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    Production of granular expandable thermoplastic compositions
    8.
    发明专利
    Production of granular expandable thermoplastic compositions 未知

    公开(公告)号：GB1030013A

    公开(公告)日：1966-05-18

    申请号：GB968363

    申请日：1963-03-12

    Applicant: BASF AG

    Inventor： DAUMILLER GUENTHER ,  HERRLE KARL ,  RAUSCHENBACH ROLF DIETER

    IPC: C08J9/00 ,  C08J9/16 ,  C08L25/00 ,  C08L27/04

    Abstract: A granular thermoplastic composition comprises an intimate mixture of (A) at least one substantially halogen free polymer or copolymer derived from aromatic or cycloaliphatic vinyl compounds, (B) at least one polymer or copolymer of vinyl chloride or vinylidene chloride, (C) 2-20% of a gaseous or liquid expanding agent, the weight of (A) being at least 1 1/2 times that of (B) and the chlorine content of the composition being 8-25%. Copolymers (A and (B) may contain up to 30 and 40% respectively of units other than those specified above. In addition to (A) and (B) the composition may contain up to 20% of other polymers and copolymers. Other additives may be: flame retardants, e.g. SbO3, 1,2,5,6,9,10-hexabromocyclododecane, hexabromocyclohexane and tris - (2,3 - di - bromopropyl) phosphate; flame retardant activators, e.g. dicumyl peroxide; plasticizers, e.g. polyvinyl pyrrolidone, hydroxyethyl cellulose, BaSO4 and CaHPO4; organic and inorganic fillers and colouring matter. The composition may be formed by polymerizing the monomer precursors of (A) in aqueous suspension, adding the monomer precursors of (B) and polymerizing them. The first polymerization may be carried out at 50-120 DEG C. in the presence of 0.1-2.0% catalysts, e.g. dibenzoyl peroxide, lauroyl peroxide or azodiisobutyronitrile and 0.0573.0% plasticizers. 0.1-3.0% of catlyst may be added before the second polymerization at 30-80 DEG C. The expanding agent may be added prior to, during or after the second polymerization. In an alternative method polymers (A) and (B) in a plasticized state may be mixed with the other additives in an extruder at 60-220 DEG C. and the resulting solidified composition may be granulated. (A) may be derived from acrylonitrile, acrylic esters, methacrylic esters, acrylamide, maleic esters, itaconic esters, divinyl benzene or butadiene in addition to styrene, a -methyl styrene, o- and p-vinyl toluene and vinyl cyclohexane. Polyvinyl cycloaliphatic compounds may be derived by hydrogenation of polyvinyl aromatic compounds. Copolymers (B) may be partially derived from acrylonitrile, maleic esters, acrylic esters, vinyl acetate, vinyl ethers or vinyl ketones; (C) may boil between 20 and 80 DEG C. and may be a pentane, hexane, cyclopentane petroleum fraction, CH2Cl2, benzene, acetone, ethyl acetate, propane butane or vinyl chloride. 4-12% may be used. In addition to (A) and (B) polymers and copolymers may be present which are derived from: acrylonitrile, itaconic esters, maleic esters, methacrylonitrile or acrylamide. In examples (1-3, 9-15) polymer (A) is derived from styrene and acrylonitrile (1), methylacrylate (11, 12), 2,5-dichlorostyrene (13), divinyl benzene (14), vinyl alcohol (14, 15) and vinyl toluene (15 and 21). Polymer (B) is derived by polymerization in the presence of (A) of vinylidene chloride (1), vinyl chloride (2, 3, 9-15), acrylonitrile (1, 9, 10) and dimethyl maleate (3, 14, 15). Polymeration was carried out in water suspension (1-3, 9, 10, 14, 15) and under nitrogen (1, 9, 10). Other additives are: blowing agents, pentane (1, 3, 9, 10, 14, 15), hexane (2,12 and 13), ethanol (3, 14, 15) and butane (11-13); polyvinylpyrrolidone (1, 9, 10); catalyst, azodiisobutyronitrile and benzoyl peroxide (2, 3, 11-13, 15); plasticizers, sodium carboxymethyl cellulose (2, 11-13) and stearic acid (3, 14, 15); polyvinyl alcohol (3); and flame retardants, SbO3 (3, 14, 15) and sodium phosphate (3, 14, 15). In examples (4-8, 16-20) (A) is derived from styrene (4-6, 8, 16-20), acrylonitrile (6), butadiene (6, 17) and vinyl cyclohexane (7). (B) is derived from vinyl chloride (4-8, 16-19, 20a, 20b), vinylidene chloride (7, 20c), vinyl isobutyl ether (20a), vinyl acetate (20b) and ethyl acrylate (20c). Granules of (A) and (B) are mixed and extruded optionally into water (4-7, 16-20). Additives are: blowing agents: hexane (4, 16), pentane (5, 6, 8, 17-20), ethyl acetate (5, 6, 18-20), acetone (7), petroleum (b.p. 35-45 DEG C.) (7) and propane (17); SbO3 (4-6, 16-19, 20a, 20b); a chloroparaffin (8); hexachlorocyclododecane (20c); polyvinylpyrrolidone (7); ferrocene (8); polybutylacrylate (19) and manganese acetylacetonate (20c). In Example (21) styrene and o-vinyl toluene are copolymerized in the presence of benzoyl peroxide, azodiisobutyronitrile, sodium acetate, and hydroxyethylcellulose.

    Self extinquishing plastic compositions
    9.
    发明专利
    Self extinquishing plastic compositions 未知

    公开(公告)号：GB1015397A

    公开(公告)日：1965-12-31

    申请号：GB3811462

    申请日：1962-10-09

    Applicant: BASF AG

    Inventor： RAUSCHENBACH ROLF DIETER ,  MEYER FERDINAND ,  WINTERSBERGER KARL ,  DAUMILLER GUENTHER

    IPC: C08F12/08 ,  C08J9/00 ,  C08K5/00 ,  C08K5/56

    Abstract: A self-extinguishing plastic composition comprises (a) a polymer or copolymer of styrene or a -methyl styrene; (b) an organic chlorine compound in amount sufficient to provide a chlorine content of 2 to 7% by weight of the composition; (c) a complex MexAry- 1(CO)z- 1, wherein X and Y are 1,2 or 3, Z is from 1 to 13, (Y - 1) + (Z - 1) is from 2 to 12; Me is Cr, Mn, Fe, Co, Ni, Mo, Tc, Ru, Rh, Pd, W, Re, Os, Ir or Pt; and Ar is a substituted or unsubstituted cyclopentadienyl or benzene radical, and, optionally (for making the composition expandable; (d) a volatile liquid expanding agent which does not dissolve the polymer and which has a boiling point below the softening point of the polymer. The polymer may be a copolymer with acrylonitrile, butadiene, an ester of acrylic or methacrylic acid, vinyl carbazole or divinyl benzene. Component (b) may be chlorinated polyvinyl chloride, chlorinated polyisobutylene, chlorinated polystyrene, chlorinated paraffins, hexachlorocyclododecane, hexachlorocyclopentadiene, hexachloroendomethylene tetrahydrophthalic acid, tetrachlorobutyrolactone or tetrachlorobutanediol diacetate. Many suitable complexes (c) are specified, those used in the examples being ferrocene and various derivatives thereof, nickelocene, dibenzene chromium, carbonyls of Mn, Mo and Co, chlorobenzene chromium tricarbonyl and various cyclopentadienyl carbonyl complexes of Cr, Mo, Co, Ni and Fe. The expanding agent (d) may be a hydrocarbon or halohydrocarbon and in the examples pentane and hexane are used. The compositions may be obtained by lead polymerization of the monomer in the presence of the ingredients (b) and (c) \sB (d), or all the components may be dissolved in an organic solvent immiscible in water (e.g. methylene chloride or dichloroethylene), following which the solution is poured into water containing a protective colloid. The products find application as moulded articles, e.g. sheet, and as coatings.

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