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EP0547091A1 - Treillis a base de styrene bromes ignifuges - Google Patents

Treillis a base de styrene bromes ignifuges

Info

Publication number
EP0547091A1
EP0547091A1 EP91915369A EP91915369A EP0547091A1 EP 0547091 A1 EP0547091 A1 EP 0547091A1 EP 91915369 A EP91915369 A EP 91915369A EP 91915369 A EP91915369 A EP 91915369A EP 0547091 A1 EP0547091 A1 EP 0547091A1
Authority
EP
European Patent Office
Prior art keywords
monomer units
ring
composition
brominated aromatic
brominated
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.)
Withdrawn
Application number
EP91915369A
Other languages
German (de)
English (en)
Inventor
Jin-Liang Wang
Nicolai A. Favstritsky
Richard S. Rose
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Great Lakes Chemical Corp
Original Assignee
Great Lakes Chemical Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Great Lakes Chemical Corp filed Critical Great Lakes Chemical Corp
Publication of EP0547091A1 publication Critical patent/EP0547091A1/fr
Withdrawn legal-status Critical Current

Links

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
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/14—Copolymers of styrene with unsaturated esters
    • 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
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
    • C08F212/16—Halogens
    • C08F212/21—Bromine
    • 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
    • C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
    • C08F218/02—Esters of monocarboxylic acids
    • C08F218/04—Vinyl esters
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/06—Copolymers with styrene
    • C08L9/08—Latex

Definitions

  • This invention relates to the composition and preparation of polymer latices, particularly to such latices including ring-halogenated, ethylenically unsaturated aromatic monomers and at least one other monomer.
  • Acrylic, styrene-acrylic and vinyl-acrylic latices are commercially used in a variety of surface coatings. In many coatings applications, the latices used are desired to have flame-retarding properties. This applies in particular where latices are used in textiles, carpeting, paints, clear coatings, adhesives, sealants, caulking, non-woven binders and so on.
  • 3,877,974 describes the admixture of an aqueous dispersion of a halogenated organic compound and metallic oxide with a polymeric adhesive binder. Although this approach has been shown to provide the desired flame retardancy, many undesirable features are again introduced. Solids ultimately separate from the latex emulsion despite any dispersion techniques employed. The dispersions tend to be high in viscosity and impede application of the latex. Latex films become stiffer due to the presence of solids, interfering with the flexibility or "hand" of the latex. In addition, solids tend to have a pigmenting effect which masks or changes the color of the substrate.
  • Liquid compounds have been added to latices as well.
  • U.S. Patent No. 3,766,189 teaches the use of liquid chlorinated paraffin in a latex to achieve fire retardancy.
  • Drawbacks to the use of liquids include migration from the polymer with time, separation from the liquid latex emulsion, adverse effect upon adhesion, plasticizing, swelling of the latex, and poor water resistance. Salts and other water soluble solids eliminate the problems of settling of solids, but contribute other problems cited as well as generally having an adverse effect upon the stability of the latex emulsion.
  • Curable resin compositions containing a basic catalyst and a water solution of polymerized halogen-containing vinyl monomer and other vinyl monomers are disclosed in Japanese Patent No. 56120754-A2, issued to Mitsui Toatsu Chemicals on September 22, 1981.
  • the Mitsui patent reports that water based suspensions or emulsions of vinyl polymers have weak resistance to water, cracking and soiling (staining), and that the proposed compositions overcome such shortcomings.
  • the Mitsui patent is limited to treatment of water, cracking and soiling properties.
  • Patent Application No. 79200768.4 filed by Stamicarbon B.V. on December 15, 1979 (published July 9, 1980 as No. 13,052-A1).
  • the Stamicarbon application is directed to the preparation of plastic materials, including polyolefins, polystyrene, and copolymers of styrene and butadiene, styrene and acrylonitrile and ABS.
  • the plastics of the Stamicarbon application require high levels of bromine, and are described as containing 20-44 weight percent of bromine.
  • polymer latices which possess desired flame retardant properties. It is also important that such latices be able to be conveniently blended with other latices in the same manner as flame retardants.
  • the polymer latices of the present invention satisfy these needs, and are useful as fire retardant fabric backcoatings, coatings, paints, adhesives, sealants, caulking, non-woven binders and a variety of other applications .
  • polymer latices which comprise copolymers of ring-halogenated, ethylenically-unsaturated aromatic monomers and alkyl acrylate and/or methacrylate monomers, and which may also include at least one other monomer.
  • the halogenated aromatic monomers are present in an amount to provide from 7 to 20 weight percent bromine in the final latex composition.
  • the halogenated aromatic monomers include polybrominated monomers, particularly to provide monomers having an average of at least about 1.5 bromines per monomer unit.
  • compositions of the present invention are exemplified by three categories of latex compositions.
  • the latices include ring-brominated aromatic monomer units and second monomer units from alkyl acrylate monomer units, alkyl methacrylate monomer units, or combinations thereof.
  • the latices include these first two types of monomer units and further include third monomer units selected from unsaturated esters of saturated carboxylic acids, halogen-free aromatic monomers or unsaturated carboxylic acid monomers.
  • the latices include four monomer units, namely ring-brominated aromatic monomer units, alkyl acrylate and/or alkyl methacrylate monomer units, unsaturated carboxylic acid monomer units, and halogen-free aromatic monomers.
  • the present invention provides polymer latex compositions having advantageous physical properties making them useful for a wide variety of applications, and which latices have improved flame retardancy over prior art compositions.
  • Past efforts have failed to provide compositions of the described type, while it has now been discovered that the inclusion of ring-brominated aromatic monomer units in polymer latices provides improved flame retardancy without deleterious affects on other physical attributes of the compositions.
  • the brominated aromatic monomers may generally be included in a variety of latex compositions, 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 compositions 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.
  • One, two or more monomers may be reacted with, for example, brominated styrene to produce the copolymer latices of the present invention.
  • Careful selection of monomers used in conjunction with the brominated aromatic monomer enables production of flame retardant latices useful in a wide range of applications. These include textile backcoatings for woven upholstery and draperies, carpet backing, non-woven filter media binders, paints, adhesives, caulks, sealants- and the like.
  • the copolymer latices of the present invention contain a ring-brominated aromatic monomer and at least one other monomer.
  • the compositions of the present invention are exemplified by three categories of latex compositions.
  • the latices include ring-brominated aromatic monomer units and units selected from alkyl acrylate monomer units, alkyl methacrylate monomer units or combinations thereof.
  • the latices include these first two types of monomer units and further include third monomer units selected from unsaturated esters of saturated carboxylic acids, halogen-free aromatic monomers or unsaturated carboxylic acid monomers.
  • the latices include four monomer units, namely ring-brominated aromatic monomer units, alkyl acrylate and/or alkyl methacrylate monomer units, unsaturated carboxylic acid monomer units, and halogen-free aromatic monomers.
  • the present invention employs ring-brominated aromatic monomer units of the formula (I):
  • ring-halogenated aromatic monomers are styrene, methylstyrene, ⁇ -methylstyrene, -methyl methylstyrene, ethylstyrene or ⁇ -methyl ethylstyrene with bromine substitution (mono, di, tri and tetra) in the phenyl nucleus. Mixtures or mixed isomers of the above monomers may also be used.
  • the preferred ring-brominated aromatic monomer is polybrominated styrene, with dibromostyrene being most preferred.
  • a preferred dibromostyrene material is one available from Great Lakes Chemical Corporation of West Lafayette, Indiana, which material normally contains about 15 percent monobromostyrene and 3 percent tribromostyrene by weight.
  • the ring-brominated aromatic monomer is included in the overall latex composition in an amount to provide sufficient bromine to yield the desired flame retardancy.
  • the ring-brominated monomer is included in an amount to provide from 7 to 20 percent bromine by weight of the overall composition. More preferably, the ring-brominated monomer is included in an amount to give from 9 to 18 percent bromine by weight .
  • the ring-brominated aromatic monomer units include polybrominated units, and that the ring-brominated monomer units include an average of at least about 1.5 bromines per unit.
  • the ring-brominated aromatic monomer units it is preferred that at most about 20% of the ring-brominated aromatic monomer units be monobrominated.
  • the latex compositions be readily prepared.
  • the ratio of monobrominated and polybrominated monomer units in the latex be such that the corresponding mixture of the unsaturated ring-brominated aromatic monomers is liquid at room temperature.
  • a preferred material for use in the preparation of the latices of the present invention is the previously identified dibromostyrene composition as produced by Great Lakes Chemical Corporation, which composition is liquid at room temperature and comprises a mixture of 15 percent monobromostyrene, 82 percent dibromostyrene and 3 percent tribromostyrene .
  • Other mono- and polybrominated aromatic monomer mixtures which are liquid at room temperature are similarly preferred for preparation of the present latex compositions.
  • the mixtures preferably include as high an overall percentage of bromine as possible while still being a liquid at room temperature.
  • the polymer latices contain the ring-brominated aromatic monomer units (I) and also include alkyl (meth) acrylate monomer units of the formula (II) :
  • R 3 in which R, is -H or -CH_ , and R is an alkyl group of 1 to 20 carbon atoms.
  • Representative alkyl acrylates useful in accordance with the present invention are methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, n-amyl acrylate, n-hexyl acrylate, isohexyl acrylate, 2-ethylhexyl acrylate, n-heptyl acrylate, isoheptyl acrylate, 1-methyl-heptyl acrylate, n-octyl acrylate, isoctyl acrylates such as 6-methyl-heptyl acrylate, n-nonyl acrylate, isononyl acrylates such as 3 , 5 , 5-trimethylhexyl acrylates such as
  • the preferred monomers are ethyl acrylate, n-propyl acrylate, n-butyl acrylate and 2-ethylhexyl acrylate, and methyl methacrylate.
  • the hydroxy alkyl esters of acrylic acid or methacrylic acid are useful in this invention.
  • the latex compositions comprise the ring-brominated aromatic monomer units and the alkyl acrylate and/or alkyl methacrylate monomer units.
  • the ring-brominated aromatic monomer units are preferably present in an amount to provide from 7 to 20 percent, and more preferably from 9 to 18 percent, bromine by weight of the overall composition.
  • the ring-brominated aromatic monomer units preferably include an average of at least about 1.5 bromines per unit.
  • the composition consists essentially of the ring-brominated aromatic monomer units and the alkyl acrylate/methacrylate monomer units.
  • the polymer latices include the ring-brominated aromatic monomer units (I) and the alkyl acrylate/methacrylate monomer units (II), and further include third monomer units of either unsaturated esters of saturated carboxylic acid monomer units (III), non-brominated aromatic monomer units (IV) or carboxylic acid monomer units (V) .
  • the acid ester monomer units have the formula (III):
  • R. is an alkyl group of 1 to 3 carbon atoms
  • Representative acid ester monomer units include vinyl acetate, vinyl propionate and vinyl butyrate, with vinyl acetate being preferred.
  • the non-brominated aromatic monomer units have the formula (IV) :
  • Typical halogen-free aromatic monomers are styrene, ⁇ -methylstyrene, methylstyrene, ⁇ -methyl methylstyrene, ethylstyrene and ⁇ -methyl ethylstyrene, with styrene or ⁇ -methylstyrene being preferred.
  • the carboxylic acid monomer units have the formula (V) :
  • R is -H or -CH_ .
  • Representative ethylenically unsaturated carboxylic acid monomers are acrylic acid, methacrylic acid, itaconic acid, maleic acid and furaaric acid.
  • the preferred acids are acrylic and methacrylic acids .
  • the latices consist essentially of the ring-brominated aromatic monomer units (I), the alkyl acrylate/methacrylate monomer units (II), and the third units selected from the group consisting of the acid ester monomer units (III), the non-brominated aromatic monomer units (IV) and the carboxylic acid monomer units (V) .
  • polymer latices including the ring-brominated aromatic monomer units (I), the alkyl acrylate/methacrylate monomer units (II), non-brominated aromatic monomer units (IV) and carboxylic acid monomer units (V).
  • the latices consist essentially of the ring-brominated aromatic monomer units (I), the alkyl acrylate/methacrylate monomer units (II), the non-brominated aromatic monomer units (IV) and the carboxylic acid monomer units (V) .
  • the latices of the present invention may be prepared in accordance with conventional methods.
  • the latices are prepared by polymerizing in the emulsion system (water, emulsifier, initiator, and chain transfer agent) 100 parts by weight total monomers in the ratio desired in the polymer.
  • Techniques for preparation of the latices include emulsion polymerization and dispersion of polymers prepared by solution, bulk or suspension polymerization.
  • Suitable initiators include the initiators used for free radical polymerization such as organic peroxides, hydroperoxides, azo or diazo compounds, persulfates, redox systems, etc.
  • Suitable emulsifiers include anionic, cationic, nonionic or amphoteric emulsifiers.
  • Useful chain transfer agents include aliphatic, aryl mercaptans and disulfides, CC1., CBr., CHI_ and CHC1 belonging , etc. Among these, 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 80°C.
  • the polymer latices of the present invention are useful as fire retardant fabric backcoatings, coatings, paints, adhesives, sealants, caulking, non-woven binders, etc. Monomer selection is based upon the final application of the latex. Criteria include the glass transition temperature (Tg), physical properties and chemical resistance desired.
  • Tg glass transition temperature
  • the flame retardant latices of the present invention may be admixed with other latex compositions, including non-flame retardant latices, to provide resulting latices and coatings having enhanced properties. In particular, 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 previously indicated, for the resulting combined latices and coatings. Improvement in properties may also be achieved for such mixtures with respect to such aspects as adhesion, film forming, chemical resistance and flexibility.
  • a series of emulsion polymerizations of dibromostyrene (DBS)/2-ethylhexyl acrylate (2-EHA) were carried out in 8 oz. bottles. All the ingredients (122.50 or 180 parts by weight deionized water, 3 parts sodium dodecyl sulfate, 0.3 parts potassium persulfate, 0.2 parts t-dodecyl mercaptan and 100 parts total monomers in the ratio desired in the polymer) were charged into 8 oz. bottles and flushed well with nitrogen, and then reacted at 50°C to about 45.8 or 36.5% solids in 15 hr.
  • DBS dibromostyrene
  • EHA ethylhexyl acrylate
  • Excellent latex compositions are similarly obtained by repetition of the foregoing methods with, for example, ethyl acrylate, n-propyl acrylate and n-butyl acrylate.
  • Examples 1-5 The general procedure of Examples 1-5 was repeated to prepare terpolymer latices which contained 0-30 percent by weight of dibromostyrene (DBS), 15-80 percent by weight of 2-ethylhexyl acrylate (2-EHA) and 10-85 percent by weight of vinyl acetate (VAc) .
  • the reaction reached 95-100% conversion at 34.7-36.5% solids in 15-16.25 hr at 50°C, as shown in Table II.
  • good latex compositions are obtained by repetition of the foregoing preparation with replacement of the 2-ethylhexyl acrylate with ethyl acrylate, n-propyl acrylate, n-butyl acrylate and methyl methacrylate, and with replacement of the vinyl acetate with vinyl propionate and vinyl butyrate.
  • the latices perform well in a variety of coating applications, and display improved flame retardancy.
  • Examples 1-5 The general procedure of Examples 1-5 was repeated to prepare terpolymer latices which contained 0-20 percent by weight of dibromostyrene (DBS) , 10-60 percent by weight of 2-ethylhexyl acrylate (2-EHA) and 20-90 percent by weight of styrene (S) .
  • the monomers were polymerized to 91-100 percent conversion at 33.2-36.5 percent solids in 15-18.25 hr at 50°C, as indicated in Table III.
  • good latex compositions are obtained by repetition of the foregoing preparation with replacement of the 2-ethylhexyl acrylate with ethyl acrylate, n-propyl acrylate, n-butyl acrylate and methyl methacrylate, and with replacement of the styrene with methylstyrene, ⁇ -methylstyrene, ⁇ -methyl methylstyrene, ethylstyrene and ⁇ -methyl ethylstyrene.
  • the latices perform well in a variety of coating applications, and display improved flame retardancy.
  • Emulsion polymerizations of dibromostyrene (DBS)/ethyl acrylate (EA) or butyl acrylate (BA)/methacrylic acid (MAA) were carried out in 8 oz. bottles.
  • the ingredients comprising 103.67 parts by weight deionized water, 3 parts sodium dodecyl sulfate, 0.3 parts potassium persulfate, 0.3 parts sodium bisulfite, with 0.2 parts or without t-dodecyl mercaptan, and 20-30 parts DBS, 0-80 parts EA or BA and 0-8 parts MAA were charged into 8 oz.
  • Examples 18-24 The general procedure of Examples 18-24 was repeated to prepare terpolymer latices which contained 20-25 percent by weight of dibromostyrene (DBS), 0-65 percent by weight of 2-ethylhexyl acrylate (2-EHA) or ethyl acrylate (EA) , and 15-23 percent by weight of methyl methacrylate (MMA) .
  • DBS dibromostyrene
  • EHA 2-ethylhexyl acrylate
  • EA ethyl acrylate
  • MMA methyl methacrylate
  • good latex compositions are obtained by repetition of the foregoing preparation with replacement of the 2-EHA or EA with n-propyl acrylate and butyl acrylate, and with replacement of the MMA with ethyl methacrylate, isopropyl methacrylate and t-butyl methacrylate.
  • the latices perform well in a variety of coating applications, and display improved flame retardancy.
  • Examples 29-30 The general procedure of Examples 29-30 was repeated to prepare tetrapolymer latices which contained 0-30 percent by weight of dibromostyrene (DBS) , 55-78 percent by weight of butyl acrylate (BA) , 0-43 percent by weight of styrene (S) and 2-3 percent by weight of methacrylic acid (MAA) .
  • the reaction reached 94-97 percent conversion at 43.9-46.2 percent solids at 65°C in 3.67-19.75 hr, as shown in Table VII.
  • the product was cooled to 30°C, strained, and the pH adjusted to 9.5 with 2-amino-2-methyl-l-propanol .
  • good latex compositions are obtained by repetition of the foregoing preparation with replacement of the butyl acrylate with ethyl acrylate, n-propyl acrylate and 2-ethylhexyl acrylate, with replacement of the styrene with methylstyrene, ⁇ -methylstyrene, ⁇ -methyl methylstyrene, ethylstyrene and ⁇ -methyl ethylstyrene, and with replacement of the methacrylic acid with acrylic acid.
  • the latices perform well in a variety of coating applications, and display improved flame retardancy, indicated by an oxygen index of 24.
  • ethylenically-unsaturated, ring-brominated aromatic monomers such as methylstyrene, ⁇ -rrtethylstyrene, ⁇ -methyl methylstyrene, ethylstyrene and ⁇ -methyl ethylstyrene (with mono, di, tri and tetra bromine substitution in the benzene ring).
  • brominated aromatic monomers including polybrominated units, and especially mixtures which are liquid at room temperature and have an average of at least 1.5 bromines per unit, permit ready preparation of the inventive latices, and yield compositions which have improved flame retardancy and good physical properties.
  • 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 products.

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  • Fireproofing Substances (AREA)

Abstract

L'invention décrit des treillis ignifuges améliorés en polymère, comprenant des copolymères à unités monomères aromatiques halogénées cycliquement et à unités monomères d'acrylate/méthacrylate alkyle et pouvant comporter de plus, un autre monomère au moins. Dans un premier aspect de l'invention, le treillis comprend des unités monomères aromatiques bromées cycliquement et des unités monomères d'acrylate alkyle et/ou de méthacrylate alkyle. Dans un deuxième aspect de l'invention, le treillis comprend ces deux premiers types d'unités monomères et comprend, de plus, un troisième type d'unités monomères provenant d'esters insaturés d'acides carboxyliques saturés, de monomères aromatiques exempts d'halogènes ou de monomères d'acides carboxyliques insaturés. Dans un troisième aspect de l'invention, le treillis comprend quatre unités monomèrs, notamment des unités monomères aromatiques bromées cycliquement, des unités monomères d'acrylate/méthacrylate alkyle, des unités monomères aromatiques exemptes d'halogènes et des unités monomères d'acides carboxyliques insaturés. Dans l'un des aspects, les monomères aromatiques halogénés sont présents en quantité suffisante pour produire entre 7 et 20 % en poids de brome dans la composition finale de latex. Dans un autre aspect, les monomères aromatiques halogénés comprennent des monomères polybromés, particuliérement pour produire des monomères dont la moyenne en brome représente au moins 1,5 par unité monomère.
EP91915369A 1990-09-06 1991-08-21 Treillis a base de styrene bromes ignifuges Withdrawn EP0547091A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US579063 1984-02-10
US57906390A 1990-09-06 1990-09-06

Publications (1)

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EP0547091A1 true EP0547091A1 (fr) 1993-06-23

Family

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Application Number Title Priority Date Filing Date
EP91915369A Withdrawn EP0547091A1 (fr) 1990-09-06 1991-08-21 Treillis a base de styrene bromes ignifuges

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EP (1) EP0547091A1 (fr)
JP (1) JPH06500812A (fr)
KR (1) KR930702408A (fr)
AU (1) AU653548B2 (fr)
CA (1) CA2049857A1 (fr)
IL (1) IL99392A (fr)
MX (1) MX174495B (fr)
TW (1) TW203614B (fr)
WO (1) WO1992004387A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101519563B (zh) * 2008-10-10 2012-03-21 兰州理工大学 溴碳丙烯酸隧道防火涂料及其制备方法

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2718851B2 (ja) * 1992-04-07 1998-02-25 帝人化成株式会社 ブロモ化スチレンの乳化重合法
US5304618A (en) * 1993-07-22 1994-04-19 Great Lakes Chemical Corporation Polymers of brominated styrene
CN105968255B (zh) * 2016-06-28 2018-03-09 合众（佛山）化工有限公司 一种自阻燃型丙烯酸乳液及其制备方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3072588A (en) * 1958-10-13 1963-01-08 Dow Chemical Co Method of preparing aqueous latex of high molecular weight vinylbenzyl halide polymer and resulting product
NL7812460A (nl) * 1978-12-22 1980-06-24 Stamicarbon Broombevattend polymeer en werkwijze voor het bereiden van een broombevattend polymeer.
US5066752A (en) * 1990-06-20 1991-11-19 Great Lakes Chemical Corporation Flame retardant brominated styrene-based polymers

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9204387A1 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101519563B (zh) * 2008-10-10 2012-03-21 兰州理工大学 溴碳丙烯酸隧道防火涂料及其制备方法

Also Published As

Publication number Publication date
IL99392A0 (en) 1992-08-18
JPH06500812A (ja) 1994-01-27
CA2049857A1 (fr) 1992-03-07
AU8449891A (en) 1992-03-30
WO1992004387A1 (fr) 1992-03-19
TW203614B (fr) 1993-04-11
KR930702408A (ko) 1993-09-09
IL99392A (en) 1994-07-31
MX174495B (es) 1994-05-18
AU653548B2 (en) 1994-10-06

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