DE2232711A1 - AQUATIC EMULSION AND THIS UNDERLYING COPOLYMERES - Google Patents

Description

ALFRfU ÜOEPPGNER

DR. JUS. ϋ- · _: »ΐ5 Ci- :.

623 FRANKFURT AM ijlAIM-HÖCHST

AWlOHSiBASitS ». j

i.

Our no. 17 976

Stauffer Chemical Company Westport, Conn., V.St.A.

Aqueous emulsion and copolymers on which it is based s

Copolymers of halogen-containing äthylenisoh unsaturated monomers such as vinyl halides are often in the form of Aqueous latices or emulsions produced in which they can be used as coating agents, pressure-sensitive adhesives, paint bases and for various purposes other uses are suitable. In some cases, especially when using them for the interior of buildings or in uses where they are exposed to high temperatures for a prolonged period of time, it is extremely desirable and advantageous when these vinyl halide copolymers are good fire or flame retardant Have properties so that they instead of more expensive Materials can be used safely.

In previous attempts, fire retardant, film-forming vinyl halide polymer latices various poly-

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mere mixtures such as copolymer latices of vinyl halides and the alkyl acrylate esters, copolymer latices of vinyl halides and vinylidene chloride and polyvinyl halide latices with a Content of specially added phosphate ester plasticizers. However, none of the above attempts have been perfect obtained satisfactory results, since the end products obtained in many cases do not have sufficient flame retardancy have, are excessively soft, have no mechanical stability, are easily degraded by UV rays or a are exposed to gradual loss of the extra added phosphate plasticizers.

The main object of the present invention is to provide of new fire retardant vinyl halide copolymer latices which have been found for a variety of uses Coating, binding and in the manufacture of laminates are suitable and characterized by the essentially complete absence of the various adverse properties formerly associated with associated with such a product. Another object of the invention is to provide a new one Class of copolymers in the form of aqueous emulsions or latices, which are particularly useful as additives for the manufacture of fire-retardant polymer mixtures, which are in the form of aqueous solutions, suspensions or, preferably, emulsions are present.

The invention is broadly based on the discovery that normally flammable polymers, in particular Polymers in the form of aqueous solutions, suspensions or preferably emulsions by incorporating new additives, the copolymers of (1) one or more halogen-containing vinyl monomers and (2) one or more phosphorus-containing Vinyl monomers as described below, ent-

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keep, fire retardant can be made, these copolymers be in the form of particles in an aqueous emulsion or a latex. In particular, it was found that through the use of aqueous emulsions of copolymers of one or more halogen-containing vinyl monomers and one or more bis (hydrocarbyl) vinyl phosphonates give the polymers modified in this way a high. Degree of fire retardancy is conferred without seriously impairing any of its essential physical properties. About that In addition, it is in fact surprising and advantageous that the polymer mixtures obtained by the process according to the invention, in particular the mixtures which are in the form of an aqueous emulsion or a latex system have a high Have a degree of compatibility since, as anyone skilled in the art is aware, physical mixtures of two or more polymers almost always have a poor tolerance.

The new copolymers that are suitable for use as fire retardant additives for normally flammable polymer substrates Suitable in the process according to the invention consist of aqueous emulsions or latices of copolymers

(l) one or more halogen-containing alpha-, beta-ethylenically unsaturated monomers, i.e. vinyl monomers such as vinyl halides, e.g., vinyl chloride, halogenated C-, - C, ρ - alkyl acrylates and methacrylates such as e.g. Methyl-alpha-chloroacrylate, vinylidene halides such as e.g. Vinylidene chloride, halogen-substituted nitriles and ethylenically unsaturated carboxylic acids such as alpha-chloroacrylonitrile and chlorinated styrenes such as alpha-chlorostyrene and 2,4-dichlorostyrene and

(2) one or more bis (hydrocarbyl) vinyl phosphonates with

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Structural formula

X O ι ti

² ^ OR - '

in which X is a hydrogen atom, a halogen atom, a cyano or aryl radical such as a phenyl radical, a C _n - C - “- alkyl radical

O 1 18

S / OR,

l which denotes the radical - P ^ qr- ', in which R and R ¹ denote hydrocarbyl and substituted hydrocarbyl radicals which consist essentially of hydrogen atoms and carbon atoms and contain up to about 18 carbon atoms, where R and R ^{1 are} identical, different or bonded to one another can, ie R and R ¹ can form a single radical.

The term "hydrocarbyl radicals" and "substituted hydrocarbyl radicals ¹ · refers here to the radicals which are obtained by removing a hydrogen atom from a hydrocarbon radical or a substituted hydrocarbon radical, which can be an aliphatic or aromatic radical. These hydrocarbyl radicals can be obtained by not interfering radicals can be substituted by any radical which does not interfere with the polymerization of the bis (hydrocarbyl) vinylphosphonate, such as chlorine, bromine or fluorine atoms, nitro, hydroxyl, sulfonate, ethoxy, methoxy, nitrile -, ether, ester and keto radicals and the like.

Examples of the aliphatic represented by R and R ' Residues are alkyl radicals, such as methyl, ethyl and hexenyl

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radicals and all corresponding isomers, cycloalkyl radicals such as Cyclopropyl, cyclohexyl and cyclohexenyl groups and the like, while typical aryl groups represented by R and R · for example phenyl, benzyl, phenethyl, 'tolyl and naphthyl radicals and the like are.

Examples of the bis (hydrocarbyl) vinyl phosphonates described above are*

Bis (beta-chloroethyl) vinyl phosphonate,

Bis (beta-chloropropyl) vinyl phosphonate,

Bis (beta-chloroethyl) l-methyl vinyl phosphonate, bis (beta-chloroethyl) l-cyanovinyl phosphonate, Bis (beta-chloroethyl) 1-chlorovinylphosphonate, Bis (beta-chloroethyl) l-phenyl vinyl phosphonate, dimethyl vinyl phosphonate,

Diethyl vinylphosphonate,

Bis (omega-chlorobutyl) vinyl phosphonate,

Di-n-butyl vinyl phosphonate,

Di-isobutyl vinyl phosphonate,

Bis (2-chloroisopropyl) l-methyl vinyl phosphonate, Diphenyl vinyl phosphonate and

Bis (2,3-dibromopropyl) vinyl phosphonate.

From the group of ΐϊβ (hydrocarbyl) vinylphosphonate monomers listed above is preferably the bis (beta-chloroethyl) vinylphosphonate for the preparation of the new aqueous emulsion copolymers of the present invention because this monomer is a commercially available material and cheaper than all of them other bis (hydrocarbyl) vinyl phosphonates. For the same The reason is vinyl chloride as a halogen-containing ethylenically unsaturated monomer in these aqueous emulsion copolymers

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preferably used. At this point it should be noted that the print "Copolymer" in the present disclosure for all Polymers is used, which are derived from two, three or more individual types of monomers.

In addition to the bis (hydrocarbyl) vinyl phosphonates described above Can also use aqueous emulsion copolymers that can be used as flame retardant additives for normally flammable Polymer substrates are suitable, prepared by (l) mono (alkyl) acid vinyl phosphonates such as Mono (ethyl) hydrogen vinyl phosphonate, mono (butyl) hydrogen vinyl phosphonate, Mono (octyl) hydrogen vinyl phosphonate, mono (betachloroethyl) hydrogen vinyl phosphonate, Mono (omega-chloroethyl) -hydrogenvinylphosphonatej (2) Mono (cycloalkyl) and mono (acrylic) hydrogen vinyl phosphonates such as mono (cyclohexyl) hydrogen vinyl phosphonate, Mono (phenyl) hydrogen vinyl phosphonate, mono- (benzyl) hydrogen vinyl phosphonate; (3) Bis (cycloalkyl) and bis (aryl) vinyl phosphonates such as bis (cyclohexyl) vinyl phosphonate and bis (benzyl) vinyl phosphonates and (4) bis (alkyl) -, Bis (cycloalkyl) and bis (aryl) allyl phosphonates such as bis (beta-chloroethyl) allyl phosphonate, Bis (cyclohexyl) allylphosphonate and bis (benzyl) allylphosphonate and mixtures of two or several of the phosphonate monomers listed above are used.

The emulsion or latex copolymers according to the invention can optionally contain one or more comonomers such as alpha-olefins, for example propylene, vinyl esters of carboxylic acids such as vinyl acetate, ethylenically unsaturated monocarboxylic acids such as acrylic and methacrylic acids, ethylenically unsaturated dicarboxylic acids, their anhydrides and their C 1 -C ₂₀ mono - and dialkyl esters such as fumar

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acid, amides of ethylenically unsaturated carboxylic acids such as acrylamide and N-methylol methacrylamide, vinyl aryl compounds such as styrene and alpha-methylstyrene, nitriles of ethylenically unsaturated carboxylic acids such as acrylonitrile and methacrylonitrile, C _{1 -C 20} -alkyl vinyl ethers such as methyl vinyl ether, dienes such as isoprene and butadiene of acrylic and methacrylic acids such as glycidyl erylate and glycidyl methacrylate and the like. The comonomers used are preferably 1-methylolacrylamide and N-methylol methacrylamide which provide the copolymer obtained with crosslinking points.

The above-described copolymers can be produced by emulsion polymerization processes produced by free radicals are initiated and which are known to the person skilled in the art. In this process, the various monomers and catalysts with one or more surfactants Emulsifiers emulsified in water, after which the polymerization reaction is initiated. For use in the manufacture Water-soluble, free radical-forming catalysts suitable for the copolymer latices according to the invention are, for example Sodium, potassium or ammonium persulfate and hydrogen peroxide, or you can use a redox system such as for example a mixture of a persulfate and an alkali bisulfit, Use thiosulphate or hydrosulphite. These catalysts should be in a concentration of about 0.05 his 5 wt .- ^, based on the total monomer charge, present be. As an emulsifier or surfactant, can one or more anionic, cationic or non-ionic emulsifiers such as alkyl carboxylic acid salts, alkyl sulfate, sulfonate, phosphate or sulfosuccinate salts, alkylaryl ether alcohols and alkylaryl polyether sulfate salts are used will. The selected emulsifier or emulsifiers

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are said to be in effective concentrations of about 0.03 "to 6.0 % By weight, based on the total monomer charge, is present be. Furthermore, a protective colloid such as polyvinyl alcohol, polyvinylpyrrolidone, methyl cellulose or Gelatin at an effective concentration of about 0.03 to 6.0 wt .- ^, based on the total monomer charge, in the recipe must be available. The protective colloid can also be incorporated into the copolymer latex after it has been produced. When this happens, the protective colloid should be in a concentration of about 0.03 to 6.0 wt .- ^, based on the total resin solids. In any case, the presence of the protective colloid serves to increase the stability the emulsion.

The actual polymerization reaction becomes ordinary depending on the particular monomer, catalysts, surfactants and polymerizer, which are used, about 1 to 24 hours at one temperature carried out from about 0 to 100 ° C. The latices obtained by this polymerization process usually have a resin solids content of about 5 to 70 wt .- ^, the Particles about 0.03 to 3 »0 microns in diameter.

With regard to the proportions, the aqueous emulsion or latex copolymer particles can contain about 1 to 90 wt .- ^ of one or more of the bis (hydrocarbyl) vinylphosphonates described above, with the remainder of the copolymer one or more halogen-containing ethylenically unsaturated monomers described above and 0 to contains about 30 weight percent of one or more of the optional comonomers described above. For use as flame retardant additives for normally flammable polymer substrates

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te are obtained the "best results when the copolymer being from about 40 to 70 f" of one or more bis (hydrocarbyl) vinyl phosphonates, and preferably bis (beta-chloroethyl) vinylphosphonate, included.

At this point it should be noted that the concentration of bis (hydrooarbyl) vinyl phosphonate in the copolymers of the invention depends largely on their subsequent use. The copolymers containing about 40 % or more of the vinyl phosphonate are soft materials that are readily capable of forming films at room temperature conditions. Accordingly, such copolymers can be used as such in the preparation of fire retardant coatings, or they can be used as fire retardant additives which are readily mixed with latices or emulsions of normally flammable polymer substrates which are themselves film forming materials. Conversely, when the aqueous emulsion copolymers of the invention contain less than about 40 wt .- ^ vinyl phosphonate, they are typically hard, non-film-forming materials particularly suitable for blending with non-film-forming, flammable polymer substrates. These non-film-forming copolymers can also optionally be mixed with normally flammable film-forming polymer substrates, especially if they have previously been spray-dried and thereby converted into a dry, finely divided form «

With regard to the quantitative ratios listed above for the aqueous emulsion or latex copolymers according to the invention it has been found that it becomes increasingly difficult to achieve good polymerization conversion rates when one tries to measure the amount of bis (hydrocarbyl) vinylphosphonate in the copolymer to a concentration of substantially more than

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Increase about 60 qew.-fo. On the other hand, the use of these copolymer emulsions as flame retardant additives for normally flammable polymer substrates becomes less and less effective if they contain substantially less than about 5% by weight of one or more bis (hydrocarbyl) vinyl phosphonates, since the resulting mixture must then contain a high concentration of the copolymer so that flame retardancy is achieved.

The use of such high concentrations of these copolymer additives can in turn degrade the inherent physical properties of the polymer substrates modified in this way.

Special aqueous emulsion copolymer mixtures with which particularly good results when used as additives for the production of fire-retardant polymer blends are j

(1) a copolymer of 40 wt .- # vinyl chloride and 60 Wt .- $ bis (beta-chloroethyl) vinyl phosphonate,

(2) a copolymer containing 60 wt-96 Bis (beta-chloroethyl) vinyl phosphonate, 37 weight - containing <jt> vinyl chloride and 3 wt .- ^ N-methylolacrylamide, and the like.

(3) a copolymer containing 60 wt .- ^ bis (beta-chloroethyl) vinyl phosphonate and 40% by weight vinyl bromide.

In the present invention, it is important between the suspension polymerization process and the Emulsionspolymerisationsver drive to distinguish. Suspension polymerization is a Polymerization process in which one or more monomers are dispersed in a suspension medium in which both the

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Monomers as well as the polymer obtained is not soluble. In general, water is used for this purpose, and thereafter an monomer-soluble polymerization initiator is introduced. The polymerization takes place in the polymerization initiator containing Uonomerphase instead. The use of the suspension medium serves to distribute the heat of reaction, see above that the polymerization reaction is easier to control. The suspension polymerization is generally carried out by dispersion of the monomer in the suspending medium, either by continuously stirring or using a suspending agent, or both happen. Various suspending agents are known in the art, for example gelatin, hydroxymethyl cellulose, Hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, Talc, clay, polyvinyl alcohol and the like.

Emulsion polymerization, on the other hand, is a process in which one or more monomers are in the form of droplets in a continuous phase are emulsified for both the emulsified Monomers as well as for the polymer obtained should be inert. In general, water is used as the continuous phase used. The emulsification of the monomers is facilitated by the use of one or more emulsifiers that reduce the tension decrease between the dispersed and the continuous phase. Typical emulsifiers are ordinary soaps, salts of long-chain carboxylic and sulfonic acids, alkylated aromatic

Sulfonic acids and salts of long chain amines.

A water soluble initiator is used and the polymer chains are believed to be continuous from the run out of aqueous phase and become in the dispersed Mqnomer-Polymerphase continue, the polymer product being obtained in a finely divided state, which in the continuous aqueous

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Medium remains emulsified. An important difference between emulsion polymerization and suspension polymerization is therefore that the monomer in the former is either is dispersed in droplets that are stabilized by an adsorbed layer of soap molecules, or in the Soap micelle present in the aqueous soap solution is solubilized. This will be done without any difficulty stable polymer emulsions obtained, while the polymer particles in the suspension polymerization of relatively larger Are mass and separate more easily from the suspension.

In all cases it has been shown that with the new aqueous emulsion or latex copolymers according to the invention Mixtures with normally flammable polymer substrates are obtained, which are distinguished by their excellent flame retardancy distinguish. According to the invention, the term "fire-retardant" relates or "flame retardant" to the special property of a material that gives it a degree of strength Gives ignition and burning. A fire retardant or flame retardant Mixture is a mixture that has low flammability and flame spread. This attribute can be tested with all standard flame retardancy tests, e.g. the ASTM test D 635 »can be determined.

As stated above, those according to the invention are suitable aqueous emulsion or latex copolymers especially for blending with normally flammable polymers, the in the form of aqueous systems, such as solutions, suspensions, or preferably emulsions. The obtained aqueous Mixtures can then be used for all purposes known to those skilled in the art of coating, gluing, laminate production and for Impregnation can be used. The aqueous mixtures can be used on all types of substrates that have fire-retardant properties wants to lend, applied and / or from these -

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be sorbed. They can therefore be used as coating agents, impregnating agents, Fillers, laminates and adhesives for substrates such as wood, paper, metals, textiles based on fibers or fiber blends, synthetic polymer films such as those based on polyolefins, regenerated cellulose, i.e. cellophane, polyvinyl chloride, polyester and the like, leather, natural or synthetic rubber, fiber board and synthetic plastics, prepared by addition or condensation polymerization processes can be used. Furthermore can the copolymers according to the invention as fire-retardant additives in spinning baths or liquids, from which rayon and acrylic fibers spun, can be used.

Any polymer substrate can be used with the bis (hydrocarbyl) vinyl phosphonate copolymer additives described above be mixed to make fire retardant mixtures. Such polymer substrates are for example!

(l) - Polymers of vinyl chloride such as polyvinyl chloride and the random and graft polymers of vinyl chloride with a minor amount of one or more of those described above Vinyl monomers, optionally as comonomers for the preparation of the aqueous emulsion copolymers according to the invention can be used;

(2) Polymers of the 0, -Cg-alkyl acrylates and methacrylates including their homopolymers and copolymers with one another and with a small amount of comonomers such as the alpha-olefins, e.g. ethylene and propylene, the vinyl esters of carboxylic acids, e.g. vinyl acetate, ethylenically unsaturated monocarboxylic acids, e.g. acrylic and methacrylic acids, ethylenically unsaturated di-

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carboxylic acid, its anhydrides and C, _{-C 2o} -hono- and dialkyl esters, e.g. maleic acid, maleic anhydride, diethyl maleate, and acid monobutyl maleate, vinylidene halides, e.g. vinylidene chloride, Cj-CgQ-alkyl vinyl ethers, e.g. ethyl vinyl ethers, amides of ethylenically unsaturated monocarboxylic acids, e.g. Vinylary! Compounds, for example alpha-methylstyrene and styrene and nitriles of alpha-, beta-ethylenically unsaturated carboxylic acids, for example acrylonitrile and methacrylonitrile;

(5) Polymers of nitriles of ethylenically unsaturated Acids such as polymethacrylonitrile, polyacrylonitrile and the copolymers of methacrylonitrile and acrylonitrile with a low Amount of one or more vinyl monomers such as the lower ones Alkyl acrylates and methacrylates, styrene and alpha-methyl styrene |

(4) aoryl nitrile butadiene styrene resins, usually "ABS" called, which generally consist of a mixture of a styrene-acrylonitrile copolymer in a ratio of 60 to 80 to 40 to 20 with about 10 to 40 weight percent of an acrylonitrile-butadiene copolymer in a ratio of 5 to 40 t 95 to 60 or a mixture of a styrene-acrylonitrile copolymer in a ratio of 60 to 80:40 to 20 with about 10 to 40% by weight of a graft polymer of this Copolymers based on polybutadiene;

(5) Poly (alpha-olefins) such as polypropylene and polyethylene and copolymers of one or more alpha olefins such as ethylene and propylene with a small amount of one or more ethylenically unsaturated monomers such as 4-methylpentene- (l), butene- (l), Norbornene and their derivatives, cyclopentadiene, cyclopentene, cyclobutene, vinyl acetate, the C, -C-. "-Alkyl acrylate and methacrylate esters as well as mixtures of homo- and copolymers of alpha-olefins with other types of thermoplastic polymers;

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(6) Polymers of styrene - such as polystyrene, poly (alphamethylstyrene) and poly (tertiary butyl styrene) and copolymers of styrene, alpha methyl styrene or tertiary butyl styrene with a small amount or more ethylenically unsaturated comonomers such as nitriles of ethylenically unsaturated carboxylic acids such as acrylonitrile and methacrylonitrile, C-j-C-jp-alkyl esters of acrylic and methacrylic acids such as methyl methacrylate and 2-ethylhexyl acrylate and graft polymers of styrene, tert-butyl styrene or alpha-methylstyrene with polybutadiene and other hydrocarbon elastomers;

(7) Cellulose resins such as cellulose esters and mixed esters such as cellulose nitrate, cellulose acetate butyrate, Cellulose acetate propionate and cellulose ethers such as ethyl cellulose;

(θ) Polyamide resins, i.e. resins produced by the condensation of diamines or polyamines with di- or polybasic Acids or by polymerization of lactams or amino acids. Typical polyamides are, for example Nylon 4 »which is made from pyrrolidone, nylon 6 which is obtained by polycondensation of caprolactam, Nylon 66 obtained by condensation of hexamethylenediamine with adipic acid; nylon 610 obtained by condensation obtained from hexamethylenediamine with sebacic acid, nylon 7 "which is a polymer of ethylaminoheptanoate, nylon 9" that is made from 9-aminononanoic acid and nylon 11, which is made from 11-aminoundecanoic acid;

(9) Polyester resins, i.e. the resins produced by the condensation of saturated or unsaturated dibasic acids

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such as terephthalic acid, maleic acid, fumaric acid, isophthalic acid, adipic acid and azelaic acid with dihydric alcohols such as Ethylene glycol, propylene glycol, diethylene glycol and dipropylene glycol getting produced. When the resin is made from an unsaturated acid, it often becomes a polymerizable one Monomers such as styrene, vinyl toluene, diallyl phthalate, methyl methacrylate, Chlorostyrene, alpha-methylstyrene, diviny! Benzene or TrialIyIcyanurat introduced into the mixture;

(10) polyurethane resins, ie resins which are produced by reacting an M or polyfunctional hydroxyl group-containing compound such as a polyether or polyester with a bi- or polyisocyanate such as toluene diisocyanate or diphenylmethane-4, -4 ¹ -diisocyanate;

(11) Polycarbonate resins, i.e. resins made by reaction a difunctional alcohol or phenol such as bis-phenol A obtained with phosgene or an alkyl or aryl carbonate;

(12) polyacetal resins, ie resins obtained by anionic polymerization of formaldehyde to form a linear molecule of the -0-CH ₂ -O-CH ₂ -O-CH ₂ - type;

(15) Polyphenylene oxide resins produced by oxidative polymerization of 2,6-dimethylphenol in the presence of a copper-amine complex catalyst getting produced;

(14). Polysulfone resins, ie resins with an SO ₂ bond, which are produced by the reaction of sulfur dioxide with olefins such as 1-butene or, preferably, by the reaction of bis-phenol A with 4,4'-di-

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- 17 chlorodiphenyl sulfone are produced;

(15) the acrylate-styrene-acrylonitrile resins, usually Called "ASA" resins, which consist of copolymers containing a major amount of a Cg-Cg alkyl acrylate ester elastomer that is about 65-95% by weight based on this copolymer, one 70 to 80 t 50 to 20 styrene-acrylonitrile copolymers grafted on is included;

(16) the methacrylate-butadiene-styrene resins, usually "MBS" resins called, which are made from a small amount of a methyl methacrylate-styrene-acrylonitrile terpolymer, that is grafted onto a polybutadiene or a copolymer of butadiene and small amounts of comonomers such as styrene and acrylonitrile and / or is mixed with it, exist;

(17) Polymers of vinyl acetate such as polyvinyl acetate and the random and graft polymers of vinyl chloride with a small amount of one or more vinyl monomers, which, as indicated above, optionally as comonomers for the production of the aqueous emulsion copolymers according to the invention can be used;

(18) Aminoplast resins obtained by polycondensation of Formaldehyde can be produced with a nitrogen-containing compound such as urea or melamine, and

(19) Phenolic resins made by polycondensation of phenols with aldehydes such as formaldehyde, acetaldehyde or furfurylaldehyde getting produced.

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Virtually any normally flammable polymer substrate can be used to make fire retardant polymer blends can be used with the new aqueous emulsion copolymer additives of the invention. These are usually flammable Polymer substrates can be thermoplastic polymers, i.e. polymers which can be plasticized by heat and which regain their original properties after cooling. It can also polymer systems, especially in the form of aqueous Emulsions, are used, the copolymers with one or more crosslinkable comonomers, i.e. monomers that contain two or more contain more functional groups such as N-methylolacrylamide, N-methylol methacrylamide, glycidyl acrylate and glycidyl methacrylate, contain. The copolymers containing one or more of these crosslinkable comonomers can be cured by the application of heat and / or the use of catalysts or are crosslinked and thereby converted into a form in which they are no longer thermoplastic, but rather are heat-curable, i.e. they do not become soft when heated. The aqueous emulsion copolymer additives according to the invention are preferably used mixed with such crosslinkable copolymer systems before the curing or crosslinking process takes place.

The actual mixing of the aqueous emulsion copolymer additives according to the invention with the selected polymer substrate, i.e. with any or any of the polymers described above, can be done by any suitable method, which leads to an intimate mixture of the additive with the bulk of the polymer substrate. So can be an aqueous emulsion or a Latex containing the particles of the copolymer additive can simply be mixed with the polymer substrate, which is preferably in Should be in the form of an aqueous solution, a latex or a suspension. The copolymer additive can also be used with the poly

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mersubstrat be mixed if both in the form of a solid powder.

The mixing can also be carried out in a process in which the polymer containing the substrate itself in the presence of one of the previously polymerized according to the invention aqueous emulsion copolymer additives is polymerized. Of the the aqueous emulsion copolymer additive containing bis (hydrocarbyl) vinyl phosphonate can also be polymerized in a system that the previously polymerized polymer substrate in a in a suitable physical form, e.g. in an aqueous solution, suspension or emulsion.

With regard to the proportions, the amount of the Bis (hydrocarbyl) vinyl phosphonate containing aqueous emulsion or latex copolymers with a normally flammable Polymer substrate can be mixed, primarily by factors such as the particular phosphonate copolymer and the polymer substrate to be mixed, the degree of flame retardancy desired for the mixture, the degree of clarity and hardness and other desirable physical properties as well as other technical and economic considerations, which are apparent to those skilled in the art. However, in order to obtain a mixture that is self-extinguishing, it is im generally desirable to have an effective concentration of the bis (alkyl) vinyl phosphonate containing aqueous emulsion copolymer solids add sufficient to the mixture obtained a content of at least about 0.5 wt .-% phosphorus and at least about 10% by weight of halogen, i.e. chlorine and / or bromine, of the ethylenically unsaturated monomers containing the halogen and also, if possible, from the bis (hydrocarbyl) vinyl

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phosphonate originates to give.

The fire retardant polymer blends of the invention can also contain various optional additives such as plasticizers, e.g. the alkyl esters of phthalic acid, adipic acid and sebacic acid, e.g. dioctyl phthalate and ditridecyl phthalate and aryl phosphate esters such as triphenyl and tricresyl phosphate and the like, lubricants and mold release agents such as stearic acid or its metal salts, waxes based on petroleum, Mineral oils, polyethylene waxes and the like, heat and light stabilizers such as barium, cadmium, calcium, zinc soaps or phenolates, basic lead compounds, organotin compounds such as dialkyltin mercaptides and dialkyltin maleates, Thiolauric anhydride and n-butylstannic acid, epoxidized Oils, alkyl diphenyl phosphites, triaryl phosphites, phenyl salicylates, o-hydroxybenzophenones and benzotriazoles and the like. For a more detailed list of plasticizers, lubricants, stabilizers and other functional additives is on the publication "Polyvinyl Chloride" by H.A. Sarvetnick, edited by Van Nostrand Reinhold Co., New York, Ν.Ϊ., 1969.

The mixtures according to the invention can also contain fillers, pigments, dyes, opacifiers, decorative additives such as reflective Metal flakes and flakes, and other embedded pests such as fiberglass, textile fibers, paper and the like, provided that they do not impair the flame retardancy of these products. Further the mixtures can contain other flame retardants such as antimony compounds, halogenated alkyl phosphates or phosphonates, alkyl acid phosphates, or low concentrations of phosphoric acid contain.

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The new fire retardant compositions according to the invention, the from mixtures of any of the polymer substrates described above and one or more of the invention Fire-retardant aqueous emulsion additives exist, can be used for all purposes known to those skilled in the art Coating, gluing, impregnation, laminate production, bonding and painting where fire retardancy of the final product obtained is desired is. For example, these mixtures can be used as adhesives for runners and carpet backs, as adhesives for glass fibers, as an underlayer for fabric, as a heat-sealable binder for nonwovens, as a floor covering material, Used as paper coating material, as paint bases and as adhesives for the production of layered structures will.

In addition to being used as fire retardant additives for the production of fire retardant mixtures with flammable polymer substrates can use the aqueous emulsion copolymer additives according to the invention as such for all purposes known to those skilled in the art of coating, painting, gluing, the laminate manufacture, used for impregnation and binding. You can therefore use them on all types of substrates you want to impart fire retardant properties, applied and / or absorbed by them. You can therefore use it as a Coating agents, impregnating agents, fillers, laminating agents and adhesives for substrates such as Wood, paper, metals, textiles, based on natural and synthetic fibers or fiber mixtures, synthetic Polymer films such as those based on polyolefins, regenerated cellulose, i.e. cellophane, polyvinyl chloride, polyester and the like, leather, more natural and synthetic

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Rubber, fiber board and synthetic plastics, the can be prepared by addition or condensation polymerization processes.

The following example serves to explain the invention. In the example, all parts are parts by weight, if nothing else is indicated.

example ι

This example illustrates the preparation of a bis (hydrocart> yl) vinyl phosphonate containing aqueous emulsion copolymers and its subsequent use for the production of a fire retardant polymer mixture.

In a 907 g (52 ounces) reaction vessel, 180 g of bis (beta-chloroethyl) vinylphosphonate, hereinafter referred to as ^M bis-beta ", 60 g of a 10% strength by weight aqueous solution of sodium lauryl sulfate, 120 g of a 5% by weight .- $ - aqueous solution of polyvinyl alcohol with a degree of hydrolysis of 80-85 tfo and 80 g of deionized water. The pH of the resulting mixture was brought by adding 3.0 g of a 58 wt .- $ aqueous solution Solution of ammonium hydroxide adjusted to 9, after which 40 g of a 10 % strength by weight solution of ammonium persulfate were added.

The reaction vessel was sealed and then cooled in a condenser for 1 1/2 hours, after which 120 g of vinyl chloride was added. The reaction vessel was closed again and the mixture heated at 50 ° C. for 12 hours while rotating at 20 revolutions per minute. After the reaction had ended, the vessel was cooled until room temperature was reached.

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had been enough. In this way, a virtually $ 100 conversion of the monomers to an aqueous emulsion copolymer containing 60 tons of 40 bis-beta vinyl chloride was obtained. This emulsion had a resin solids content of about 50% by weight with the copolymer particles averaging about 0.06-0.19 microns in diameter. Analysis of these copolymer particles showed that they contained 8.02 % phosphorus and 36.5 % chlorine.

This emulsion was then with an aqueous emulsion containing 46 wt .- ^ polybutyl acrylate polymer particles, whose films are normally flammable, mixed. A number of such mixtures have been prepared in which the concentrations of bis-beta copolymer solids 5 »10, 20 and 30 pbw based on the polybutyl acrylate polymer solids, cheat. Films with a dry thickness of 0.127 0.254 mm (5-10 mils) were made from each of these polymer blends cast, and the flame retardancy of these films was then quantified using their Limiting Oxygen Index (L.O.I.) was calculated using the ASTM D-2863 method also described by Fenimore and Martin in the November 1966 issue of Modern PlaBtics ". Briefly summarized, this method directly relates flame retardancy to a Measurement of the minimum percentage of oxygen in an oxygen-nitrogen mixture at which the sample is present burns} the LOI values are calculated as followsi

L.O.I. «X 100

A higher L.O.I value therefore shows a higher degree of

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Flame retardancy.

The table below contains the results of this determination »

Concentration of bis-beta copolymer

solids in the fmlie H) LOI

0 17.3

5 18.4

10 19.7

20 21.9

30 23.4

The above data shows how the novel copolymer additives of the present invention provide flame retardancy from normally improve flammable polymer films.

Similar results were also obtained using the following copolymers as flame retardant additives:

(1) a 6Oi37 »3 (weight) bis-betaj vinyl chloride! N-methylol acrylamide copolymer and

(2) a 6O «4O (weight) bis-beta t vinyl bromide copolymer.

2 0 9 B Π 3/1 Π R I

Claims (1)

Patent claims: 1. An aqueous emulsion containing particles of a copolymer of (l) at least one halogen-containing ethylenically unsaturated monomers and (2) about 1 to 90 wt -. <Fo at least a bis (hydrocarbyl) vinyl phosphonate of the general formula X O « ^M ORU - C - P" L ' in which X is a hydrogen atom, a halogen atom, a cyano or aryl radical, a CL-C ₁₀ - alkyl radical or the radical J. Xb -P / means in which R and R 'hydrocarbyl radicals or ^ -OR ' Substituted hydrocarbyl radicals which can be identical, different or linked to one another. 2. The copolymer on which the emulsion according to claim 1 is based, characterized in that the halogen-containing ethylenically unsaturated monomer is a vinyl halide, vinylidene halide, chlorinated styrene, halogenated C 1 -C 4 alkyl acrylate or methacrylate or a halogen-substituted nitrile of ethylenically unsaturated carboxylic acids. 2 09 8 83/1084 J. Copolymer according to Claim 2, characterized in that that the halogen-containing ethylenically unsaturated monomer is vinyl chloride, vinyl fluoride or vinyl bromide. 4. The emulsion according to claim 1 underlying copolymer, characterized in that it is about 40 to 70 Contains by weight bis (hydrocarbyl) vinyl phosphonate. 5. The emulsion according to claim 1 underlying copolymer, characterized in that the bis (hydrocarbyl) vinyl phosphonate Is bis (beta-chloroethyl) vinyl phosphonate. 6. Aqueous emulsion according to claim 1, containing particles of a copolymer of vinyl chloride and about 40 to 70 Wt .- ^ bis (beta-chloroethyl) vinyl phosphonate. 7. The emulsion of claim 1 underlying copolymer, characterized in that one or more optional Comonomers in a concentration of up to about 30% by weight available. 8. Aqueous emulsion according to claim 1, characterized in that it is an effective concentration of a protective colloid contains. 9 · Fire retardant polymer blend, consisting of an intimate blend of at least one normally flammable Polymer substrate and an effective concentration of the aqueous emulsion according to claim 1. 2 ο 9 ?, <Ή / 1 η a 10. Mixture according to claim 9 * characterized in that that the halogen-containing ethylenically unsaturated monomers of the aqueous emulsion copolymer is a vinyl halide, vinylidene halide, chlorinated styrene, halogenated C 1 -C, 2-alkyl acrylate or methacrylate or a halogen-substituted nitrile of ethylenically unsaturated carboxylic acids. 11. Mixture according to claim 10, characterized in that the halogen-containing ethylenically unsaturated monomers of the aqueous emulsion copolymer is vinyl chloride, vinyl fluoride or vinyl bromide. 12. Mixture according to claim 9 »characterized in that. that the aqueous emulsion copolymer is about 40 to 70 wt .- ^ of bis (hydrocarbyl) vinyl phosphonate. 13. Mixture according to claim 9 »characterized in that the bis (hydrocarbyl) vinyl phosphonate of the aqueous emulsion copolymer Is bis (beta-chloroethyl) vinyl phosphonate. 14 «Mixture according to claim 9» characterized in that that the aqueous emulsion copolymer is a copolymer of vinyl chloride and about 40 to 70 wt .- ^ S bis (beta-chloroethyl) vinyl phosphonate is. 209883/1084 15 · Mixture according to claim 9 »characterized in that that the polymer sutostrat is in the form of an aqueous emulsion, suspension or solution is available. For: Stauffer QWemical Company Dr.H.J.Woia Lawyer 209883/1084