Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
  • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
  • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
  • C08F236/10—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with vinyl-aromatic monomers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D109/00—Coating compositions based on homopolymers or copolymers of conjugated diene hydrocarbons
  • C09D109/10—Latex

Definitions

• This invention relates to flame retardant latex coatings, and particularly to coatings prepared from compositions such as dibromostyrene-butadiene and
• Styrene based copolymers and terpolymers have found many applications in the prior art.
• Styrene-butadiene rubbers (SBR) containing low styrene proportions (15-35%) have been used for many applications, including tires, retreading, belting, footwear, wire and cable coating, sponge rubber, pressure-sensitive tape, reinforcement plastics and
• Styrene-butadiene latices containing varying amounts of styrene (15-65%) have been used in fabric-to-rubber
• these flame retardants have a major disadvantage in that the processing of plastics incorporating brominated flame retardants can give rise to problems.
• the flame retardant or decomposition products thereof may be released during processing. This can cause an offensive odor, and in certain cases noxious compounds may be
• these flame retardants may be any flame retardants released.
• these flame retardants may be any flame retardants released.
• bromine-containing flame retardants for the most part they also have the disadvantage of adversely influencing the mechanical properties of the plastics.
• copolymer coatings comprising ring-halogenated, ethylenically unsaturated aromatic monomers and aliphatic conjugated dienes having from 4 to 10 carbon atoms.
• Copolymer coatings according to the present invention include compositions represented by the formula:
• n is an integer;
• R 1 is H or CH 3 ;
• R 2 is H or a C 1 - 4 lower alkyl group;
• R 3 is H, Cl or CH 3 ; and
• x 1 to 4.
• Terpolymers according to the present invention include compositions represented by the formula:
• n is an integer;
• R 1 is H or CH 3 ;
• R 2 is H or a
• the copolymer and terpolymer coatings of the present invention have a molecular weight of at least about 25,000. Preferably, the molecular weight is at least about 100,000.
• a further object of the present invention is to provide coatings utilizing ring-halogenated aromatic monomers in partial or total substitution for non-halogenated aromatic monomers used in prior art compositions.
• the present invention provides styrene based coatings having improved flame retardancy.
• styrene-butadiene rubbers, styrene-butadiene resins and styrene-butadiene latices imparts fire retardancy and
• the brominated aromatic monomers may generally be included in a variety of latex coatings, including but not limited to those in which non-brominated aromatic monomers have been known to be useful.
• the brominated monomers may be used in partial or total replacement of such non-brominated monomers. It is an aspect of the present invention that the described ring-brominated aromatic monomers may be used in the wide-ranging prior art coatings in which non-brominated aromatic monomers have been employed, with the consequent advantage being the achievement of improved flame retardancy without detrimental impact on the physical properties of the latex.
• coatings is used in a broad sense and is intended to include applications to a substrate both as a laminate or as an interstitial filler. For example, included are uses as textile backcoatings for woven
• flame retardant copolymer coatings comprising units from ring-halogenated
• flame retardant terpolymer coatings comprising units from
• the ring-halogenated monomers of both the copolymer and terpolymer coatings include mono-, di-, tri- and tetrabromoforms of styrene, methylstyrene, ⁇ -methylstyrene,
• dibromostyrene normally contains about 15 percent
• the ring halogen may be either chlorine or bromine, and is preferably bromine.
• the ring-halogenated aromatic monomers are included in an amount to provide between about 10 and about 60 percent of bromine by weight based on the total weight of the coating.
• the conjugated diene monomers for both the copolymers and terpolymers preferably have from 4 to 10 carbon atoms, and may be of the type used in related prior art compositions. Representative of the conjugated diene monomers are
• chloroprene piperylene and other hydrocarbon homologs of 1,3-butadiene.
• the preferred monomer is butadiene,
• chloroprene or isoprene particularly butadiene.
• the ring-halogenated aromatic monomer is used in an amount to provide from about 95 to about 5 percent by weight of the monomer based on total weight of the copolymer.
• ring-halogenated aromatic monomer is about 88 to about 25 percent by weight. Also for the
• the conjugated diene is used in an amount to provide from about 5 to about 95 percent by weight, preferably from about 12 to about 75 percent by weight, of the conjugated diene monomer based on total weight of the coating.
• Copolymer coatings according to the present invention include compositions represented by the formula:
• n is an integer;
• R 1 is H or CH 3 ;
• R 2 is H or a C 1 - 4 lower alkyl group;
• R 3 is H, Cl or CH 3 ; and
• x 1 to 4.
• halogen-free aromatic monomers as well as the ring-halogenated aromatic monomers and the conjugated diene monomers.
• Representative halogen-free aromatic monomers are styrene, ⁇ -methylstyrene, methylstyrene, ⁇ -methyl
• methylstyrene ethylstyrene and ⁇ -methyl ethylstyrene.
• the preferred halogen-free aromatic monomer is styrene or ⁇ -methylstyrene.
• the ring-halogenated aromatic monomer is used in an amount to provide from about 90 to about 5 percent by weight of the monomer based on total weight of the coating.
• ring-halogenated aromatic monomer is about 40 to about 20 percent by weight.
• the terpolymer coatings comprises about 5 to about 95 weight percent, preferably about 10 to about 68 weight percent, based on total weight of the coating. Also for the terpolymer coatings, the
• conjugated diene is used in an amount to provide from about 90 to about 5 percent by weight, preferably from about 50 to about 12 percent by weight, of the aliphatic conjugated diene monomer based on total weight of the coating.
• Terpolymer coatings according to the present invention include compositions represented by the formula:
• n is an integer;
• R 1 is H or CH 3 ;
• R 2 is H or a
• the copolymer and terpolymer coatings of the present invention have a molecular weight of at least about 25,000. Preferably, the molecular weight is at least about 100,000.
• Suitable initiators include the initiators used for free radical polymerization such as organic peroxides,
• hydroperoxides azo or diazo compounds, persulfates, redox systems, etc.
• Useful emulsifiers include anionic, cationic, nonionic or amphoteric.
• Chain transfer agents include
• CHI 3 and CHCl 3 etc.
• mercaptans are preferred.
• Polymerization may be carried out in the presence of air. Faster reactions are observed in the absence of oxygen at temperatures ranging from -30° to 110°C, with preferred
• temperatures ranging from about 0°C to about 60°C.
• Polymerization may be terminated short of completion to yield products having selected molecular weights. For example, termination at 45-75% conversion generally yields product wnich is non-crosslinked latex and its coagulated polymer.
• Termination at 75-100% conversion generally produces product comprising crosslinked latex and its coagulated polymer.
• the latices and the resultant coatings can be stabilized by incorporation of 0.5 to 4 parts antioxidant per 100 parts polymer, preferably 1 to 2 parts antioxidant. Suitable
• antioxidants include alkylated-arylated bisphenolic phosphite, tris(nonyl ⁇ henyl)phosphite, styrenated phenol,
• the flame retardant latices used in the present invention may be admixed with other latex compositions, including
• the combination of the flame retardant latices used herein with other latices will yield coatings having improved flame retardancy.
• the latices of the present invention may then be provided with sufficient levels of bromine to yield the desired levels, such as
• a soap solution (a mixture of 180 parts deionized water, 5 parts sodium dodecyl sulfate, 0.3 parts potassium persulfate, and 0.3 parts sodium bisulfite) was prepared and charged into a 32 oz. bottle. To the bottle, a mixture of 20-88 parts
• the bottle (with cap) was weighed on a balance, and 12-80 parts butadiene added slowly until an excess (1 to 2 parts) was present. The cap was then placed loosely on the neck of the bottle, and the butadiene was allowed to evaporate until the correct weight was established. The cap was sealed with rubber and TEFLON gaskets and was then tightened quickly by hand using rubber gloves. The bottle was placed in a clamp in a 50°C water bath and rotated. The reaction was allowed to run for a certain period of time (2 to 20.75 hr), after which the bottle was removed from the water bath and placed in ice-water for 10 minutes.
• the chilled bottle was then tested for pressure by inserting a needle through the cap. When no pressure was apparent, the bottle was opened and the contents dripped into a 6% aqueous MgSO 4 solution under stirring, followed by
• Vanox L butylated reaction product of p-cresol
• a 2 1 Parr reactor was charged with a soap solution of 1014 g deionized water, 28 g sodium dodecyl sulfate, 1.87 g sodium bicarbonate, 1.87 g potassium persulfate and 1.87 g sodium bisulfite.
• soap solution 1014 g deionized water, 28 g sodium dodecyl sulfate, 1.87 g sodium bicarbonate, 1.87 g potassium persulfate and 1.87 g sodium bisulfite.
• soap solution was added a mixture of 420 g dibromostyrene and 0.98 g n-dodecyl mercaptan, followed by the addition of 140 g butadiene.
• the contents of the reactor were allowed to react for one and a half hours to 30 percent solids; the
• Example 11 The general procedure of Example 11 was repeated here to prepare a terpolymer which contained 19 weight percent of dibromostyrene, 67 weight percent of styrene and 14 weight percent of butadiene.
• the monomers were polymerized to approximately 100 percent conversion at 37 percent solids in 2.5 hr, and the temperature was gradually increased from room temperature to 65°C.
• the coagulated terpolymer was soluble in tetrahydrofuran, chloroform and toluene and had an average molecular weight of 119,000 relative to polystyrene.
• Table V The result of the preparation is tabulated in Table V.
• ethylenically-unsaturated, ring-brominated aromatic monomers such as methylstyrene, ⁇ -methylstyrene, ⁇ -methyl
• methylstyrene, ethylstyrene and ⁇ -methyl ethylstyrene (with mono, di, tri and tetra bromine substitution in the benzene ring).
• the latices yield coatings which have improved flame retardancy and good physical properties and are useful in a variety of coating applications.
• superior flame retardant latex compositions are obtained by preparations according to the earlier Examples with the use of alternate monomers as described previously in the text. The choice of monomers is primarily dependent on the physical properties desired for the resulting latices, and the presence of the ring-brominated aromatic monomer units provides increased flame retardancy for the resultant coatings.
• the latex preparation described in Examples 21 was used to prepare a latex containing 30% by weight of monomer dibromostyrene, 40% by weight styrene, and 30% by weight of butadiene.
• the resulting latex was allowed to cool and applied to the back of an 8 oz/yd 2 100% polyester velvet with a lab coating device. Total add-on after drying was 1.2 oz/yd 2 .
• Example 22 The latex composition of Example 22 was placed into a tray. A non-woven polyester fiber filter medium weighing about 1.25 oz/yd 2 was pulled through the latex, assuring complete immersion. Upon drying at 300°F for one minute, the filter media was weighed and found to have a dry pick up of
• a second sample of latex was prepared substituting 30 parts styrene for dibromostyrene.
• the dry pick up was 81%.
• Both filter media samples were tested for flammability by exposure to a 4 in. high, 1950°F propane flame from a Fisher Burner.
• the filter medium was held 2-1/2 in. over the top of the burner at a 15° angle from horizontal.
• Precoat compounds were applied to carpet direct from a tufting machine.
• the carpet consisted of 100% nylon face fibers having a weight of 29 oz/yd 2.
• the following procedure was used to prepare the latex emulsion: 105.7 parts (by weight) deionized water, 3.5 parts sodium dodecyl sulfate, 0.3 parts potassium persulfate, and 0.3 parts sodium bisulfite were added to a quart bottle.
• the bottle was capped and rotated about a
• the latex emulsion was neutralized to pH 7 with ethylenediamine.
• a second latex was made similarly, substituting 18 parts dibromostyrene for 18 parts styrene.
• For each 100 parts by weight of solids in the latex emulsions 0.5 parts sodium hexametaphosphate, 0.5 Dow Corning Antifoam B, 600 parts CaCO 3 , and 2.5 parts Rohm & Haas ASE-60 acrylate thickeners were added.
• a labcoater was used to obtain an applied weight of 18 oz/yd 2 on the carpet back once the carpet was oven dried. Table VII below summarizes the results of DOC.
• the precoated carpet in Example 24, Number 1 was used as a substrate for a secondary jute backing. This precoating carpet does not meet the flammability criteria of DOC.
• the latex compositions were prepared essentially as in
• Example 24 the only changes being a modification in polymer ratio and reduction of the CaCO 3 filler level to improve adhesion. Upon drying, the secondary jute backing adhered well to the carpet even after repeated mild flexing.
• dibromostyrene can be used in either the precoat or secondary backing adhesive to confer flame retardancy. It should be noted that after exposure to ultraviolet light, the latex C showed little or no discoloration. A darkening was observed for latex B, indicating that aromatic monomers used in conjunction with dibromostyrene may be undesirable in some applications.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Wood Science & Technology (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Paints Or Removers (AREA)

Applications Claiming Priority (2)

Publications (1)

Family

ID=24428603

Family Applications (1)

Country Status (7)

Families Citing this family (2)

• 1991
  • 1991-10-23 WO PCT/US1991/007807 patent/WO1992007915A1/en not_active Application Discontinuation
  • 1991-10-23 JP JP4501827A patent/JPH06502672A/ja not_active Withdrawn
  • 1991-10-23 AU AU90609/91A patent/AU9060991A/en not_active Abandoned
  • 1991-10-23 EP EP19920900667 patent/EP0555386A1/en not_active Withdrawn
  • 1991-10-29 IL IL9988891A patent/IL99888A/en not_active IP Right Cessation
  • 1991-10-30 MX MX9101860A patent/MX174003B/es not_active IP Right Cessation
  • 1991-10-30 CA CA 2054499 patent/CA2054499A1/en not_active Abandoned

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events