DE2014385A1 - Process for the production of plastics including foams - Google Patents

Description

FARBENFABRIKEN BAYER AG

LEVERKU S EN-Bayeiwerk GM / Bn Petitioner Abbey

2 March 4. 1970

Process for the production of plastics - including foams _

The present invention relates to a method of manufacture of plastic and cross-linking of aqueous dispersions of reactive polymers with polyisocyanates.

It is known and the general state of the art, polymers to implement with reactive groups with polyisocyanates. For example, polyesters containing hydroxyl groups or Polyethers according to methods customary in the art with polyisocyanates, optionally with the use of water, Stabilizers, blowing agents, catalysts, retarders and other polyurethane foams of various types and for manufactured for a wide variety of purposes. A comprehensive description can be found in: Kunststoff-Handbuch, | Volume VII, "Polyurethane", editor Prof. Dr. R. Vieweg and Dr. A. Höchtlen, Carl Hanser Verlag, Munich 1966 and in Houben-Weyl, - Volume'XIV, 2, "Macromolecular substances", part 2, Georg Thieme Verlag, Stuttgart, 1963.

Water is used in small quantities in these processes, which releases gaseous carbon dioxide through reaction with the isocyanate, which causes foaming of the masses produced serves.

Le A 12 844 - 1 -.

109842/1795

20H385

Surprisingly, it has now been found that when mixing polyisocyanates with aqueous dispersions of polymers, which contain substituent groups capable of reacting with polyisocyanates play no or only a subordinate role playful reaction of the polyisocyanate with water to the corresponding polyurea occurs, but that on the contrary the reaction of the polyisocyanate with the reactive groups of the polymer is preferred, and that the property profile of the polymer crosslinked in this way is determined by the polyisocyanate used.

In the manner according to the invention described in more detail below, it is possible by suitable combination of polyisocyanates polymers crosslinked with aqueous dispersions of copolymers to achieve, the characteristics of which can be adapted to many uses.

_S i from the German Auslegeschrift 1,420,142 t is known to produce films, coatings, impregnations or adhesive bonds characterized in that aqueous polymer dispersions or solutions having pendant carboxyl, aldehyde or carboxamide groups with water-soluble resin-forming formaldehyde condensation products and optionally Condensation catalysts mixed and thermally aftertreated.

Compared to this crosslinking process, the process according to the invention has the advantage that no formaldehyde is used during the crosslinking is set free, which is also annoying because of the formaldehyde's own odor and its toxicity.

Also known is a method of making foams in which a latex with reactive groups, e.g. Carboxyl groups mixed with, for example, a melamine or urea-formaldehyde resin, the resulting mixture foams, the Foam is gelled and then hardened and dried.

Le A 12 844 - 2 -

109842/1795

A disadvantage of the method, however, is that when using the usual melamine or urea-formaldehyde resins as Crosslinker large amounts of formaldehyde are produced during the curing stage, which is because of the intense and strong mucous membranes the irritating odor of formaldehyde and its toxicity cause considerable nuisance during foam production leads.

It is also disadvantageous that after this method produced foams only low wet strength and boil wash resistance have and that their fillability with fillers is very limited. -. ~

... · ■■ - ■ · - ■

The present invention is a process for the production of plastics including foams by Reaction of copolymers containing reactive hydrogen atoms of polymerizable monomers with polyisocyanates, optionally in the presence of auxiliaries, characterized in that reactive hydrogen atoms Copolymers of polymerizable monomers in aqueous. ger dispersion can be used.

According to the present invention, an aqueous dispersion is used a copolymer having reactive hydrogen atoms with a. Polyisocyanate around.

As groups with reactive hydrogen atoms, e.g. in question: carboxylic acids, di- and polycarboxylic acids, primary and secondary amines, carboxamides, which at least one Carry hydrogen atom on nitrogen, or their free or closed methylol compounds, primary, secondary and tertiary aliphatic alcohols, phenols, oximes, sulfonamides, Hydrazines, hemiacetals, enols, mercaptans, imides, imines.

To produce the starting material to be used according to the invention, at least two polymerizable olefinically unsaturated monomers are copolymerized in an emulsion system to form a latex copolymer, Le A 12. 844-3 -

1098 42/1795

20U3BB

customary auxiliaries such as cationic or anionic or nonionic surfactants or emulsifiers can be used.

According to the invention are also copolymers polymerized in solution, which are then converted into the latex form can be used.

At least one of the monomers which are used to prepare the polymeric aqueous dispersion consists of a polymerizable olefinically unsaturated monomer which has an isocyanate-reactive substituent -P has group with at least one reactive hydrogen atom.

Examples of such monomers are: acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, Ethyl maleate, 2-sulfoethyl acrylate, 2-sulfoethyl methacrylate, SuIfot. butyl methacrylate, 2-aminoethyl methacrylate hydrochloride, Vinylbenzylamine, glycidyl methacrylate, hydroxystyrene, allyl alcohol, yinylbenzyl alcohol, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, acrylamide, methacrylamide, Bis-N-methylolacrylamide and its ethers, esters or urethanes, N-methylolacrylamide and its ethers, esters or urethanes, Bis-N-Methylolinethaerylamid as well as its ethers, esters or ™ Urethane, N-methylol methacrylic acid and its ethers, esters or urethanes, N-ß-Hydroxyätliy 1-

acrylamide, N-ß-hydroxyethy methacrylamide, ß-hydroxypropyl acrylate, ß-hydroxypropyl methacrylate, C ^ -hydroxypropyl acrylate, OOHydroxypropyl methacrylate, 6-hydroxyhexyl acrylate, 6-hydroxyhexyl methacrylate, N "~:; methyl sulfonate, Na-o-styrolate iinnoä'thylaorylathydrochlorid, 2-MethylaminoäthyJmethacrylathydroch] orid, 3-Methylaminopropylacrylathydr <jchJorid, 3-Mothy laminopropylmethacrylathydrochlorid, ί-Me LJi.y] ami nobuty J acr / 1 - 'hyclrouty] a1. ry nietami. ]) ydrocJji '> rUi _t ^ - EthylaminopropylacrylMthydroch] orid, ' {■■ '■ ^! -i '-r ;; iij'i,' ■ '■■ ■ <■ nincry J ami d.

BATH Cni

-sr

Suitable monomers are also those which have substituent groups carry, which can be converted into substituent groups with or after the polymerization Isocyanate groups able to react, such as esters, Nitriles, amides or .. salts which can be hydrolyzed to reactive acid, amine, amide or hydroxyl groups.

Examples of comonomers which, in combination with the reactive, polymerizable monomers can be used, are among others. aromatic alkeny compounds, derivatives of olefinic unsaturated acids such as acrylic esters, methacrylic esters, Acrylonitrile, esters of unsaturated dicarboxylic acids, unsaturated | Alcohol esters, unsaturated aldehydes and ketones, conjugated olefins and other compounds that contain one or more Contain olefinic bonds that require additional polymerization allow.

Examples of such olefinically unsaturated compounds are: styrene, txL-methylstyrene, ar-ethylstyrene, ^ -ar-dimethylstyrene, Ar-ardimethylstyrene, Ar-tert.butylstyrene, vinylnaphthalene, Methoxystyrene, cyanostyrene, acetylstyrene, monochlorostyrene, Dichlorostyrene and other halostyrenes, methyl

Methyl acrylate,
methacrylate / ethyl acrylate, butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, lauryl methacrylate, phenyl acrylate, acrylonitrile, methacrylonitrile, ethyl - <? d-chloroacetate, diethyl maleate, | Polyglycol maleate, vinyl chloride, vinyl bromide, vinylidene chloride, vinylidene bromide, vinyl methyl ketone, methyl isopropenyl ketone, vinyl ethyl ether, 1,3-butadiene, isoprene, 2-cyanobutadiene, chloroprene and the like.

Copolymers are preferred which consist of at least two polymerizable olefinically unsaturated monomers, 0.1 to 30 wt .- ^, preferably .0.5 to 15 wt .- ^ of these monomers consist of at least one monomer which at least one with isocyanate groups Has reactive substituent group with at least one active hydrogen atom.
Le A12 844. '' ·. ■ - 5 - '

10 9 8 4 2/179 B

BATH ORIGINAL

7014385 b

The reactive latices can be prepared by emulsion copolymerization of selected monomers as described above.

However, such latices can be replaced by water dispersions of preformed polymers which have been modified are, e.g., by grafting or by other means, to obtain pendant substituent groups that react with isocyanates capital.

Likewise, such water dispersions of preformed, optionally reinforced polymers with attached reactive Groups are used which are obtained by subsequent dispersion of the polymer with the addition of dispersing aids have been manufactured.

Polymers which can be hydrolyzed to form aqueous dispersions of polymers with such reactive groups are also used.

According to the invention, a process is therefore preferred in which the copolymers used are those of at least two polymerizable ones olefinically unsaturated monomers, 0.1 to 50% by weight, preferably 0.5 to 15% by weight, of these monomers consist of at least one monomer which has at least one isocyanate-reactive substituent group with at least having an active hydrogen atom can be used.

As already indicated, such copolymers are particularly preferred

-COOH-, -CO-NH ₂ -, NH ₂ -, -CO-NH-CH ₂ -OH-, -CO-NH-CH ₂ -OR-

(R = C ₁ -C ₁₂ -AlCyI), -OH groups.

Le A 12 844 - 6 -

795

A preferred copolymer according to the invention is one consisting of 30 to ⁰ % by weight of butadiene, 60 to 10 % by weight of styrene and 15 to 1% by weight of a monomer having -COOH groups.

A copolymer consisting of 50 to 80% by weight of butadiene, 60 to 10% by weight, is also preferred according to the invention. Acrylonitrile, 15 to 1 wt .- # of a -COOH groups Monomers. '·

A copolymer with 30 to 80% by weight of butadiene, 60 to 10% by weight of styrene, 15 to 1% by weight of a monomer having OH groups is also preferred.

According to the invention, it is also preferred as a copolymer one consisting of 99 to 85% by weight of chloroprene and 1 to 15% by weight of an N-t-ethylol ether group Monomers. . . .

Further, as a copolymer in the present invention, there is one preferred, consisting of>

30 ... - 80% by weight butadiene
60-0 "styrene

60 -0.5 "(meth) acrylic acid ester

60 - 0 "'acrylonitrile and I.

1-15 "of a monomer containing -COOH groups.

A copolymer composed of is likewise preferred according to the invention

30 - 80 wt. Fo butadiene

60 - 0 "styrene. /

60-0.5 "(metal acrylic acid ester 60-0" acrylonitrile and
1--15 "of a monomer having -CONHp groups.

Le A 12 8AA ■ _ 7 _

1 0 9 8 /, 4/1 7 night -5

BATH

20H385

There is also a copolymer of 30-80 % by weight of butadiene 60-0 "styrene

60-0.5 "(meth-acrylic acid ester 60 0" acrylonitrile and

1-15 »of a monomer having -OH groups is preferred according to the invention.

Furthermore, a copolymer is preferred consisting of 30-80% by weight of butadiene

60 - 0 Il Styrene 60 - 0 I! (Meth) acrylic acid esters 60 - 0 Il Acrylonitrile 0 - 15th Il a -COOH groups and 0.5 - 15th It one having N-methylol ether groups Monomers.

Plyisocyanates to be used according to the invention are used such of any and conventional type in question, e.g. aliphatic, cycloaliphatic, araliphatic ^, aromatic and heterocyclic difunctional and higher functional isocyanates. The polyisocyanates can be both in free form, preferably but can also be used in disguised form. The production of masked polyisocyanates is known per se and takes place e.g. by reacting the free polyisocyanates with blocking agents such as phenols, oximes, sulfites or Malon star. Sulfites as capping agents are preferred. As examples of polyisocyanates to be used according to the invention may be mentioned: butane-1,4-diisocyanate, hexamethylene-1,6-diisocyanate, Diphenylmethane-4,4'-diisocyanate, phenylene-1,4-diisocyanate, Naphthylene-1,5-diisocyanate, toluylene-2,4- and / or -2,6-diisocyanate, isophorone diisocyanate, hexahydrotoluylene-2,4- and / or 2,6-diisocyanate, polyphenylpolymethyl polyisocyanates such as those produced by aniline-formaldehyde condensation and subsequent phosgenation can be produced

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polyisocyanates containing carbodiimide groups, such as those prepared, for example, in accordance with German Patent 1,092,007 can be.

Also suitable are less volatile, higher molecular weight polyisocyanates obtained by reacting polyisocyanates with polyalcohols in proportions such that free isocyanate groups are still present after the addition. Examples of prepolymers include reaction products of the above-mentioned polyisocyanates with polyhydroxy compounds, for example saturated or unsaturated diols, triols and polyols such as glycerol, trimethylolpropane , etc. with linear or branched polyesters or polyethers containing hydroxyl groups or polyethers with small amounts of water, aldazines including straight-chain ones containing carboxyl groups or branched polyesters or polyethers, which can optionally also be unsaturated. It is also possible to use polyisocyanates which have been formed by the di- or trimerization of low molecular weight polyisocyanates as described above with the formation of uretdiones or isocyanurates. Furthermore, partially or completely closed polyisocyanates are also suitable, which are obtained from low molecular weight polyisocyanates or from prepolymers containing free isocyanate groups by reaction with, for example, the following components which are reactive with isocyanate groups are manufactured: imidazoles, phthalimide, acetoacetic esters, malonic esters, acetylacetone, caprolacta? n> phenols, primary, secondary, tertiary alcohols, hydrogen sulfite. Mixtures of different isocyanate compounds can be used. It can be particularly advantageous if the solid polyisocyanate is used in solution in a liquid polyisocyanate. Aliphatic and cycloaliphatic polyisocyanates with low vapor pressure are preferred according to the invention.

Le A12 844 . - y -

109842/17

20H385

Optionally, in the reaction between reactive latices and polyisocyanates, the use of in the Isocyanate chemistry customary catalysts and / or retarders may be advantageous. Examples of catalysts are:

Basic compounds such as pyridine, Ν, Ν'-dimethylpiperazine, Triethylenediamine, N, N'-dimethylaminocyclohexane, diethanolamine, triethanolamine, alkylmorpholines, tri-n-butylphosphine, and metal salts, organic metal complexes and organometallic compounds, for example of the dibutyltin laurate type.

Compounds with an acidic character such as mineral acids, acid chlorides, carbamic acid chlorides * p-toluenesulfonic acid, boric acid and others are particularly suitable as retarders.

The reactive latex and the polyisocyanate are used in such amounts that the mixture contains the polyisocyanate in an amount of about 0.1 to 100% by weight (preferably 0.2 to 30% ) of the copolymer of the latex.

Because of the high reactivity of the polyisocyanates, they are normally only added to the latex mixture when other components of the mixture, such as fillers, thickeners, dispersants, etc., have already been added to the latex mixture. Polyisocyanates which are liquid at room temperature are usually added to the latex directly or in emulsified form. Solid polyisocyanates are preferably added in the dispersed state or they are added to the latex in the dissolved or molten state either directly or as an emulsion. The finished mixture is then processed, depending on the intended use, for example by brushing, spraying, dipping, pouring or applying with the aid of application rollers or doctor blades. The water is then usually removed at temperatures of 20 and 200 ^° C. and the crosslinking is carried out.

Le A 12 844 -IU-

109842/1795

2Q14385

When choosing the individual components of the mixture, care should be taken to ensure that they interact with one another and with the reactive ones Groups of the latex polymer and with the polyisocyanates used are compatible.

If no special effects are desired, additives are avoided, which contain a high concentration of functional groups with active hydrogen.

The pH of the mixture will be if the mixture is not the desired one PH level is usually set between about 2 and about 13. The regulation of the PH range can I with the usual acidic or alkalizing agents such as acetic acid, citric acid, diluted mineral acids, ammonium hydroxides, Alkali hydroxides, ammonium salts, etc. can be made. '

The production of foams by the process according to the invention is carried out in a preferred embodiment as follows: A mixture of reactive latex and additives such as fillers, thickeners, dispersants, foam auxiliaries, foam stabilizers and, if appropriate, the additives customary in isocyanate chemistry such as activators, catalysts, retarders, etc. g is foamed in a manner customary in latex foam production, for example by foaming in a commercially available foam head to 3 to 12 times its original volume. The polyisocyanate is metered directly into the foam head during the foaming process, optionally with the use of catalysts, activators, retarders, etc. customary in isocyanate chemistry. Polyisocyanates which are liquid at room temperature are usually added to the latex directly or in emulsified form. Solid polyisocyanates are preferably added in the dispersed state or they are added in the dissolved or molten

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zen state either directly or as an emulsion to the latex added.

Although it is not necessary to practice the present invention, specific gelling agents such as sodium fluosilicate, zinc oxide, ammonium salts, etc. can be used. If these auxiliaries are used, they are usually added towards the end of the foaming process. The foamed mixture is poured into molds, or spread out on a flat sheet or it can be "carrier materials coated therewith · ^1.

The term "carrier materials" includes materials such as paper, fabric, cloth, leather, felt, glass or metal any shape on which the foamed mixture adheres after application and hardening.

Gelation of the foam is usually carried out at temperatures below 10O ⁰ C. In the process according to the invention it is possible to vary the gelling conditions to a large extent by means of suitable combinations of reactive latices, polyisocyanates, catalysts and surface-active agents. For example, nonionic surface-active agents from the group of ethoxylated alkylphenols, fatty acids and fatty alcohols generally delay the onset of gelation. In the present invention, the hardening stage is a continuation of the gelling process, the polyisocyanate and the reactive latex polymer reacting further.

The curing of the foam can be carried out in a temperature range from ⁰ ° C. to just below the melting or decomposition temperature of the material composition. However, since higher temperatures accelerate both the curing rate and the drying rate, the

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The hardening stage is often carried out at temperatures between approx. 90 ^° C. to 200 ^° C. While large amounts of formaldehyde are liberated in the curing of latex foams, which are made with resin-forming, water-soluble formaldehyde condensation products as a curing agent, which exerts because of the strong irritant, formaldehyde on the mucous membranes, is very unpleasant, it is an important advantage According to the present invention, when polyisocyanates are used as curing agents, no odor nuisance occurs when the foam is cured.

The latex foams produced according to the method of the present invention can be used for numerous areas of application, * e.g. for the production of pillows, mattresses, upholstered furniture,

Corsetry, carpet coatings, insulating materials.

In addition, however, are due to the range of variation both in the case of the aqueous dispersions which can be used according to the invention the reactive polymers as well as the polyisocyanates used for crosslinking, the areas of application very diverse.

The process is particularly suitable, for example, for production of films, coatings, coatings or bonds that can be microporous, as well as for the production of microporous Plastics different from foams. |

The planar structures, coatings and impregnations produced according to the type of crosslinking listed above are distinguished characterized by some excellent properties. So show them good resistance to wet, hot wash and hydrolysis. Furthermore, it is resistant to solvents and plasticizers outstanding. The high elasticity of the polymers crosslinked according to the invention should also be emphasized.

Le A 12 844 - - 13 - ■ ". ■.

10 9 8 4 2/1795

20143öS

Although it is not necessary to practice the present invention, vulcanizing agents,
Accelerators, zinc oxide, antioxidants, gelling agents, plasticizers, mineral fillers, carbon blacks and other common ones
Rubber latex auxiliary products are used as components of the mixture.

Le A 12 844 - ¹ 4

109842/1795

2074385

is-

The invention is illustrated by the following examples, in which all parts represent parts by weight. The amounts of the ingredients in the latices are based on each other 100 parts of polymer based.

Latex A

The latex was made from 45.0 parts by weight of butadiene by the batch process
18.0 parts by weight styrene

29.5 parts by weight of acrylonitrile and

7.5 parts by weight of methacrylamide. ™

using 4.5 i ° (relative to monomers) prepared potassium oleate as an emulsifier, which was obtained by a complete polymerization of solid 35% aqueous dispersion which is concentrated by subsequent evaporation of water to about 46.5 i "solid on became. The latex has a pH of 8.3 and a Brookfield viscosity of 730 cps.

Latex B

The latex B was made according to the batch process

60.0 parts by weight of butadiene j

34.0 parts by weight of styrene and _;

6.0 parts by weight of 2-hydroxypropyl methacrylate using 2 56 (based on monomers used) sodium lauryl sulfate as an emulsifier and 0.3 ^c ß> tertiärem'dodecylmercaptan as a regulator, a solid 50 # aqueous dispersion was obtained by polymerization which was concentrated ^{to approx. 57 0} A solid by subsequent evaporation of water. The pH was 6.1 and the Brookfleid viscosity was 1000 cps.

Le A12 844 . - 15 -

10984 2/179 5

20U385

Latex C

The latex C was prepared analogously to polymer C, but as monomers
60.0 parts by weight of butadiene
34.0 parts by weight styrene

3.0 parts by weight of methacrylic acid and 3.0 parts by weight maleic acid

were used. After concentration, this aqueous dispersion had a concentration of 57 ° solid. | l pH value: 6.5; Brookfield viscosity: 580 cps.

Latex D

The latex D was out
60.0 parts by weight of butadiene
30.0 parts by weight of styrene and
10.0 parts by weight of methacrylic acid

using 2.0 % (based on monomers used) sodium lauryl sulphate as emulsifier and 0.3% tertiary dodecyl mercaptan as regulator, 10% of the emulsifier and 15 $ of the monomer mixture were initially charged and, after the reaction had started, the remaining 85% of the monomers fc and 90 io of the emulsifier were fed evenly to the reaction vessel within 8 hours. An aqueous dispersion with 55 ° solid was obtained by polymerisation. The pH was 6.0 and the Brookfield viscosity was 153 cps.

Latex E *,

The latex E was out

90.0 parts by weight of chloroprene and

10.0 parts by weight of methacrylic acid amide-N-methylol-methyl ether using 5 # (based on monomers used)

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1 0 9 8 A 2/17 9 5 Bad original

.20143B5 '

Na salt of a mixture of dihydro- and dehydroametic acid as emulsifier and 0.2 % n-dodecyl mercaptan as regulator at pH 12 Ms to a conversion of 10 %. The residual monomer was removed by degassing, and the latex was concentrated by creaming with alginate. The latex obtained in this way had about 50 % solids, a pH of 11.0 and a Brookfield viscosity of 123 cps,

Polyisocyanate 1

Polyisocyanate 1 is a liquid polyisocyanate which contains about 95 i ° 4, i'-diisocyanateO'-diphenylmethane and which contains small amounts of 2,4'-isomers and higher condensates ^

is contaminated. ^

It was obtained by anilift formaldehyde condensation and subsequent phosgenation of the polyphenylpolymethylene polyamine obtain, ·

Polyisocyanate 2

Polyisocyanate 2 is 1,6-diisocyanatohexane.

Polyisocyanate 3 ''

Polyisocyanate 3 is a liquid polyisocyanate which is obtained by reacting 3.0 mol of 1,6-diisoeyanatohexane with 1.0 mol of water. The polyisocyanate has a molecular weight of 522 and-containing ca, 24 mol io free isocyanates g This polyisocyanate is manufactured according to the teachings of the German patent 1,101,394.

Polyisocyanate 4

Polyisocyanate 4 is 3 "isocyanatomethyl-3» 5 »5-trimethylcyclohexyl isocyanate,

PoT.yisocyanate p

Polyisocyanate 5 is an organic polyisocyanate which is obtained by reacting 3 moles of 2,4-diisacyanato ~ toluene with 1 mole of trimethylolpropane, and which contains approx. 18 moles of free isocyanate,

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109842/1795

20U3H5 AS

Polyisocyanate 6

Polyisocyanate 6 is a liquid containing carbodiimide groups 4,4'-diisocyanatodiphenylmethane and contains small amounts of higher molecular weight fractions. It is made according to the teaching of German patent specification 1 092 007.

Polyisocyanate 7

Polyisocyanate 7 is a blocked polyisocyanate that was obtained by reacting polyisocyanate 2 with 2 moles of potassium bisulfite. The product has a molecular weight of 466 and contains about 20 mol % of W NCO groups blocked by potassium bisulfite.

Polyisocyanate 8

Polyisocyanate 8 is a capped polyisocyanate obtained by reacting polyisocyanate 5 with 3 moles of phenol. The product has a molecular weight of 938 and contains approx. 14 mol $ NCO groups blocked by phenol.

Example 1:

4 samples of 215 parts each of latex A were mixed with 6 parts each of the polyisocyanates 1, 2, 3, 4. The finished mixtures were poured onto clay plates and dried at room temperature (samples 2, 3, 4, 5). The films obtained were then heated ^{at 80 ° C. for 15 minutes.} As a comparative sample, a film without the addition of polyisocyanates was produced in the same way (sample 1).

Example 2;

4 samples of 176 parts each of Latex B were made with 6 parts each of polyisocyanates 1, 2, 3, 4 mixed (samples 7,8,9,10).

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As in Example 1, films were produced therefrom and ^{heated at 80 °} C. for 15 minutes. A film which was produced without the addition of polyisocyanate (sample 6) was used as a comparative sample.

Example 3:

4 samples of 176 parts each of Latex C were made with 6 parts each of the polyisocyanates 1, 2, 3, 4 mixed (samples 12, 13, 14, 15) As in Example 1, films were produced therefrom and heated at 80 ° C. for 15 minutes. Comparative sample (sample 11):

Film without added polyisocyanate.

Example 4; '

4 samples each of 200 parts of latex E were mixed with 6 parts each of the polyisocyanates 1, 2, 3, 4 (samples 17, 18, 19, 20). The films were produced as in Example 1, the heating time was 15 minutes at 80 ⁰ C. Comparative sample (sample 16): film without added polyisocyanate.

The tensile strengths obtained from the films of the latices A, B, C and E in the tensile test according to DIN 53504, standard rod 3 are summarized in Table 1.

Le A 12 844 - 19 -

1098 4 2/1795

20H3Ö5

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Le A12 844

- 20 -

10 9842/1795

20H38S

Like a comparison with the values of the films without the addition of polyisocyanate (samples "1,6,11,16).,. shows, the film strengths have been increased by the addition of Polyisocyanates greatly improved. The sharp increase in tensile strength shows the reaction of the polyisocyanate with. the polymer. For a given latex, the values obtained depend on the type of polyisocyanate.

Example 5ϊ

9 samples of 176 parts each of latex C were the following substances added: ·. · |

100.0 parts by weight of chalk '

3.0 parts by weight of sodium lauryl sulfate

1.0 part by weight of nonylphenol with approx. 20 ethylene oxide

0.25 weight part carboxymethyl cellulose

The components of the mixture were stirred with a stirrer. Of the 9 latex mixtures obtained, 8 were with 6 parts of each of the polyisocyanates 1,2,3,4,5,6,7,8 are added (samples A, B, C, D, E, F, G, H) and with a whisk foamed. The polyisocyanates 1,2,3,4 »6», which are liquid at room temperature, were added directly to the mixture, the polyisocyanates 5 and 8 as a 30% solution in | Ethyl acetate and polyisocyanate 7 as 50% aqueous Dispersion.

The latex foams obtained were then painted to a height of 5 mm on a thin cotton fabric and cured at 150 ^° C. in a hot air oven. The foams obtained were highly elastic, white, non-sticky, fine-pored and smooth. Surface. Their physical data are listed in Table 2 .

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109842/1795

20U3B5

Mixture 9 was mixed with 12 parts of a 50% aqueous solution of a partially etherified melamine-formaldehyde resin and a foam was produced therefrom by foaming with a whisk. As the foam was 5 mm high spread on a cotton fabric and cured at 15O ⁰ C in a hot air oven at the mixes 1-8. The foam obtained was elastic and white, but had a cracked surface. Its physical data are also shown in Table 2 (sample i).

Le A 12 844 - 22 -

109842/1795

CM Φ Φ

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! # 0642/1795

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The foam samples made according to the invention with polyisocyanates have been crosslinked (samples A-H), have better separation strengths and significantly better boil-wash resistances on than the foam sample I, the one with melamine-formaldehyde resin has been produced as a crosslinker. The foam sample that has been crosslinked with melamine-formaldehyde resin (sample i), dissolved in 7.5% mild detergent solution during cooking from the tissue after a short time.

Example 6:

6 samples of 176 parts each of Latex D were tested with the following

Substances added:

3.0 parts by weight of sodium lauryl sulfate

1.0 part by weight of nonylphenol with approx. 20 ethylene oxide

0.25 part by weight of carboxymethyl cellulose.

Now 2 mixtures each with 100, 150 and 200 parts of chalk were mixed. 3 of the mixes with a chalk content 6 parts of polyisocyanate 1 and 0.1 part of triethylenediamine were then added to 100, 150 and 200 parts (Samples K, L, M), the remaining 3 mixtures (samples N, 0, P) with 12 parts of a 50% aqueous solution of a partially etherified melamine-formaldehyde resin. The foam production and curing took place as in Example 5. The composition of the mixture and the physical data of the foams are summarized in Table 3.

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Tabel

sample Latex D chalk Polyiso-
cyanate 1 Melamine-
Formaldehyde-
resin density
cm Trennfe
kg
dry sturdiness
•/cm
n.30 ^f
Cooking wet K 176 100 6.0 _ 0.269 4.2 1.3 L. 176 150 6.0 - 0.305 3.6 0.8 M. 176 200 • 6.0 ■■ - 0.359 2.9 0.4 N 176 100 - 12.0 0.243 4.0 foam 0 176 150 - 12.0 0.279 3.7 from the P. 176. 200 - 12.0 0.305 2.8 Tissue ■ j ^ solved ** "{

cn

? 0H38ft

While the foam samples K-M, which have been crosslinked with polyisocyanates, even have a filling level of 200 After 30 minutes of cooking in a 7.5% mild detergent solution, chalk divides usable separation strengths when wet showed, the foam samples that have been cross-linked with melamine-formaldehyde resin are already loosening from the tissue after a short cooking time.

Instead of the polymers containing methacrylic acid (Example 6) or methacrylic acid and maleic acid (Example 5) can also those with acrylic acid, fumaric acid, itaconic acid, acrylamide, methacrylic acid-2-hydroxypropyl ester, Methacrylic acid amide-N-methylol methyl ether and mixtures thereof occur with essentially equivalent results.

The tests used in the examples are as follows described:

Separation Strength:

An 80 20 χ 5 mm piece of foam with a thin cotton fabric as the carrier material, is attached to the foam side glued with a wooden board of the same size (80x20x 5 mm) that on both sides of the glued sample the foam and the wooden board each protrude 40 mm.

Now the foam is cut approx. 2.5 mm deep along the adhesive edge of the wooden board (cut length is equal to width is equal to 20 mm). The finished sample is clamped in the jaws of a tearing machine and torn. The value obtained gives the separation strength (dry). To determine the separation strength (wet), the sample is boiled for 30 minutes in 7.5% mild detergent solution, removed, cooled to room temperature and torn when wet.
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The separation strength in lig / cm "is: force j kg]

2, D ei

Compression module:

2 Round yon Bphaumpröben 2'5. mm diameter and 5 mm height, with a thin Baütpw'pilgeVetje as carrier material j are placed with the sides of the hemisphere together and the resulting 10 mm high cylinder in a Roelig-Délifurigs machine to 25 / ° (ie Ms 7.5 miii ") and to 5D fo (ie up to 5 mm) compressed.
The compression modulus in kg / cm is:

total Kpinpressipnskraft, (kg.). ,. \.

■ - '■ · - · ■ - ■ - ·. ■ - ·. -v4,9 about ² ^ - ■ · "> ■■■ - ■ ■ · .- ■■ -V- · ■ - ■■■ .-: ^·;... · · ■

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Claims (13)

Patent claims: 'τ) Process for the manufacture of plastics, including Foams can be polymerized by reacting copolymers containing reactive hydrogen atoms Monomers with polyisocyanates, optionally in the presence of auxiliaries, characterized in that Copolymers of polymerizable monomers containing reactive hydrogen atoms in aqueous dispersion be used. 2. The method according to claim 1, characterized in that the copolymers of such at least two polymerizable olefinically unsaturated monomers, wherein 0.1 to 50 wt -io these monomers consist of at least one monomer. Comprising at least one reaction with isocyanates substituent group having at least one having active hydrogen atom can be used. 3. The method according to claim 1 and 2, characterized in that such as copolymers with -COOH-, -CO-NH ₂ -, NH ₂ -, -CO-NH-CH ₂ -OH-, -CO-NH-CH ₂ -OR- (R = Cj-C ^ -alkyl), -OH- Groupings are used. 4. The method according to claim 1 to 3 t, characterized in that a copolymer consisting of 30 to 80 wt .-% butadiene, 60 to 10 wt .-% styrene and 15 to 1% by weight of a -COOH group-containing monomer is used. 5. The method according to claim 1 to 3 »characterized in that that as a copolymer such, consisting of 30 to 80 wt. 56 butadiene, 60 to 10 wt. # Acrylonitrile, 15 to 1% by weight of a -COOH-group-containing monomer is used will. Le A 12 844 - 28 - 109842/17 6. The method according to claim 1 to 3 »characterized in that that as a copolymer such with 50 to 80 wt .- ^ Butadiene, 60 to 10 wt. $ Styrene, 15 to 1 wt. $ One Monomers containing OH groups is used. 7. The method according to claim 1 to 3, characterized in that that as a copolymer such a consisting of 99 to 85 wt .-% chloroprene and 1 to 15 wt .-% of an N-methylol ether group containing monomers is used. 8. The method according to claim 1 to 3, characterized in that that a copolymer consisting of ". |" 30-80 wt .- $ butadiene ^l 60-0 "styrene
60 -0.5 "(meth) acrylic acid ester 60 - Q" acrylonitrile and 1-15 "of a monomer containing -COOH groups, is used. 9. The method according to claim 1 to 3, characterized in that such a copolymer consisting of 30-80 wt. Fo butadiene 60-0 »styrene 60-0.5 "(meth) acrylic acid ester 60 - 0 »Acrylonitrile and '' 1 -. 15 "of a -CONH ₂ ^{-017 111} PP ⁶¹¹ having monomers is used. 10. The method according to claim 1 to 3, characterized in that that a copolymer consisting of 30-80 wt .- ^ butadiene "■ -." 60 - O »styrene 60 - 0.5 "(meth) acrylic acid ester * _; 60 - 0" acrylonitrile and · 1-15 "of a monomer containing -OH groups. Is used.. Le A12 844 - 29 - * 109842/1795 20U385 11. The method according to claim 1 to 3, characterized in that the copolymer consists of such a 30-80% by weight of butadiene 60-0 "styrene 60-0" (meth) acrylic acid ester 60-0 "acrylonitrile 0-15 "of a -COOH group and 0.5-15" of an N-methylol ether group Monomers, is used. 12. The method according to claim 1 to 11, characterized in that the polyisocyanates used are those in masked form will. 13. The method according to claim 1 to 12, characterized in that aliphatic and cycloaliphatic polyisocyanates can be used with low vapor pressure. Le A 12 844 - 30 - 109842/1795