 and then dried in forced air for 25 minutes at 149 ° C. to form a surface skin. The finished foam has a good structure and a height increased by 16%. If the foam is tested according to ASTM procedure D-1055-56T (3/1957), it shows a compression settling (based on compressed height) of 3 ^ * 3 % * It also shows a compression deviation (ASTM-156M) of 555 g each 6.5 cm with 503 »iger deviation.

Operation B

The same latex is prepared again using 11.3 grams of the same mixed resin. The foam density after foaming for 3 minutes is about 235 g per liter. After spreading the foam on fabric, heat treating it and drying it as in step A, the finished foam shows an expansion of 8 % and only 205? Compression withdrawal, as well as 865 g per 6.5 cm compression deviation.

Example 1

This example illustrates the effect of 109839/1614

Changes in the amount of melamine resin on the extent of curing of latex polymer as measured by tensile properties of films.

A latex is prepared in a 1,893 liter polymerization vessel. The components are: 689.5 kg of water; 5 ¹ I ¹ J, 3 kg of butadiene-1,3; 181.4 kg of styrene; 29.0 kg of the sodium salt of a linear alkylarylsulfonic acid; 2.90 kg of calcined soda; 0.09 kg of a mixed tertiary mercaptan; 14.5 kg of potassium persulfate; and 1.09 kg of the sodium salt of ethylenediaminetetraacetic acid. This batch is allowed to react for 35 hours at 49 ° C., after which time it has a total solids content of 43.6%. The reaction is terminated by adding 1.45 kg of hydroxylamine sulfate dissolved in 25.4 kg of water. The latex is then steam stripped to reduce the residual unreacted styrene content to 0.01 % .

Three films are prepared as follows: To 162.1 g (100 g on a dry basis) of the latex, add 1.3 g of a 75? igen dispersion of a phenolic antioxidant (bis-phenol sulfide), 13.8 g of a 40 # diammonium phosphate solution, (0, 3.75 or 7.5 g) of an 803> solution of mixed melamine-formaldehyde resins of the composition described in Example 1, 5.0 g of a 15% solution of a copolymer of siloxane and xthylene oxide, and 10.0 g of a lOySigen solution of the Sodium salt of a linear alkyl aryl sulfonic acid added. These Latex combinations are not foamed and spread out on glass plates with an estimated thickness to keep them dry

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To give film about 2.5 mm thick. The combinations allowed to dry for 24 hours at room temperature. Air-dried films are cut into three pieces, which hardened at 149 C for 10, 15 and 20 minutes, respectively. Each strip is tested for its tensile properties with results, which are compiled in the following table:

Amount of resin 300 S module
kg / cm tensile strenght Elongation at break no 3.5 24.6 780 3 10.6 28.8 670 6th 8.4 30.9 580

Elongation at break and tensile strengths are sensitive hardening indicators for latex films. As can be seen from the table, as the amount of the resin curing agent is increased, the elongation decreases and the tension increases, indicating that the crosslinking (vulcanization) of the polymer increases.

Example 5

This example shows the effect of different resin grades on . illustrates the film properties.

To compare a number of resins of different compositions, one uses the same latex and the basic recipe like the one that was used in example 4 above.

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was turned. The combination comprises 0.5 g of a 50% solution of tetrapotassium pyrophosphate and each of the resins is applied at 6 dry parts per 100 dry parts of latex. The tested Substances and the resulting tensile properties are given in the table below:

resin

Tensile strength elongation hardening kg / cm %

Melamine resin 27.4 500 Yes 1. Hexamethoxymethylol
melamine 11.8 650 Yes 2. mixed di- and tri
methylol melamine 15.5 550 Yes 3. like 2, with the exception of the height
rer condensation 36.6 700 Yes 1. alkylated melamine formal
dehydration 22.5 180 Yes 5. alkylated melamine
formaldehyde

Phenolic resin

6. Resorcinol formaldehyde

Urea resin

7. Dimethylol ethylene urea

8. Urea formaldehyde

9. Tetramethylurea

10. Dimethoxy-methyl-urea

8.1

530

Yes

17.6 780 Yes 23.9 850 Yes 19.7 780 Yes 26.0 760 Yes

Even if the resorcinol resin (6) caused hardening as judged by the last stretch, one notices

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but that the film is very sensitive. This sensitivity could well be from a solubility effect of the resin and polymer result that could be overcome by the hardening conditions (such as the pH value) are equalized. However, this material tends to be strongly colored and have an odor. Nevertheless, it appears to be able to cure the polymer. The urea resins give an increase tensile strength without such a large reduction in elongation as is encountered in melamine systems. This is a very desirable effect because it leads to the ability to use higher levels of inert fillers without the Elongation is reduced too much.

Example 6

This example illustrates how to make a Foam without the use of a silicone surfactant.

A latex is prepared in a 76 liter reaction vessel using the same basic polymerization recipe as used in Example * J above. The parts are 75 butadiene / 25 styrene, 95 water, * », 0 sodium alkylarylsulfonate, 0.4 part sodium sulfate, 0.20 part mixed tertiary mercaptans, 2.00 parts potassium persulfate and 0.075 parts sodium EDTA.

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The latex combination is prepared as follows: The following is added to 163.9 g (100 g dry weight) of the latex: 10 g of a 20% sodium lauryl sulfate solution, 1.3 g of a 75% dispersion of a phenolic antioxidant (bis-phenol sulfide ), 18.3 g of a 30% diammonium phosphate solution, 0.62% of a 4O3% tetrapotassium pyrophosphate solution, 8.8 g of an 80% solution of a mixture of melamine resins (present in a ratio of 1: 3: 2 of dimethylol, trimethoxytrimethylol and hexamethoxyhexamethylol -Melamin), and 100 g clay filler. This mass is foamed in a planetary mixer and results in a wet foam density of 361 g per liter. The foam was spread onto woven, heat it to the surface for 30 seconds at a temperature of 2L8 ° C, and then dried 24 minutes at 149 ⁰ C in air driven. The finished foam has a good structure and when tested according to ASTM procedure D-1055-56T (3/1957) it shows a compression settling (based on compressed height) of 34.0 %. He also has a compression deviation (DDD-C95) of 4.35 kg per 6.5 cm with a 50% deviation.

Various advantages accrue from the application of the curing system described above. For example, are Products made from the aqueous mass are essentially odorless. The hardening resins are non-pickling. You can use cheap fillers like silica flour, calcium carbonate (chalk), alumina hydrate, clay and the like be added to the aqueous mass in the dry state. Furthermore, the fillers can be used up to a relatively high content

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add, for example up to 200 parts by weight per 100 parts by weight of the latex on a dry basis without the latex in the aqueous mass is destabilized.

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Claims (10)

- 19 claims Composition for producing foam products in particular , characterized by an aqueous medium with a pH value in the range from about 6.5 to 11, this mass comprising a mixture of a polymer latex which contains unsaturated bonds and a reactive resin in an amount which range from about 1 to 75 wt. per 100 parts by weight of the polymer latex present, determined on a dry basis, with the reactive resin containing at least two substituent groups which are mutually reactive and which react with the polymer, or which contain groups which react to form groups during processing rearrange which react together or react with the polymer, these reactive groups being methylol groups attached to a nitrogen atom; modified methylol groups which have been alkylated with an alcohol having 1 to 4 carbon atoms when such groups are attached to a nitrogen atom; and methylol groups attached to the aromatic ring of a phenolic compound. 2. Composition according to claim 1, characterized in that the polymer latex is at least one polymer of a conjugated Has diene or copolymer, which is based on a conjugated diene with one or more ethylenically unsaturated, copolymerizable Monomers was prepared, or mixtures of these 109839/1614 Has homopolymers and copolymers, the copolymers containing up to about 85 % of the ethylenically unsaturated monomers. 3. Composition according to claim 1, characterized in that the polymer latex is natural rubber, butadiene-acrylonitrile copolymer -, butadiene-styrene-acrylonitrile terpolymer, butadiene-styrene copolymer, polyisobutylene or ethylene-propylene-oien-terpolymer elastomer is. 4. Composition according to claim 1, characterized in that the reactive resins melamine-formaldehyde7, urea-formaldehyde, methylated melamine-formaldehyde, methylated urea-formaldehyde, butylated melamine-formaldehyde, butylated Urea-formaldehyde or phenol-formaldehyde condensates are. 5. Composition according to claim 4, characterized in that the reactive resins are in the form of compounds which are able to form the resins in situ. 6. Composition according to claim 1, characterized in that it contains up to about 200 parts by weight of filler per 100 parts Has latex solids. 7. Composition according to claim 6, characterized in that the filler is in the range of about 20 to 125 parts by weight. 109839 / 16U 8. Use of the mass according to claim 1 to 7 for producing a cured product from elastomeric material, which is crosslinked and reinforced by a reactive resin, the amount of reactive resin in the range from about 1 to 75 wt .- ^, preferably from about 3 to 15% by weight, based on the elastomeric material. 9. Use of the composition according to claim 1 to J, for producing a cured foam product made of elastomeric material which is crosslinked and reinforced by a reactive resin, the amount of reactive resin in the range from about 1 to 75% by weight, preferably from about 3 to 15% by weight , based on the elastomeric material, the elastomeric material being at least one polymer of conjugated diene or a copolymer which is prepared from a conjugated diene with one or more ethylenically unsaturated, copolymerizable monomers, or mixtures of these homopolymers and copolymers, the copolymers containing up to about 85 % of ethylenically unsaturated monomers and the elastomeric material preferably natural rubber, butadiene-acrylonitrile copolymer, butadiene-styrene-acrylonitrile terpolymer, butadiene-styrene copolymer, polyisobutylene or is ethylene-propylene-diene terpolymer; and the reactive resins are melamine-formaldehyde, urea-formaldehyde, methylated melamine-formaldehyde, methylated urea-formaldehyde, butylated melamine-formaldehyde, butylated urea-formaldehyde, or phenol-formaldehyde condensate; and the product further has a filler in one 10 9 8 3 9/1814 Amount of up to 200 parts by weight, preferably from about 20 to 125 parts by weight, per 100 parts by weight of the elastomer Materials. 109839/1614