CA1050677A - Flame retardant binder for flammable materials - Google Patents
Flame retardant binder for flammable materialsInfo
- Publication number
- CA1050677A CA1050677A CA211,889A CA211889A CA1050677A CA 1050677 A CA1050677 A CA 1050677A CA 211889 A CA211889 A CA 211889A CA 1050677 A CA1050677 A CA 1050677A
- Authority
- CA
- Canada
- Prior art keywords
- bis
- phosphonate
- vinyl
- chloroethyl
- beta
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
FLAME RETARDANT BINDER FOR FLAMMABLE MATERIALS
Abstract of the Disclosure A flame retardant composition comprises the following components: (a) a polymer latex comprising (i) a bis(hydro-carbyl)vinyl phosphonate, preferably bis(.beta.-chloroethyl)vinyl phosphonate, (ii) a vinyl halide or vinylidene halide such as vinyl chloride or vinylidene chloride, (iii) an alkyl acrylate and optionally, (iv) another derivative of acrylic acid or methacrylic acid; (b) a phosphorus source selected from (i) a co-condensate of bis(.beta.-chloroethyl)vinyl phosphonate and dimethyl methyl phosphonate or a condensate of bis(.beta.-chloroethyl) vinyl phosphonate, (ii) tetrakis (hydroxymethyl) phosphonium halide or hydroxide, (iii) N-hydroxymethyl-3-(dimethylphosphoro) propionamide, (iv) tris(2,3-dibromopropyl phosphate), (v) water-insoluble ammonium polyphosphate and (vi) water-insoluble ammonium salt of metaphosphoroamidic acid; (c) urea; (d) an aminoplast selected from a melamine formaldehyde or urea formaldehyde; and (e) optionally, a phosphate plasticizer. These compositions are useful as binders, saturants, impregnants and coatings for flammable materials.
Abstract of the Disclosure A flame retardant composition comprises the following components: (a) a polymer latex comprising (i) a bis(hydro-carbyl)vinyl phosphonate, preferably bis(.beta.-chloroethyl)vinyl phosphonate, (ii) a vinyl halide or vinylidene halide such as vinyl chloride or vinylidene chloride, (iii) an alkyl acrylate and optionally, (iv) another derivative of acrylic acid or methacrylic acid; (b) a phosphorus source selected from (i) a co-condensate of bis(.beta.-chloroethyl)vinyl phosphonate and dimethyl methyl phosphonate or a condensate of bis(.beta.-chloroethyl) vinyl phosphonate, (ii) tetrakis (hydroxymethyl) phosphonium halide or hydroxide, (iii) N-hydroxymethyl-3-(dimethylphosphoro) propionamide, (iv) tris(2,3-dibromopropyl phosphate), (v) water-insoluble ammonium polyphosphate and (vi) water-insoluble ammonium salt of metaphosphoroamidic acid; (c) urea; (d) an aminoplast selected from a melamine formaldehyde or urea formaldehyde; and (e) optionally, a phosphate plasticizer. These compositions are useful as binders, saturants, impregnants and coatings for flammable materials.
Description
-~S~'7'~
FL~ME RETAR~ANT BINDER FOR FLAMMABLE MATERIALS
BACKGROUND OF THE INVENTION
. . ~
Copolymers of vinyl halides, vinylidene halides and various phorpho~us-containin~ vinyl monomers have been fre-quently used as fire retardant agents for various flammable materials, such as paper, cellulosic textlles and non-woven fabrics. For light weight and flexible substrates, there is a limit to how much polymer the substrates can pick up before flexibility and a soft hand are lost. In these cases, there is insufficient add-on to give reduced flammability. Inorganic salts such as diammonium phosphate and ammonium sulfamate have heretofore been used for this purpose; however, their water solubility has rendered their flame retardant property non-durable.
Thus, in accordance with the present teachings, a flame retardant polymer latex binder composition is provided which comprises (a) a polymer latex containing ~l) a bis(hydro- -carbyl) vinyl phosphonate of the formula: :
X O
~ OR' CH2 = C - P
~ OR, wherein X is selected from the group consisting of hydrogen, ~:
halogen, cyano 9 phenyl, C1-Cl8 alkyl and Il OR' ~ OR, and each of R and R' are hydrocarbyl or substituted hydrocarbyl having from 1 to 18 carbon atoms (2) a vinyl halide or vinylidene halide, (3) a Cl to C20 alkyl ester of acrylic acid, and optionally (4) a comonomer selected from the group consisting of acrylicacid, methacrylic acid, amides of acrylic acid and methacrylic acid, N-methylol derivati~es of the amides of acrylic acid and methacrylic acid, and diacetone derivatives of the amides of acrylic acid and methacrylic acid, (b) at least ~ ~ -2~
-1~5~ 77 one phorphorus containing compound selected ~rom the group consisting of a co-condensate of bist~ ~chloroethyl)vinyl phos-phonate and dimethyl methyl phosphonate, a condensate of bis (~ -chloroethyl)vinyl phosphonate~ tetrakisthydroxymethyl) phosphonium chloride or hydroxide, ~l~hydroxymethyl-3-(dimethyl-phosphoro)propionamide, tris(2,3-dibromopropyl phosphonate) and water-insoluble ammonium polyphosphate, water-insoluble ammonium salt of metaphosphoramidic acid, and mixtures thereo~, said water-insoluble phosphorus compounds being characterized by a water solubility of less than 25g/lOOcc at lO~C., (c) :
optionally urea, (d) an aminoplast selected from the group consisting of melamine formaldehyde and urea formaldehyde, and (e) optionally a phosphate plasticizer. -It has now been found that excellent and non-after~
glowing durable flame retardant properties are imparted to :
flammable materials when they are treated with a composition comprising the following components: (a) from about 20 to about 70 weight % of a polymer latex, (b) from about 3 to about 50 weight % of a phosphorus source, (c) from O to about 50 weight %
20 of urea, (d) a melamine formaldehyde or urea formaldehyde amino- ~- :
plast in about 10 to about SO weight ~, and (e) a phosphate ;; .
plasticizer in O to about 20 weight %. The components will now be more fully described.
Component (aj is a polymer latex derived from at least three monomers: (1) a bis(hydrocarbyl)vinyl phosphonate, (2) a vinyl halide or vinylidene halide, (3) an alkyl acrylate, and optionally (4) another derivative of acrylic or methacrylic :
' ' -2a-: . , . - , , ~: - ;:: , -,, ~ :
. - -s~
acid as more fully described below.
The bis(hydrocarbyl)~inyl phosphonate has thestrurture:
X O
' " OR'~
C~2 = C - p OR ,/
wherein X is selected from ~he group consisting of hydrogen, halogen, cyanot aryl such as phenyl, Cl-C18 alkyl and OR'`~
~ OR _l R and R' are hydrocarbyl and substituted hydrocarbyl groups consisting essentially of hydrogen and carbon and containing up to about 18 carbon atoms inclusive with the proviso that R and R' may be the same, different or conjoint, i.e., R and R' may combine to form one single radical. `~;~
The use, in this disclosure, of the expression ~ ;
"hydrocarbyl" and "substituted hydrocarbyl groups" in the definition of the suitable bis~hydrocarbyl)vinyl phosphonatss given hereinabove~ref~rs to the radicals obtained upon the remoYal of a hydrogen from a hydrocarbon or substituted hydro-carbon group which may be either an aliphatic or aro~atic group. These hydrocarbyl groups may be substituted with any ~on-interfering groups, i.e.~ with any group which does not interfere with the polymerization of the bis(hydrocarbyl)vinyl phosphonate. Such substituent groups include, for example, chloro, bromo, fluoro, nitro, hydroxy, sulfone, ethoxyt methoxy, nitrile, ether, ester and keto groups and the like.
, Illustrative of the aliphatic and aromatic groups as are represented by R and R' in the structure of-the bis(hydro- -carbyl~vinyl phosphonate givenhereinabove are alkyl groups, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, nonyl, and the like; alkenyl groups such as pentenyl and hexenyl groups and all of their respective isomers; cycloalkyl groups, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the liks;
cycloalkenyl groups, such as cyclohexenyl, and the like; typical aryl groups include phenyl, benzyl, phenethyl, tolyl, naphthyl, and the like.
~epresentative of the above-defined bis(hydrocarbyl~
vinyl phosphonat~s are:
bis(~-chloroethyl)vinyl phosphonate;
bis(~-chloropropyl)vinyl phosphonate;
bis(~-chloroethyl) l-methylvinyl phosphonate;
bis(~-chloroethyl) l-cyanovinyl phosphonate;
bis(~chloroethyl) l-chlorovinyl phosphonate;
bis(~chloroethyl) l-phenylvinyl phosphonate;
dimethyl vinyl phosphonate;
diethyl vinyl phosphonate;
bis(~-chlorobutyl)vinyl phosphonate;
di-n-butyl vinyl phosphonate;
di-isobutyl vinyl phosphonate;
bis(2-chloroisopropyl) l-methylvinyl phosphonate;
diphenyl vinyl phosphonate; and bis(2,3-dibromopropyl)vinyl phosphonate From the group of bis(hydrocarbyl)vinyl phosphonate monomers, it is preferred to employ bis(~-chloroethyl)vinyl phosphonate in preparing the novel aqueous emulsion polymers of this invention since the latter monomer is a commercially n available material and lower in cost than any of the other bis(hydrocarbyl)vinyl phosphonates.
The vinyl hallde or vinylidene halide may be, for example, vinyl chloride, vinyl bromide, vinyl fluoride, vinyli-dene chloride, vinylidene bromide, vinylidene chlorobromide or vinylidene fluoride. Preferred are vinyl chloride and vinylidene chloride.
~ The alkyl acrylate may be any Cl to C20 alkyl ester of acrylic acid, such as methyl acrylate, ethyl acrylate, n- .-butyl acrylate, sec.-butyl acrylate, 2-ethylhexyl acrylate, , 0~7~
lauryl acrylate or mixture thereoE. Preferred monomers are the C4-C8 alkyl acrylates such as n-butyl acrylate and 2-ethylhexyl acrylate.
The fourth monomer is another derivative of acrylic acid or a derivative of methacrylic acid, or may be the respec~
tive acids themselves. Among the derivatives are the amides and t.he N-mathylol and diacetone derivatives of the æmides. `:
Preferred are N-methylol acrylamide, acrylamide, acrylic acid ~ :~
and methacrylic acid. s The proportions of the various monomers forming component (a) are as follows: from about 10 to a~out 75 weight % of bis(h~drocarbyl)vinyl phosphonate, from about 20 to about 85 weight % of vinyl halide or vinylidene halide, from a~cut 5 to about 35 weight.% of alkyl acrylate, and from 0 to about 10 weight ~ of the fourth comonomer~
Specific latex polymers for component ~a) include .
the following: ;
: (1) a terpolymer of 30 parts by weight of vinylidene chloride, 20 parts by weight o~ n-bu~yl ae~rylate and 5O parts by weight of bis(beta-chloroethyl)vinyl phosphonate;
t2) a terpolymer containing 15 parts by weight o~
di-n-butyl vinyl phosphonate, 20 parts by weight of di-2-ethyl-hexyl acrylate and 65 parts by weight of vinylidene chloride; :
(3) a polymer containing 50 parts of bis(beta-chloroethyl)vinyl phosphonate, 25 parts of vinylidene chloride, - 20 parts of 2-ethylhexyl acrylate~ and 5 parts of N-methylol acrylamide;
~ 4) a polymer containing 45 parts by weight of vinylidene chloride, 35 parts by weight of bis(beta-chloroethyl) vinyl phosphonate, 15 parts by weight of n-butyl acrylate and ~5t~'7~
5 parts by weight of N-methylol acrylamide; and ~ 5) a polymer containing 30 parts by weight of bis(beta-chloroethyl)vinyl phosphonate, 5 parts by weight of propylene, 60 parts by weight of vinyl chloride and 5 parts by weight of N-methylol acryl~mide.
The polymers of the presen~ invention can be prepared by means of free radical initiated e!mulsion polymerization techniques well known to those skilled in the art. In these procedures r the various monomers and catalysts are emulsiied, in water, by means of one or more surface-active emulsifiers whereupon the polymerization reaction is then initiated.
Suitable water soluble, free radical initiating catalysts for use in preparing the copolymer latices of this invention include sodium,potassium and ammonium persulfate and hydrogen peroxide or one may use a redox system such, for example, as a mixture of a persulfate with an al~ali metal bisulfite, thiosulfate or -hydrosulfite. These catalysts should be present in a concentra-tion of from about 0.05 to 5.0%, by weight, of the total monomer charge. With respect to the emulsiier or surfactant, it is possible to utilize one or more anionic, cationic, or non-ionic emulsifiers such, for example, as the alkyl carboxylic ~ ;
acid salts; the alkyl sulfate, sulfonate, phosphate, or sul~o-succinamate salts; the alkyl aryl ether alcohols, and the alkyl aryl polyether sulfate salts. The selected emulsifier or emulsifiers should be present in effective concentration of from about 0.3 to 6.0%, hy weight, of the total monomex charge.
In addition, a protective colloid such 25 polyvinyl alcohol, polyvinyl pyrrolidone, methyl cellulose or gelatin can also, if desired, be present in the recipe in an effective concentra-tion of from about 0.03 to 6.0%, by weight, of the total ~3~;'7'7 ~-monomer charge. Alternatively, the protective colloid may be introduced into the copolymer latex subsequent to its prepara-tion. When post-added in this ma~ner, the protective colloid should be present in a concentration of from about 0.03 to 6.o~, by weight, of the total resin solids. In any event, the pre-sence of the protective colloid serves to enhance the mechanical stability of the emulsion.
The actual polymerization raaction will ordinarily be conducted at a temperature of from about 0 to 100C. for a period of from about 1 to 24 hoursJ depending upon such factors as the particular monomer, catalysts, surfactants and polymeriza-tion apparatus that is being utilized. The latices resulting from this polymerization process will ordinarily have a resin solids content of from about 5 to 7~, by weight, wherein the particles have a diameter which ranges in size from about 0.03 to 3.0 microns.
Component (b) is a source of phosphorus selected from the following: (i) a co-condensate of bis(~3-chloroethyl)vinyl phosphonate and dimethyl metbyl phosphonate or a condensate of bis(~3- chloroethyljvinyl phosphonate, (ii) tetrakis (hydroxymethyl) phosphoni~m halide or hydroxide, (iii) (N-'nydroxymethyl-3-dimethyl-phosphoro) propionamide, (iv) tris(2,3-dibromopropyl)phosphate3 (v) water-insoluble ammonium polyphosphate, and (vi) water-insoluble ammonium salt of metaphosphoroamidic acid.
The co~condensate of bis(~ -chloroethyl)vinyl phosphonate and dimethyl methyl phosphonate or the condensate of vinyl phosphonate is prepared by heating the mixtures of the two components or bis(f3-chloroethyl)vinyl phosphonate alone at about 100 to 250C. with a basic catalyst for about 2 to 12 hours resulting in a fluid liquid. A mixture of ethylene dichloride and methyl chloride or ethylene dichloride is generated as a by-product.
: - . - ,. -. - . . : , . . .
~05~'77 Tetrakis(hydroxymethyl) phosphonium chloride or hydroxide, also Xnown as ~IPC or THPOH has the structure:
(HOCH2)~PCl or (H()CH2)~PO~
and is sold by Hooker Chemical Corporation, a division of Occidental Petroleum Corporation.
N-hydroxymethyl-3-(dimethylphosphoro)propionamide has the structure:
O
(CH30)2-P-CH2CH2C-NHCH20H
and is sold under the trademark PYROVATEX CP by Ciba-Geigy Corporation.
, Tris(2,3-dibromopropyl phosphate) has the structure:
(cH2BrcHBrcH2o)3p=o and is sold under the trademark FYROL HB32 by Stauffsr Chemical Company.
Water-insoluble ammonium polyphosphate is made by heating ~-, ammonium phosphate with urea, and is known commercially as PHOSCHEK P30 sold by Monsanto Company.
~he water-insoluble ammonium salt of metaphosphoramidicacid ~ ;
is made by the reaction of ammonia with phosphorus pentoxide. -The term "water-insoluble" is meant to denoteij~that :' , :
the solubility of the phosphorus compound in water is less than ., 25g/lOOcc at 10C. or less than 75g/lOOcc at 70C.
Component (c), whose presence is optional, is urea. ` ;
Component (d) is a melamine formaldehyde or urea ;
formaldehyde aminoplast. Typical aminoplasts include such `
melamine/formaldehyde resins as AEROTEX M-3, AEROTEX 23 Special, AEROTEX MW and AEROTEX ResLn 44, all of said resins being available from American Cyanamid Company.
~ 7'~
Componsnt (e), whose presence is also optional, is a phosphate plasticizer. To illustrate, it can be alkyl acid phosphates, i.e., methyl acid phosphate, butyl acid phosphate; trialkyl phosphates, i.e., trioctyl phosphate, tri-dodecyl phosphate; triaryl phosphates, i.e., tricresyl phcsphate,cresyl diphenyl phosphate, i.e., octyl diphenyl phosphate, hutyl dicresyl phosphate, and the like.
The flammable materials treated by the compositions of this invention include cellulose, regenerated cellulose ~uch as rayon cellulose esters and mixed esters such as, for exampleO
cellulose nitra.te, cellulose acetate, cellulose acetate-butyrate, ;
cellulose acetate propionate and cellulose ethers such as, for example, ethyl cellulose and combinations thereof. In addition, ~ -tha~e flammable materials can be blended with polyesters such as polyethylene terephthalate, poly(cyclohexane-1,4-dimethylene) terephthalate; polyamides; mineral fibers such as asbestos and glass fibers. The flammable m~terials can be in the form of paper, woven textlle fabrics or non-woven fabxics.
The binder compositions are applied to the flammable material by methods well known in the art, such as, for exa~ple, by immersion in a.bath containing the binder t or by knife- .
~oating.
The practice of this invention is shown by the follow-ing examples, which are included here for purposes of illus~ra- .
25 tion only and are not intended as lLmitations. .:
. EXAMPLE 1 A polymer latex composition was prepared having the following constituents: 48% bis(~-chloroethyl)vinyl phosphonate, 29~ vinylidene chloride, 19% n-butyl acrylate, and 4~ N-methylol acrylamide, all percentages being by weight. The composition . ~ ,. .. . .. .
~50~'7'/' was prepared as an emulsion of 50% of solid content.
A pad bath was then charged with:
lOOg - above-described po]ymer latex t50% active) lOg - co-condensate of bis(~-chloroethyl)vinyl phosphonate and dimethyl methyl phosphonate tlOO% active) 25g - melamine-formaldehyde condensate, AEROTEX M-3, American Cyanamid Company (50% active) 20g - urea 0-8g - ~NH4)2S28 ~ -50g ~ ~2 ~ ~`
A sample of 1 1/2 ounce/square yard weight commercial non-woven celIulosi~ is employed as the flammable substrate. -The mixture in the pad bath was stirred to uniformity, and samples of the cellulosic cloth immersed therein. The exce s liquid was squeezed out and the sample cured at 170C.for 8 minutes. The dried samples were then burned according to ~TCC
method 34-1966. The results of the burn test are as follows: ;
% Add On Char Lenyth After Test .. :: -20 50 3" - non-burning 4 1/2" - non-burning 5" - non-burning 6" - non-burning 6 1/~" - non-burning ;~
0 burn entire length The samples were also washed for 5 minutes at 30C.
in water to test retention of fire retardant properties. The fire retardant propeFties remained.
--10-- ~
-~I~S~7'7 EX~MP_LE 2 In this example, the flammable substrate i5 a cloth of 65/35 blend of polyester/rayon. Th~ same pad bath and the procedure as employed in Example 1 gave a flame retardant fabric, the flame retardant property of whic:h was not lost by washing.
In these examples, the co-condensate of bis(~-chloro-ethyl)vinyl phosphonate and dimethyl methyl phosphonate in the formulation of Example 1, was replaced by an equal weight of PYROVATEX CP, THPOH, PHOSCHECX P30, respectively. The resulting baths imparted durable flame retardant properties to textile fabrics and non-woven fabrics, which if not treated with the latex will burn the entire length by the test described in Example 1.
. .
,, ~. '.,, . ~
FL~ME RETAR~ANT BINDER FOR FLAMMABLE MATERIALS
BACKGROUND OF THE INVENTION
. . ~
Copolymers of vinyl halides, vinylidene halides and various phorpho~us-containin~ vinyl monomers have been fre-quently used as fire retardant agents for various flammable materials, such as paper, cellulosic textlles and non-woven fabrics. For light weight and flexible substrates, there is a limit to how much polymer the substrates can pick up before flexibility and a soft hand are lost. In these cases, there is insufficient add-on to give reduced flammability. Inorganic salts such as diammonium phosphate and ammonium sulfamate have heretofore been used for this purpose; however, their water solubility has rendered their flame retardant property non-durable.
Thus, in accordance with the present teachings, a flame retardant polymer latex binder composition is provided which comprises (a) a polymer latex containing ~l) a bis(hydro- -carbyl) vinyl phosphonate of the formula: :
X O
~ OR' CH2 = C - P
~ OR, wherein X is selected from the group consisting of hydrogen, ~:
halogen, cyano 9 phenyl, C1-Cl8 alkyl and Il OR' ~ OR, and each of R and R' are hydrocarbyl or substituted hydrocarbyl having from 1 to 18 carbon atoms (2) a vinyl halide or vinylidene halide, (3) a Cl to C20 alkyl ester of acrylic acid, and optionally (4) a comonomer selected from the group consisting of acrylicacid, methacrylic acid, amides of acrylic acid and methacrylic acid, N-methylol derivati~es of the amides of acrylic acid and methacrylic acid, and diacetone derivatives of the amides of acrylic acid and methacrylic acid, (b) at least ~ ~ -2~
-1~5~ 77 one phorphorus containing compound selected ~rom the group consisting of a co-condensate of bist~ ~chloroethyl)vinyl phos-phonate and dimethyl methyl phosphonate, a condensate of bis (~ -chloroethyl)vinyl phosphonate~ tetrakisthydroxymethyl) phosphonium chloride or hydroxide, ~l~hydroxymethyl-3-(dimethyl-phosphoro)propionamide, tris(2,3-dibromopropyl phosphonate) and water-insoluble ammonium polyphosphate, water-insoluble ammonium salt of metaphosphoramidic acid, and mixtures thereo~, said water-insoluble phosphorus compounds being characterized by a water solubility of less than 25g/lOOcc at lO~C., (c) :
optionally urea, (d) an aminoplast selected from the group consisting of melamine formaldehyde and urea formaldehyde, and (e) optionally a phosphate plasticizer. -It has now been found that excellent and non-after~
glowing durable flame retardant properties are imparted to :
flammable materials when they are treated with a composition comprising the following components: (a) from about 20 to about 70 weight % of a polymer latex, (b) from about 3 to about 50 weight % of a phosphorus source, (c) from O to about 50 weight %
20 of urea, (d) a melamine formaldehyde or urea formaldehyde amino- ~- :
plast in about 10 to about SO weight ~, and (e) a phosphate ;; .
plasticizer in O to about 20 weight %. The components will now be more fully described.
Component (aj is a polymer latex derived from at least three monomers: (1) a bis(hydrocarbyl)vinyl phosphonate, (2) a vinyl halide or vinylidene halide, (3) an alkyl acrylate, and optionally (4) another derivative of acrylic or methacrylic :
' ' -2a-: . , . - , , ~: - ;:: , -,, ~ :
. - -s~
acid as more fully described below.
The bis(hydrocarbyl)~inyl phosphonate has thestrurture:
X O
' " OR'~
C~2 = C - p OR ,/
wherein X is selected from ~he group consisting of hydrogen, halogen, cyanot aryl such as phenyl, Cl-C18 alkyl and OR'`~
~ OR _l R and R' are hydrocarbyl and substituted hydrocarbyl groups consisting essentially of hydrogen and carbon and containing up to about 18 carbon atoms inclusive with the proviso that R and R' may be the same, different or conjoint, i.e., R and R' may combine to form one single radical. `~;~
The use, in this disclosure, of the expression ~ ;
"hydrocarbyl" and "substituted hydrocarbyl groups" in the definition of the suitable bis~hydrocarbyl)vinyl phosphonatss given hereinabove~ref~rs to the radicals obtained upon the remoYal of a hydrogen from a hydrocarbon or substituted hydro-carbon group which may be either an aliphatic or aro~atic group. These hydrocarbyl groups may be substituted with any ~on-interfering groups, i.e.~ with any group which does not interfere with the polymerization of the bis(hydrocarbyl)vinyl phosphonate. Such substituent groups include, for example, chloro, bromo, fluoro, nitro, hydroxy, sulfone, ethoxyt methoxy, nitrile, ether, ester and keto groups and the like.
, Illustrative of the aliphatic and aromatic groups as are represented by R and R' in the structure of-the bis(hydro- -carbyl~vinyl phosphonate givenhereinabove are alkyl groups, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, nonyl, and the like; alkenyl groups such as pentenyl and hexenyl groups and all of their respective isomers; cycloalkyl groups, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the liks;
cycloalkenyl groups, such as cyclohexenyl, and the like; typical aryl groups include phenyl, benzyl, phenethyl, tolyl, naphthyl, and the like.
~epresentative of the above-defined bis(hydrocarbyl~
vinyl phosphonat~s are:
bis(~-chloroethyl)vinyl phosphonate;
bis(~-chloropropyl)vinyl phosphonate;
bis(~-chloroethyl) l-methylvinyl phosphonate;
bis(~-chloroethyl) l-cyanovinyl phosphonate;
bis(~chloroethyl) l-chlorovinyl phosphonate;
bis(~chloroethyl) l-phenylvinyl phosphonate;
dimethyl vinyl phosphonate;
diethyl vinyl phosphonate;
bis(~-chlorobutyl)vinyl phosphonate;
di-n-butyl vinyl phosphonate;
di-isobutyl vinyl phosphonate;
bis(2-chloroisopropyl) l-methylvinyl phosphonate;
diphenyl vinyl phosphonate; and bis(2,3-dibromopropyl)vinyl phosphonate From the group of bis(hydrocarbyl)vinyl phosphonate monomers, it is preferred to employ bis(~-chloroethyl)vinyl phosphonate in preparing the novel aqueous emulsion polymers of this invention since the latter monomer is a commercially n available material and lower in cost than any of the other bis(hydrocarbyl)vinyl phosphonates.
The vinyl hallde or vinylidene halide may be, for example, vinyl chloride, vinyl bromide, vinyl fluoride, vinyli-dene chloride, vinylidene bromide, vinylidene chlorobromide or vinylidene fluoride. Preferred are vinyl chloride and vinylidene chloride.
~ The alkyl acrylate may be any Cl to C20 alkyl ester of acrylic acid, such as methyl acrylate, ethyl acrylate, n- .-butyl acrylate, sec.-butyl acrylate, 2-ethylhexyl acrylate, , 0~7~
lauryl acrylate or mixture thereoE. Preferred monomers are the C4-C8 alkyl acrylates such as n-butyl acrylate and 2-ethylhexyl acrylate.
The fourth monomer is another derivative of acrylic acid or a derivative of methacrylic acid, or may be the respec~
tive acids themselves. Among the derivatives are the amides and t.he N-mathylol and diacetone derivatives of the æmides. `:
Preferred are N-methylol acrylamide, acrylamide, acrylic acid ~ :~
and methacrylic acid. s The proportions of the various monomers forming component (a) are as follows: from about 10 to a~out 75 weight % of bis(h~drocarbyl)vinyl phosphonate, from about 20 to about 85 weight % of vinyl halide or vinylidene halide, from a~cut 5 to about 35 weight.% of alkyl acrylate, and from 0 to about 10 weight ~ of the fourth comonomer~
Specific latex polymers for component ~a) include .
the following: ;
: (1) a terpolymer of 30 parts by weight of vinylidene chloride, 20 parts by weight o~ n-bu~yl ae~rylate and 5O parts by weight of bis(beta-chloroethyl)vinyl phosphonate;
t2) a terpolymer containing 15 parts by weight o~
di-n-butyl vinyl phosphonate, 20 parts by weight of di-2-ethyl-hexyl acrylate and 65 parts by weight of vinylidene chloride; :
(3) a polymer containing 50 parts of bis(beta-chloroethyl)vinyl phosphonate, 25 parts of vinylidene chloride, - 20 parts of 2-ethylhexyl acrylate~ and 5 parts of N-methylol acrylamide;
~ 4) a polymer containing 45 parts by weight of vinylidene chloride, 35 parts by weight of bis(beta-chloroethyl) vinyl phosphonate, 15 parts by weight of n-butyl acrylate and ~5t~'7~
5 parts by weight of N-methylol acrylamide; and ~ 5) a polymer containing 30 parts by weight of bis(beta-chloroethyl)vinyl phosphonate, 5 parts by weight of propylene, 60 parts by weight of vinyl chloride and 5 parts by weight of N-methylol acryl~mide.
The polymers of the presen~ invention can be prepared by means of free radical initiated e!mulsion polymerization techniques well known to those skilled in the art. In these procedures r the various monomers and catalysts are emulsiied, in water, by means of one or more surface-active emulsifiers whereupon the polymerization reaction is then initiated.
Suitable water soluble, free radical initiating catalysts for use in preparing the copolymer latices of this invention include sodium,potassium and ammonium persulfate and hydrogen peroxide or one may use a redox system such, for example, as a mixture of a persulfate with an al~ali metal bisulfite, thiosulfate or -hydrosulfite. These catalysts should be present in a concentra-tion of from about 0.05 to 5.0%, by weight, of the total monomer charge. With respect to the emulsiier or surfactant, it is possible to utilize one or more anionic, cationic, or non-ionic emulsifiers such, for example, as the alkyl carboxylic ~ ;
acid salts; the alkyl sulfate, sulfonate, phosphate, or sul~o-succinamate salts; the alkyl aryl ether alcohols, and the alkyl aryl polyether sulfate salts. The selected emulsifier or emulsifiers should be present in effective concentration of from about 0.3 to 6.0%, hy weight, of the total monomex charge.
In addition, a protective colloid such 25 polyvinyl alcohol, polyvinyl pyrrolidone, methyl cellulose or gelatin can also, if desired, be present in the recipe in an effective concentra-tion of from about 0.03 to 6.0%, by weight, of the total ~3~;'7'7 ~-monomer charge. Alternatively, the protective colloid may be introduced into the copolymer latex subsequent to its prepara-tion. When post-added in this ma~ner, the protective colloid should be present in a concentration of from about 0.03 to 6.o~, by weight, of the total resin solids. In any event, the pre-sence of the protective colloid serves to enhance the mechanical stability of the emulsion.
The actual polymerization raaction will ordinarily be conducted at a temperature of from about 0 to 100C. for a period of from about 1 to 24 hoursJ depending upon such factors as the particular monomer, catalysts, surfactants and polymeriza-tion apparatus that is being utilized. The latices resulting from this polymerization process will ordinarily have a resin solids content of from about 5 to 7~, by weight, wherein the particles have a diameter which ranges in size from about 0.03 to 3.0 microns.
Component (b) is a source of phosphorus selected from the following: (i) a co-condensate of bis(~3-chloroethyl)vinyl phosphonate and dimethyl metbyl phosphonate or a condensate of bis(~3- chloroethyljvinyl phosphonate, (ii) tetrakis (hydroxymethyl) phosphoni~m halide or hydroxide, (iii) (N-'nydroxymethyl-3-dimethyl-phosphoro) propionamide, (iv) tris(2,3-dibromopropyl)phosphate3 (v) water-insoluble ammonium polyphosphate, and (vi) water-insoluble ammonium salt of metaphosphoroamidic acid.
The co~condensate of bis(~ -chloroethyl)vinyl phosphonate and dimethyl methyl phosphonate or the condensate of vinyl phosphonate is prepared by heating the mixtures of the two components or bis(f3-chloroethyl)vinyl phosphonate alone at about 100 to 250C. with a basic catalyst for about 2 to 12 hours resulting in a fluid liquid. A mixture of ethylene dichloride and methyl chloride or ethylene dichloride is generated as a by-product.
: - . - ,. -. - . . : , . . .
~05~'77 Tetrakis(hydroxymethyl) phosphonium chloride or hydroxide, also Xnown as ~IPC or THPOH has the structure:
(HOCH2)~PCl or (H()CH2)~PO~
and is sold by Hooker Chemical Corporation, a division of Occidental Petroleum Corporation.
N-hydroxymethyl-3-(dimethylphosphoro)propionamide has the structure:
O
(CH30)2-P-CH2CH2C-NHCH20H
and is sold under the trademark PYROVATEX CP by Ciba-Geigy Corporation.
, Tris(2,3-dibromopropyl phosphate) has the structure:
(cH2BrcHBrcH2o)3p=o and is sold under the trademark FYROL HB32 by Stauffsr Chemical Company.
Water-insoluble ammonium polyphosphate is made by heating ~-, ammonium phosphate with urea, and is known commercially as PHOSCHEK P30 sold by Monsanto Company.
~he water-insoluble ammonium salt of metaphosphoramidicacid ~ ;
is made by the reaction of ammonia with phosphorus pentoxide. -The term "water-insoluble" is meant to denoteij~that :' , :
the solubility of the phosphorus compound in water is less than ., 25g/lOOcc at 10C. or less than 75g/lOOcc at 70C.
Component (c), whose presence is optional, is urea. ` ;
Component (d) is a melamine formaldehyde or urea ;
formaldehyde aminoplast. Typical aminoplasts include such `
melamine/formaldehyde resins as AEROTEX M-3, AEROTEX 23 Special, AEROTEX MW and AEROTEX ResLn 44, all of said resins being available from American Cyanamid Company.
~ 7'~
Componsnt (e), whose presence is also optional, is a phosphate plasticizer. To illustrate, it can be alkyl acid phosphates, i.e., methyl acid phosphate, butyl acid phosphate; trialkyl phosphates, i.e., trioctyl phosphate, tri-dodecyl phosphate; triaryl phosphates, i.e., tricresyl phcsphate,cresyl diphenyl phosphate, i.e., octyl diphenyl phosphate, hutyl dicresyl phosphate, and the like.
The flammable materials treated by the compositions of this invention include cellulose, regenerated cellulose ~uch as rayon cellulose esters and mixed esters such as, for exampleO
cellulose nitra.te, cellulose acetate, cellulose acetate-butyrate, ;
cellulose acetate propionate and cellulose ethers such as, for example, ethyl cellulose and combinations thereof. In addition, ~ -tha~e flammable materials can be blended with polyesters such as polyethylene terephthalate, poly(cyclohexane-1,4-dimethylene) terephthalate; polyamides; mineral fibers such as asbestos and glass fibers. The flammable m~terials can be in the form of paper, woven textlle fabrics or non-woven fabxics.
The binder compositions are applied to the flammable material by methods well known in the art, such as, for exa~ple, by immersion in a.bath containing the binder t or by knife- .
~oating.
The practice of this invention is shown by the follow-ing examples, which are included here for purposes of illus~ra- .
25 tion only and are not intended as lLmitations. .:
. EXAMPLE 1 A polymer latex composition was prepared having the following constituents: 48% bis(~-chloroethyl)vinyl phosphonate, 29~ vinylidene chloride, 19% n-butyl acrylate, and 4~ N-methylol acrylamide, all percentages being by weight. The composition . ~ ,. .. . .. .
~50~'7'/' was prepared as an emulsion of 50% of solid content.
A pad bath was then charged with:
lOOg - above-described po]ymer latex t50% active) lOg - co-condensate of bis(~-chloroethyl)vinyl phosphonate and dimethyl methyl phosphonate tlOO% active) 25g - melamine-formaldehyde condensate, AEROTEX M-3, American Cyanamid Company (50% active) 20g - urea 0-8g - ~NH4)2S28 ~ -50g ~ ~2 ~ ~`
A sample of 1 1/2 ounce/square yard weight commercial non-woven celIulosi~ is employed as the flammable substrate. -The mixture in the pad bath was stirred to uniformity, and samples of the cellulosic cloth immersed therein. The exce s liquid was squeezed out and the sample cured at 170C.for 8 minutes. The dried samples were then burned according to ~TCC
method 34-1966. The results of the burn test are as follows: ;
% Add On Char Lenyth After Test .. :: -20 50 3" - non-burning 4 1/2" - non-burning 5" - non-burning 6" - non-burning 6 1/~" - non-burning ;~
0 burn entire length The samples were also washed for 5 minutes at 30C.
in water to test retention of fire retardant properties. The fire retardant propeFties remained.
--10-- ~
-~I~S~7'7 EX~MP_LE 2 In this example, the flammable substrate i5 a cloth of 65/35 blend of polyester/rayon. Th~ same pad bath and the procedure as employed in Example 1 gave a flame retardant fabric, the flame retardant property of whic:h was not lost by washing.
In these examples, the co-condensate of bis(~-chloro-ethyl)vinyl phosphonate and dimethyl methyl phosphonate in the formulation of Example 1, was replaced by an equal weight of PYROVATEX CP, THPOH, PHOSCHECX P30, respectively. The resulting baths imparted durable flame retardant properties to textile fabrics and non-woven fabrics, which if not treated with the latex will burn the entire length by the test described in Example 1.
. .
,, ~. '.,, . ~
Claims (13)
1. A flame retardant polymer latex binder composi-tion comprising (a) a polymer latex containing (1) a bis(hydro-carbyl)vinyl phosphonate of the formula:
wherein X is selected from the group consisting of hydrogen, halogen, cyano, phenyl, C1-C18 alkyl and and each of R and R' are hydrocarbyl or substituted hydrocarbyl having from 1 to 18 carbon atoms, (2) a vinyl halide or vinyli-dene halide, (3) a C1 to C20 alkyl ester of acrylic acid, and optionally, (4) a comonomer selected from the group consisting of acrylic acid, methacrylic acid, amides of acrylic acid and methacrylic acid, N-methylol derivatives of the amides of acrylic acid and methacrylic acid, and diacetone derivatives of the amides of acrylic acid and methacrylic acid, (b) at least one phosphorus containing compound selected from the group consisting of a co-condensate of bis(.beta.-chloroethyl)vinyl phos-phonate and dimethyl methyl phosphonate, a condensate of bis (.beta.-chloroethyl)vinyl phosphonate, tetrakis(hydroxymethyl) phosphonium chloride or hydroxide, N-hydroxymethyl-3-(dimethyl-phosphoro)propio:namide, tris(2,3-dibromopropyl phosphonate) and water-insoluble ammonium polyphosphate, water-insoluble ammonium salt of metaphosphoramidic acid, and mixtures thereof, said water-insoluble phosphorus compounds being characterized by a water solubility of less than 25g/100cc at 10°C., (c) optionally urea, (d) an aminoplast selected from the group consisting of melamine formaldehyde and urea formaldehyde, and (e) optionally a phosphate plasticizer.
wherein X is selected from the group consisting of hydrogen, halogen, cyano, phenyl, C1-C18 alkyl and and each of R and R' are hydrocarbyl or substituted hydrocarbyl having from 1 to 18 carbon atoms, (2) a vinyl halide or vinyli-dene halide, (3) a C1 to C20 alkyl ester of acrylic acid, and optionally, (4) a comonomer selected from the group consisting of acrylic acid, methacrylic acid, amides of acrylic acid and methacrylic acid, N-methylol derivatives of the amides of acrylic acid and methacrylic acid, and diacetone derivatives of the amides of acrylic acid and methacrylic acid, (b) at least one phosphorus containing compound selected from the group consisting of a co-condensate of bis(.beta.-chloroethyl)vinyl phos-phonate and dimethyl methyl phosphonate, a condensate of bis (.beta.-chloroethyl)vinyl phosphonate, tetrakis(hydroxymethyl) phosphonium chloride or hydroxide, N-hydroxymethyl-3-(dimethyl-phosphoro)propio:namide, tris(2,3-dibromopropyl phosphonate) and water-insoluble ammonium polyphosphate, water-insoluble ammonium salt of metaphosphoramidic acid, and mixtures thereof, said water-insoluble phosphorus compounds being characterized by a water solubility of less than 25g/100cc at 10°C., (c) optionally urea, (d) an aminoplast selected from the group consisting of melamine formaldehyde and urea formaldehyde, and (e) optionally a phosphate plasticizer.
2. A flame retardant polymeric latex binder composi-tion for application to flammable materials comprising (a) from about 20 to about 70 weight % of a polymer latex containing:
(1) a bis(hydrocarbyl)vinyl phosphonate of the formula:
wherein X is selected from the group consisting of hydrogen, halogen, cyano, phenyl, C1-C18 alkyl and and each of R and R' are hydrocarbyl or substituted hydrocarbyl having from 1 to 18 carbon atoms, (2) a vinyl halide or vinyli-dene halide, (3) a C1-C20 alkyl ester of acyrlic acid, and optionally, (4) a comonomer selected from the group consisting of acrylic acid r methacrylic acid, amides of acrylic acid and methacrylic acid, the N-methylol derivatives of the amides of acrylic acid and methacrylic acid, and diacetone derivatives of the amides of acrylic acid and methacrylic acid, (b) from about 3 to about 50 weight % of a phosphorus containing compound selected from the group consisting of a co-condenstae of bis(.beta.-chloroethyl)vinyl phosphonate and dimethyl methyl phosphonate, a condensate of bis(.beta.-chloroethyl)vinyl phosphonate, tetrakis (hydroxymethyl)phosphonium chloride or hydroxide, N-hydroxymethyl-3-(dimethylphosphoro)propionamide, tris(2,3-dibromopropyl phosphate), and water-insoluble ammonium polyphosphate, water-insoluble ammonium salt of metaphosphoramidic acid and mixtures thereof, said water-insoluble phosphorus compounds being characterized by a water solubility of less than 25g/100cc at 10°C., (c) from 0 to about 50 weight %
of urea, (d) from about 10 to about 50 weight % of an aminoplast selected from the group consisting of a melamine formaldehyde or a urea formaldehyde, and (e) from 0 to about 20 weight % of a phosphate plasticizer.
(1) a bis(hydrocarbyl)vinyl phosphonate of the formula:
wherein X is selected from the group consisting of hydrogen, halogen, cyano, phenyl, C1-C18 alkyl and and each of R and R' are hydrocarbyl or substituted hydrocarbyl having from 1 to 18 carbon atoms, (2) a vinyl halide or vinyli-dene halide, (3) a C1-C20 alkyl ester of acyrlic acid, and optionally, (4) a comonomer selected from the group consisting of acrylic acid r methacrylic acid, amides of acrylic acid and methacrylic acid, the N-methylol derivatives of the amides of acrylic acid and methacrylic acid, and diacetone derivatives of the amides of acrylic acid and methacrylic acid, (b) from about 3 to about 50 weight % of a phosphorus containing compound selected from the group consisting of a co-condenstae of bis(.beta.-chloroethyl)vinyl phosphonate and dimethyl methyl phosphonate, a condensate of bis(.beta.-chloroethyl)vinyl phosphonate, tetrakis (hydroxymethyl)phosphonium chloride or hydroxide, N-hydroxymethyl-3-(dimethylphosphoro)propionamide, tris(2,3-dibromopropyl phosphate), and water-insoluble ammonium polyphosphate, water-insoluble ammonium salt of metaphosphoramidic acid and mixtures thereof, said water-insoluble phosphorus compounds being characterized by a water solubility of less than 25g/100cc at 10°C., (c) from 0 to about 50 weight %
of urea, (d) from about 10 to about 50 weight % of an aminoplast selected from the group consisting of a melamine formaldehyde or a urea formaldehyde, and (e) from 0 to about 20 weight % of a phosphate plasticizer.
3. A composition according to claim 2 in which the polymer latex contains (1) from about 10 to about 75 weight %
of bis(hydrocarbyl)vinyl phosphonate, (2) from about 20 to about 85 weight % of vinyl halide or vinylidene halide, (3) from about 5 to about 35 weight % of alkyl ester of acrylic acid, and from 0 to about 10 weight % of the comonomer.
of bis(hydrocarbyl)vinyl phosphonate, (2) from about 20 to about 85 weight % of vinyl halide or vinylidene halide, (3) from about 5 to about 35 weight % of alkyl ester of acrylic acid, and from 0 to about 10 weight % of the comonomer.
4. A composition according to claim 3 in which, in the bis(hydrocarbyl)vinyl phosphonate, each of R and R' are alkyl, alkenyl, cycloalkyl or cycloalkenyl.
5. A composition according to claim 3 in which the bis(hydrocarbyl)vinyl phosphonate is selected from the group consisting of:
bis(.beta.-chloroethyl)vinyl phosphonate;
bis(.beta.-chloropropyl)vinyl phosphonate;
bis(.beta.-chloroethyl) 1-methylvinyl phosphonate;
bis(.beta.-chloroethyl) 1-cyanovinyl phosphonate;
bis(.beta.-chloroethyl) 1-chlorovinyl phosphonate;
bis(.beta.-chloroethyl) 1-phenylvinyl phosphonate;
dimethyl vinyl phosphonate;
diethyl vinyl phosphonate;
bis(.omega.-chlorobutyl)vinyl phosphonate;
di-n-butyl vinyl phosphonate, di-isobutyl vinyl phosphonate;
bis(2-chloroisopropyl) 1-methylvinyl phosphonate;
diphenyl vinyl phosphonate; and bis(2,3-dibromopropyl)vinyl phosphonate.
bis(.beta.-chloroethyl)vinyl phosphonate;
bis(.beta.-chloropropyl)vinyl phosphonate;
bis(.beta.-chloroethyl) 1-methylvinyl phosphonate;
bis(.beta.-chloroethyl) 1-cyanovinyl phosphonate;
bis(.beta.-chloroethyl) 1-chlorovinyl phosphonate;
bis(.beta.-chloroethyl) 1-phenylvinyl phosphonate;
dimethyl vinyl phosphonate;
diethyl vinyl phosphonate;
bis(.omega.-chlorobutyl)vinyl phosphonate;
di-n-butyl vinyl phosphonate, di-isobutyl vinyl phosphonate;
bis(2-chloroisopropyl) 1-methylvinyl phosphonate;
diphenyl vinyl phosphonate; and bis(2,3-dibromopropyl)vinyl phosphonate.
6. A composition according to claim 5 in which the bis(hydrocarbyl)vinyl phosphonate is bis(.beta.-chloroethyl)vinyl phosphonate, the vinyl halide is vinyl chloride, the vinylidene halide is vinylidene chloride, the alkyl ester of acrylic acid is n-butyl acrylate or 2-ethylhexyl acrylate, and the comonomer is selected from the group consisting of acrylic acid, methacrylic acid, acrylamide and N-methylol acrylamide.
7. Composition according to claim 6 in which the phosphorus containing compound is a co-condensate of bis(.beta.-chloroethyl)vinyl phosphonate and dimethyl methyl phosphonate.
8. Composition according to claim 6 in which the phosphorus containing compound is (N-hydroxymethyl-3-dimethyl-phosphoro)propionamide.
9. Composition according to claim 6 in which the phosphorus containing compound is tetrakis(hydroxymethyl) phosphonium chloride or hydroxide.
10. Composition according to claim 6 in which the phosphorus containing compound is tris(2,3-N-dibromopropyl phosphonate).
11. Composition according to claim 6 in which the phosphorus containing compound is ammonium polyphosphate.
12. Composition according to claim 6 in which the phosphorus containing compound is ammonium salt of metaphos-phoramidic acid.
13. Composition according to claim 6 in which the phosphorus containing compound is a condensate of bis(.beta.-chloroethyl)vinyl phosphonate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA211,889A CA1050677A (en) | 1974-10-21 | 1974-10-21 | Flame retardant binder for flammable materials |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA211,889A CA1050677A (en) | 1974-10-21 | 1974-10-21 | Flame retardant binder for flammable materials |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1050677A true CA1050677A (en) | 1979-03-13 |
Family
ID=4101420
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA211,889A Expired CA1050677A (en) | 1974-10-21 | 1974-10-21 | Flame retardant binder for flammable materials |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1050677A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10993437B2 (en) | 2013-06-18 | 2021-05-04 | Chemgreen Innovation Inc. | Anti-microbial polymer incorporating a quaternary ammonium group |
-
1974
- 1974-10-21 CA CA211,889A patent/CA1050677A/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10993437B2 (en) | 2013-06-18 | 2021-05-04 | Chemgreen Innovation Inc. | Anti-microbial polymer incorporating a quaternary ammonium group |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3883463A (en) | Flame retardant binder for flammable materials | |
| EP3004288B1 (en) | Non-halogen flame retardant polymers | |
| US3682871A (en) | Low temperature curing vinylidene-halide-unsaturated monocarboxylic acid-n-alkylol amide polymers | |
| US4397759A (en) | Fire retardant for polyolefins | |
| US4343854A (en) | Flame retardant composition | |
| US8568625B2 (en) | Aqueous dispersion of flame retardant for textiles and process for producing same | |
| US2832745A (en) | Aqueous flameproofing compositions and cellulosic materials treated therewith | |
| US3906136A (en) | Process of flame retarding substrates by applying hexahydratriazine phosphonate derivatives | |
| US3691127A (en) | Fire retardant vinyl chloride copolymer latices | |
| US4847143A (en) | Binder composition and nonwoven fabrics and impregnated papers using the same | |
| US3948842A (en) | Fire retardant polymeric additives of vinylidene halides with bis(hydrocarbyl) vinyl phosphonates and C1 -C20 alkylesters of acrylic and methacrylic acids | |
| CA1050677A (en) | Flame retardant binder for flammable materials | |
| EP0444647B1 (en) | Flame retardant composition and method of use | |
| US3695925A (en) | Process for flameproofing textiles | |
| KR20200020806A (en) | Copolymers, Resin Compositions, Processing Agents and Processed Products | |
| US4457969A (en) | Fire-resistant, light stable textile structure | |
| US4139476A (en) | Fire retardant polyolefins | |
| US3904570A (en) | Flame-retardant binder comprising vinylidene halide-bis(hydrocarbyl) vinyl phosphonate polymer latices blended with antimony oxide | |
| US4014839A (en) | Fire retardant polymeric additives | |
| IL45911A (en) | Flame retardant polymer latex binder compositions containing phosphorus compounds | |
| US4031054A (en) | Flame-retardant binder comprising vinylidene halide-bis(hydrocarbyl)vinyl phosphonate polymer latices blended with antimony oxide and chloroparaffin | |
| US3935149A (en) | Fire retardant aqueous emulsion copolymer additives | |
| US4014838A (en) | Fire retardant polymeric additives | |
| CA1052924A (en) | Fire retardant stable bis(hydrocarbyl) vinyl phosphonate copolymer latices | |
| CN108603332A (en) | Fibre finish, the manufacturing method of fiber process product and fiber process product |