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Patent US4014839 - Fire retardant polymeric additives - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inAdvanced Patent SearchPatentsA fire retardant additive comprising particles of a polymer of: 1. at least one halogen-containing alpha, betaethylenically unsaturated monomer; 2. at least one bis(hydrocarbyl)vinyl phosphonate having the structure: ##STR1## wherein X is selected from the group consisting of hydrogen, halogen, cyano,...http://www.google.com/patents/US4014839?utm_source=gb-gplus-sharePatent US4014839 - Fire retardant polymeric additivesAdvanced Patent SearchPublication numberUS4014839 APublication typeGrantApplication numberUS 05/646,121Publication dateMar 29, 1977Filing dateJan 2, 1976Priority dateSep 17, 1973Publication number05646121, 646121, US 4014839 A, US 4014839A, US-A-4014839, US4014839 A, US4014839AInventorsPaul Kraft, Siegfried AltscherOriginal AssigneeStauffer Chemical CompanyExport CitationBiBTeX, EndNote, RefManPatent Citations (4), Referenced by (7), Classifications (41), Legal Events (1) External Links: USPTO, USPTO Assignment, EspacenetFire retardant polymeric additivesUS 4014839 AAbstract A fire retardant additive comprising particles of a polymer of:
What is claimed is: 1. An aqueous emulsion comprising particles of an emulsion polymer consisting essentially of:1. from about 10 to 98% by weight of a vinyl or vinylidene halide; 2. from about 1% to 89% by weight of at least one bis (hydrocarbyl) vinyl phosphonate having the structure: ##STR5## wherein X is selected from the group consisting of hydrogen, halogen, cyano, aryl, C1 -C18 alkyl and ##STR6## wherein R and R' are hydrocarbyl and substituted hydrocarbyl groups which can be the same, different or conjoint; and 3. from about 1% to 45% by weight of at least one third comonomer selected from the alpha olefins.
3. An aqueous emulsion as defined in claim 1 wherein the alpha olefin is selected from the group consisting of ethylene, propylene and butylene.
6. An aqueous emulsion as defined in claim 1 wherein the emulsion polymer consists essentially of vinylidene chloride, bis(beta-chloroethyl) vinyl phosphonate, and propylene.
7. An aqueous emulsion as defined in claim 1 wherein the emulsion polymer consists essentially of about 15% by weight of bis(beta-chloroethyl) vinyl phosphonate, about 80% by weight of vinylidene chloride and about 5% by weight propylene.
8. An aqueous emulsion comprising particles of an emulsion polymer consisting essentially of:1. from about 10 to 98% by weight of a vinyl or vinylidene halide; 2. from about 1% to 89% by weight of at least one bis (hydrocarbyl)vinylphosphonate having the structure: ##STR7## wherein X is selected from the group consisting of hydrogen, halogen, cyano, aryl, C1 -C18 alkyl and ##STR8## wherein R and R' are hydrocarbyl and substituted hydrocarbyl groups which can be the same, different or conjoint; 3. from about 1% to 45% by weight of at least one third comonomer selected from the alpha olefins; and
RELATED APPLICATIONS This is a division of Application Ser. No. 397,515 filed Sept. 17, 1973 and now U.S. Pat. No. 3,948,842, granted Apr. 6, 1976 which, in turn, is a continuation-in-part of application Ser. No. 49,204, filed June 23, 1970, now U.S. Pat. No. 3,725,509, granted Apr. 3, 1973, and the now abandoned application Ser. No. 160,905, filed July 8, 1971, the latter application, in turn, being a continuation-in-part of the former application. The respective disclosures of both of said applications are incorporated herein by reference.
BACKGROUND OF THE INVENTION Polymers of halogen-containing ethylenically unsaturated monomers, such as the vinyl or vinylidene halides, are often prepared as aqueous latices or emulsions in which form they may be conveniently used as coatings, adhesives, paint bases, binders for non-woven fabrics, coatings for woven fabrics including fabrics prepared from natural, synthetic, mineral or glass fibers and in various other types of applications. In many instances, particularly where they are being considered for use in building interiors or in uses requiring their prolonged exposure to high temperatures, it is highly desirable and advantageous that these latices should display enhanced fire or flame retardant properties and color stability so that they may be safely employed in place of more costly materials. Moreover, it is highly desirable and advantageous that these latices when applied to flexible substrates, should impart a desirably soft "hand" to said substrates.
Prior attempts to provide fire retardant, film-forming vinyl or vinylidene halide polymer latices have involved the preparation of various polymeric compositions including copolymer latices of vinyl halides and alkyl acrylates, copolymer latices of vinyl halides and vinylidene chloride and polyvinyl halide latices containing an extraneously added phosphate ester plasticizer. Other attempts have involved the use of interpolymers of bis(β-chloroethyl) vinyl phosphonate with lower alkyl acrylates or methacrylates and acrylic or methacrylic nitriles. These interpolymers could additionally optionally include vinyl halides or vinylidene halides. Still other attempts have involved interpolymerization of vinylidene halide monomers with carboxylic acid monomers and N-alkylol acrylamide monomers. These latter interpolymers could optionally include other polymerizable comonomers such as esters of acrylic acid or methacrylic acid, vinyl acetate, acrylonitrile, methacrylonitrile, acrylamide or methacrylamide, styrene of bis(β-haloalkyl) vinyl phosphonates. However, despite the many and varied attempts to obtain a completely satisfactory polymeric latex, none of the above-described approaches has proven to be completely satisfactory as the resultant products are found, in many cases, to be lacking in either sufficient fire retardancy, color stability, mechanical stability, ultraviolet stability, softness of the polymers or the products are subject to the gradual loss of their extraneously added phosphate plasticizers.
TECHNICAL DISCLOSURE OF THE INVENTION In its broadest aspect, this invention resides in the discovery that a wide variety of polymers, particularly polymers in the form of solids, aqueous solutions, suspensions or, most preferably, emulsions, as well as a wide variety of fiber and fabric substrates may be rendered fire retardant by the incorporation therein or the application thereto of the novel polymeric additives of the present invention. These additives comprise polymers of: (1 ) one or more halogen-containing vinyl monomers with (2) one or more phosphorus-containing vinyl monomers as hereinafter defined, and (3) one or more additional comonomers as hereinafter further defined, these polymers being in the form of solid particles or particles in an aqueous emulsion or latex. More particularly, it has now been discovered that the use of aqueous emulsion or latex polymers or the coagula or dried particles thereof formed from one or more halogen-containing vinyl monomers with one or more bis(hydrocarbyl) vinyl phosphonates and one or more additional comonomers as hereinafter defined, impart to the resulting composition or material a high degree of fire retardance and excellent color stability without adversely affecting any of the significant physical properties thereof. In addition, it has been found that the polymers of the present invention impart a desirably soft hand to materials upon which they are coated or within which they are impregnated. Moreover, it is truly surprising and advantageous to find the polymer blends resulting from the process of this invention, particularly those blends which are in the form of an aqueous emulsion or latex system, display an outstanding degree of compatibility since, as is well known to those skilled in the art, physical blends of two or more polymers are almost always characterized by their inherently poor compatibility.
1. at least one halogen-containing, alpha, betaethylenically unsaturated monomer, i.e., vinyl monomers including vinyl halides such as, for example, vinyl chloride, vinyl fluoride and vinyl bromide, halogenated C1 -C12 alkyl acrylates and methacrylates such as, for example, methyl alphachloroacrylate and methyl alpha-bromoacrylate; vinylidene halides such as, for example, vinylidene chloride, vinylidene bromide, vinylidene chlorobromide and vinylidene fluoride; halo-substituted nitriles of ethylenically unsaturated carboxylic acids such as, for example, alpha-chloroacrylonitrile; and the chlorinated styrenes such as, for example alpha-chlorostyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, and 2,4-dichlorostyrene;
3. at least one comomoner including alpha olefins such as ethylene, propylene and butylene; vinyl esters of carboxylic acids, such as vinyl acetate, vinyl butyrate and vinyl stearate; and C1 -C20 alkyl esters of acrylic and methacrylic acid such as methyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, sec.-butyl acrylate, tert.-butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate and the like; ethylenically unsaturated dicarboxylic acids, their anhydrides and their C1 -C20 mono- and dialkyl esters such as aconitic acid, fumaric acid, maleic acid, itaconic acid, citraconic acid, maleic anhydride, dibutyl fumarate and monoethyl maleate; amides of ethylenically unsaturated carboxylic acids such as acrylamide and methacrylamide and their N-methylol and diacetone derivatives such as N-methylol acrylamide, N-methylol methacrylamide and diacetone acrylamide; vinyl aryl compounds such as styrene and alpha-methyl styrene; C1 -C20 alkyl vinyl ethers such as methyl vinyl ether, ethyl vinyl ether and stearyl vinyl ether; dienes such as isoprene and butadiene; and glycidyl esters of acrylic and methacrylic acid such as glycidyl acrylate and glycidyl methacrylate. The preferred comonomers are the C1 -C20 alkyl esters of acrylic and methacrylic acid especially the lower (C4 -C8) alkyl acrylates.
Representative of the above-defined bis(hydrocarbyl) vinylphosphonates are:
In addition to the above described bis(hydrocarbyl) vinylphosphonates, it is also possible to prepare aqueous emulsion polymers useful as flame retardant additives by employing: (1) mono (alkyl) acid vinylphosphonates such as, for example, mono(ethyl) hydrogen vinylphosphonate, mono(butyl) hydrogen vinylphosphonate, mono(octyl)hydrogen vinylphosphonate; mono(beta-chloroethyl)hydrogen vinylphosphonate, mono (omega-chlorooctyl)hydrogen vinylphosphonate; (2) mono(cycloalkyl) and mono(aryl)hydrogen vinylphosphonates such as, for example, mono(cyclohexyl)hydrogen vinylphosphonate, mono(phenyl) hydrogen vinylphosphonate, mono(benzyl)hydrogen vinylphosphonate; (3) bis(cycloalkyl) and bis(aryl)vinylphosphonates, such as, for example, bis(cyclohexyl)vinylphosphonate and bis(benzyl) vinylphosphonates; and, (4) bis(alkyl), bis(cycloalkyl), and bis(aryl) allylphosphonates, such as, for example bis(beta-chloroethyl)allylphosphonate, bis(cyclohexyl) allylphosphonate and bis(benzyl)allylphosphonate as well as mixtures of any two or more of the above described phosphonate monomers.
3. a terpolymer containing 15 parts by weight bis(betachloroethyl)vinylphosphonate, 5 parts by weight propylene and 80 parts by weight vinylidene chloride;
In all cases, the novel aqueous emulsion or latex polymers of this invention or the coagula or dried particles thereof have been found to provide blends with ordinarily flammable polymers in either emulsion, latex or dry, solid form; the emulsion or latex polymers of the invention also serve as binders for non-woven fabrics or coating for woven fabrics which are characterized by their outstanding fire retardancy. As used in this disclosure, the term "fire retardant" or "flame retardant" is intended to refer to that particular property of a material which provides it with a degree of resistance to ignition and burning. Thus, a fire or flame retardant composition is one which has a low level of flammability and flame spread. This property may be conveniently evaluated by means of any of the standard flame retardancy tests such, for example, as the ASTM test D-635.
As has been indicated, hereinabove, the aqueous emulsion or latex polymers of this invention are particularly suitable for blending with ordinarily flammable polymers which are in the form of aqueous systems such as solutions, suspensions, or, most preferably, emulsions. The resulting aqueous blends, like the aqueous emulsions or latex polymers of the present invention per se, may then be used in any of the various coating, adhesive, binding, laminating and impregnating applications known to those skilled in the art. Thus, these aqueous blends may be coated upon and/or absorbed by all types of substrates to which it is desired to impart fire retardant properties. They may, therefore, be used as coatings, impregnants, fillers, laminants, and adhesives for such substrates as wood; paper; metals; non-woven fabrics and woven textiles based on either natural, synthetic, mineral or glass fibers or blends thereof, for example, woven and non-woven fabrics and textiles made from fibers of cotton, wool, silk, polyester, nylon, rayon, asbestos, fiber glass and blends thereof; synthetic polymer films such as those based upon polyolefins, regenerated cellulose, i.e., cellophane, polyvinyl chloride, polyesters and the like; leather; natural and synthetic rubber; fiber-board; and synthetic plastics prepared by means of either addition or condensation polymerization techniques.
1. Polymers of vinyl chloride including polyvinyl chloride and the random and graft copolymers of vinyl chloride with a minor proportion of one or more of the above-described group of vinyl monomers which are included as comonomers for use in preparing the aqueous emulsion copolymers of this invention;
2. Polymers of the C1 -C8 alkyl acrylates and methacrylates including their homopolymers and their copolymers with each other and with a minor proportion of such comonomers 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 dicarboxylic acids their anhydrides and their C1 -C20 mono- and dialkyl esters, e.g. maleic acid, maleic anhydride, diethyl maleate and monobutyl acid maleate; vinylidene halides, e.g. vinylidene chloride; C1 -C20 alkyl vinyl ethers, e.g. methyl vinyl ether; amides of ethylenically unsaturated monocarboxylic acids, e.g. acrylamide and the N-methylol and diacetone derivatives; vinyl aryl compounds, e.g. alphamethyl styrene and styrene; and, nitriles of alpha, beta-ethylenically unsaturated carboxylic acids, e.g. acrylonitrile and methacrylonitrile.
10. Polyurethane resins, i.e., the resins formed by the reaction between a bi- or polyfunctional hydroxyl containing compound, such as polyether or polyester, and a di- or polyisocyanurate such as toluene diisocyanate or diphenylmethane-4,4'-diisocyanate;
15. The acrylate:styrene:acrylonitrile resins commonly referred to as "ASA" resins, which comprise copolymers containing a major proportion of a C2 -C8 alkyl acrylate ester elastomer upon which is grafted about 65 - 95%, by weight of the latter copolymer, of a 70 - 80:30 - 20 styrene: acrylonitrile copolymer;
In effect, one may utilize any ordinarily flammable polymeric material in preparing fire retardant polyblends with the novel polymer additives of this invention. These ordinarily flammable polymeric materials may be thermoplastic polymers, i.e., polymers which can be softened by heat and which then regain their original properties on cooling. Also applicable are polymer systems comprising copolymers containing one or more crosslinkable comonomers, i.e., monomers containing two or more dissimilar functional groups, such, for example, as N-methylol acrylamide, N-methylol methacrylamide, glycidyl acrylate and glycidyl methacrylate. Thus, the polymers containing one or more of these crosslinkable comonomers can be cured or crosslinked, by the use of heat and/or catalysts and are thereby converted into a form in which they will no longer be thermoplastic but will, rather, be thermosetting, i.e., they will not dissolve in contact with a solvent or water. Ideally, the novel polymer additives of this invention would be blended with such crosslinkable copolymer systems prior to the time they undergo this curing or crosslinking operation.
The fire retardant polymer compositions of this invention can be prepared so as to contain various optional additives which may include plasticizers such as the alkyl esters of phthalic, adipic and sebacic acids such, for example, as dioctyl phthalate and ditridecyl phthalate and aryl phosphate esters such, for example, as triphenyl and tricresyl phosphate, etc.; lubricants and mold release agents such as stearic acid or its metal salts, petroleum based waxes, mineral oils and their halogenated products, polyethylene waxes and their halogenated product etc.; and heat and light stabilizers such as barium, cadmium, calcium, zinc soaps or phenates, basic lead compounds, organo-tin compounds, such as dialkyl tin mercaptides and dialkyl tin maleates, thiolauric anhydride and n-butyl stannoic acid, epoxidized oils, alkyl diphenyl phosphites, triaryl phosphites, phenyl salicylates, o-hydroxy benzophenones and benzotriazoles, etc. For a more complete listing of plasticizers, lubricants, stabilizers and other functional additives, one may consult "Polyvinyl Chloride" by H. A. Sarvetnick published by Van Nostrand Reinhold Co., New York, N.Y., in 1969.
The compositions of this invention may also contain fillers, pigments, dyes, opacifying agents, decorative additives such as reflective metal foils or flakes, and other imbedded solid objects such as fiber glass, textile fibers, asbestos, and the like, provided that they do not detract from the flame retardancy of these products. In addition, the compositions may contain other flame retardants such as antimony compounds, zinc borate, aluminum hydrate, halogenated alkyl phosphates or phosphonates, alkyl acid phosphonates, or small concentrations of phosphoric acid.
1. Color Stability Film samples cast from various latices are placed in a forced air oven set at 60� C. for 8 hours. The samples are then rated as possessing good color stability if they remained clear and colorless and as possessing poor color stability if they turned yellow to brown.
2. FR Properties Film samples cast from various latices are held in a vertical position and ignited for 2 seconds with a Bunsen burner. The burner is then removed. Samples which self-extinguished and would not continue to burn within 5 seconds after the burner was removed were noted as possessing good FR properties. Samples which continued to burn for more than 5 seconds after removal of the burner or burn the entire length within 5 seconds were noted as possessing poor FR properties.
3. Hand Hand is evaluated by flexing films cast from various latices. A hard film can be readily distinguished from a soft film upon flexing of the film.
EXAMPLE 1 Into a 32 ounce polymerization vessel, there are charged 120 parts bis(beta-chloroethyl)vinylphosphonate, hereinafter referred to as "bis-beta", 90 parts n-butyl acrylate, 90 parts vinylidene chloride, 110 parts deionized water, 60 parts of a 10% aqueous solution of sodium lauryl sulfate and 120 parts of a 5% aqueous solution of polyvinyl alcohol. The pH of the resulting mixture is adjusted to a value of about 8 by addition of 3.3 parts of 58% aqueous solution of ammonium hydroxide, whereupon 110 parts of a 5% aqueous solution of ammonium persulfate is added to the mixture. The air space above the liquid level in the reactor is purged with nitrogen and the vessel is sealed. The vessel is shaken to form a stable emulsion. Polymerization is effected at a temperature of 55� C. over a period of 12 hours with a polymerization vessel being continuously subjected to a tumbling agitation. A stable latex of good color stability is obtained. When the latex is poured onto a Petri dish and dried, a film exhibiting a soft hand is recovered. When ignited with a Bunsen burner for two seconds and the burner then removed, the film does not support combustion and therefore exhibits good FR properties.
EXAMPLES 2-8 The following polymers are prepared as set forth below:
EXAMPLES 9-10 These examples compare polymers obtained in accordance with the present invention containing bis-beta, n-butyl acrylate and vinylidene chloride with prior art polymers containing bis-beta, n-butyl acrylate, vinylidene chloride and acrylic acid (U.S. Pat. No. 3,682,871) and polymers containing bis-beta, n-butyl acrylate, vinylidene chloride and acrylonitrile (U.S. Pat. No. 3,489,706).
EXAMPLES 11-12 Examples 11 and 12 illustrate that a soft hand can be imparted to the polymers of the present invention by substituting vinylidene chloride for vinyl chloride in the polymer. Surprisingly, as shown in the comparative examples, copolymers of bis beta and either vinyl chloride of vinylidene chloride are characterized by a hard hand and poor color stability; whereas, a bis-beta copolymer with n-butyl acrylate, while possessing good color stability and soft hand exhibits poor FR properties.
TABLE II__________________________________________________________________________COMPOSITION PARTS       Example 11              Example 12                      Comparative Examples__________________________________________________________________________Bis-Beta     120   120     120 120 120n-Butyl Acrylate         90    90     --  --  180Vinylidene    90   90      --  180 --  --VinylChloride     --     90     --   90 --Time Hrs      12    12      12  12  12Temp. � C         55    55      55  55  55Deionized H2 O        110   110     110 110 110Sodium Lauryl Sulfate(10% Soln)    60    60      60  60  60Ammonium Persulfate(5% Soln)    110   110     110 110 110Polyvinyl Alcohol(5% Soln)    120   120     120 120 120Conc NH4 OH        3.3   3.3     3.3 3.3 3.3        FILM EVALUATIONColor Stability        Good  Good    Poor                          Poor                              GoodFR Properties        Good  Good    Good                          Good                              Poor"HAND"       Soft  Hard    Hard                          Hard                              Soft__________________________________________________________________________
EXAMPLES 13-14 Examples 13 and 14 as compared with the comparative example illustrate that even among similar terpolymers, the particular combination of comonomers in the terpolymers of the present invention provide terpolymers of significantly better properties as compared to such similar terpolymers.
TABLE III______________________________________           Example  Example  ComparativeComposition Parts           13       14       Example______________________________________Bis-Beta        120      120      120n-Butyl Acrylate           90       90       --VinylideneChloride        90       --       90VinylChloride        --       90       90Time Hrs        12       12       12Temp. � C           55       55       55Deionized H2 O           110      110      110Sodium Lauryl Sulfate           60       60       60(10% Soln)Ammonium Persulfate           110      110      110(5% Soln)Polyvinyl Alcohol           120      120      120(5% Soln)Conc NH4 OH           3.3      3.3      3.3FILM EVALUATIONColor Stability Good     Good     PoorFR Properties   Good     Good     Good"HAND"          Soft     Hard     Hard______________________________________
EXAMPLES 15-17 Examples 15 to 17 illustrate that terpolymers exhibiting excellent properties can be obtained with a wide variety of crosslinking agents.
TABLE IV______________________________________COMPOSITIONPARTS          Example 15                    Example 16                              Example 17______________________________________Bis-Beta       25        120       120n-Butyl Acrylate          59        90        90Vinylidene     50        90        90ChlorideGlycidyl       --        10        --methacrylateDi Acetone     --        --        10AcrylamideN-Methylol     1.5       --        --AcrylamideTime Hrs.      12        12        12Temp. � C          60        55        55Deionized H2 O          100       110       110Sodium Lauryl Sulfate          100       60        60(10% Soln)Ammonium Persulfate          --        110       110(5% Soln)NaCO3 /NaHCO3          1/1       --        --Ammonium Persulfate          0.4       --        --Polyvinyl Alcohol          --        120       120(5% Soln)Conc NH4 OH          --        3.3       3.3        FILM EVALUATIONColor Stability          Good      Good      GoodFR Properties  Good      Good      Good"HAND"         Soft      Soft      Soft______________________________________
EXAMPLE 18 Two pad baths were prepared by mixing the following ingredients:
Two pieces of a 11/2 oz non-woven fabric consisting of cotton fibers laminated on a rayon scrim were used in this test. One was immersed in bath A and the other in bath B. They were squeeze-dried and then heated at 170� C. for 8 minutes. The dried fabrics were cut into 2 inches � 12 inches test strips for flammability testing after conditioning for 24 hours at 78� F. and 80% relative humidity.
EXAMPLE 19 A commercial stocking of nylon 6,6(poly-hexamethylene adipamide) was cut into 2 pieces and treated with bath A and bath B separately as described in Example 18. Flammability tests showed that samples treated with bath A were self-extinguishing upon removal of flame and samples treated with bath B burned the entire length.
EXAMPLE 20 A commercial garment of 65/35 polyester/rayon blend was cut into 2 pieces and treated with bath A and bath B separately, as described in Example 18. Flammability tests showed that samples treated with bath A were self-extinguishing and samples treated with bath B burned the entire length.
EXAMPLE 21 Two pad baths were prepared by mixing the following ingredients:
______________________________________              C       D______________________________________A polymer latex prepared accordingto Example 6 (adjusted to 48% solids)                --        100 partsA commercial all-acrylic latex(48% solids)         200 parts 100 partsAqueous pigment dispersion(Inmont 26-9750 blue)                 10 parts  10 parts10% glass coupling agent solution -(10% hydrolyzed Dow-Corning                100 parts 100 parts10% oxalic acid in water                 10 parts  10 parts______________________________________
Pieces of glass fabric, 4.5 oz. per square yard Beta casement fabric, were impregnated with either bath C or bath D, squeezed with a roller and dried in air, followed by placing in a 100� C oven for 10 minutes. The fabrics weight increased by 6.5%. Strips of 2 inches � 12 inches were cut for flammability tests after conditioning for 24 hours at 76� F and 85% relative humidity. They were kept in a vertical position and ignited by 2 successive 3-second contacts with the flame of a Bunsen burner. After ignition, samples treated with bath C burned the entire length; whereas, samples treated with bath D were difficult to ignite and self-extinguished after removal of the burner flame.
Patent CitationsCited PatentFiling datePublication dateApplicantTitleUS3682871 *Jun 10, 1970Aug 8, 1972Goodrich Co B FLow temperature curing vinylidene-halide-unsaturated monocarboxylic acid-n-alkylol amide polymersUS3691127 *Sep 10, 1970Sep 12, 1972Stauffer Chemical CoFire retardant vinyl chloride copolymer laticesUS3883463 *Sep 27, 1973May 13, 1975Stauffer Chemical CoFlame retardant binder for flammable materialsUS3948842 *Sep 17, 1973Apr 6, 1976Stauffer Chemical CompanyFire retardant polymeric additives of vinylidene halides with bis(hydrocarbyl) vinyl phosphonates and C1 -C20 alkylesters of acrylic and methacrylic acids* Cited by examinerReferenced byCiting PatentFiling datePublication dateApplicantTitleUS4788008 *Apr 6, 1987Nov 29, 1988Gencorp Inc.Flame retardant vinylidene chloride latexes and coatings thereofUS4822861 *Mar 15, 1988Apr 18, 1989Polychrome CorporationMethod for the preparation of polyvinyl phosphonic acidUS5444123 *Feb 28, 1994Aug 22, 1995Basf AktiengesellschaftBlend of polyphenylene ether, polystyrene, homo or copolymeric phosphorus compound and low molecular weight phosphorus compounds as flameproofing agents; toughnessUS6030562 *Dec 4, 1997Feb 29, 2000Masonite CorporationMethod of making cellulosic composite articlesUS6265082 *Apr 9, 1999Jul 24, 2001Kevin L. DunhamAdhered to cured filmUS6713168Jul 12, 2001Mar 30, 2004J.M. Huber CorporationFire retardant wood composite materialsEP0530692A2 *Aug 28, 1992Mar 10, 1993BASF AktiengesellschaftHalogen-free flame resistant thermoplastic moulding masses based on polyphenylenether and polystyrene* Cited by examinerClassifications U.S. Classification524/807, 525/209, 526/345, 526/332, 526/316, 526/338, 526/278, 526/274, 526/321, 427/408International ClassificationC08L67/00, D06M15/356, C08F214/04, C08L101/00, C08L1/00, C08L23/02, C08K5/5333, C08F30/02, C08L43/02, C08L75/04Cooperative ClassificationC08L27/06, C08F214/04, C08F30/02, C08L67/00, C08L101/00, C08K5/5333, C08L1/00, C08L23/02, C08L43/02, D06M15/3564, C08L75/04European ClassificationC08F30/02, C08L23/02, C08L1/00, C08L67/00, C08L75/04, C08L43/02, C08L101/00, C08F214/04, D06M15/356P, C08K5/5333Legal EventsDateCodeEventDescriptionMar 13, 1989ASAssignmentOwner name: AKZO AMERICA INC., A CORP. OF DE, NEW YORKFree format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:STAUFFER CHEMICAL COMPANY;REEL/FRAME:005080/0328Effective date: 19890213RotateOriginal ImageGoogle Home - Sitemap - USPTO Bulk Downloads - Privacy Policy - Terms of Service - About Google Patents - Send FeedbackData provided by IFI CLAIMS Patent Services