Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K7/00—Use of ingredients characterised by shape
  • C08K7/02—Fibres or whiskers

Definitions

• This invention is directed to an improved polycarbonate composition of an aromatic carbonate polymer in intimate admixture with an unsized fibrous reinforcing ngent and a small amount of a hydrogen siloxane.
• Applicant finds superior results with unsized glass fibers, if a hydrogen-siloxane is selected, and then used in amounts below 1.0%, and especially below the 0.5% lower limit of Alewelt et al.
• the falling ball ductile impact with such specific hydrogen polysiloxanes is, as will be illustrated later, more than ten times greater than with the dimethylpolysiloxanes used in Alewelt et al.
• Bialous et al., U.S. 3 , 971 , 756 is also relevant to the present invention, but only insofar as it shows that from 0.01 to about 5 weight % of a polysiloxane having silicon-bonded hydrogens can be used to prevent dripping in flame retardant polycarbonate compositions.
• sizing agents on the fibrous reinforcement or separately added must be absent because these either evoke adhesive bonds between the matrix and fiber, or they prevent reactions between the hydrogen polysiloxane and the fiber, or both;
• polysiloxane for best combination of high modulus and creep performance, is preferably kept below 1.0% and, especially preferably, below 0.5%;
• the polysiloxane used must contain hydrogen silicon bonds.
• thermoplastic compositions comprising per 100 parts by weight (a), (b) and (c) , an intimate admixture of :
• aromatic carbonate polymer or copolymer is used in its broadest aspects. Suitable are those described in the above-mentioned U.S. 3,971,756 and 4,147,707, the disclosures of which are incorporated herein by reference.
• aromatic carbonate polymers are homopolymers and copolymers that are prepared by reacting a dihydric phenol with a carbonate precursor.
• Suitable dihydric phenols are bis (4-hydroxyphenyl)methane; 2,2bis (4-hydroxyphenyl)propane (hereinafter referred to as bisphenol-A); 2,2-bis (4-hydroxy-3-methylphenyl)propane; 4, 4-bis (4-hydroxyphenyl)heptane; 2, 2-bis (4-hydroxy-3,5dichlorophenyl)propane; 2,2-bis (4-hydroxy-3, 5-dibromophenyl) propane; 2, 2-bis (4-hydroxy-3,5-dimethylphenyl)propane, and the like; dihydric phenol ethers such as bis (4-hydroxyphenyl) ether, and the like; dihydroxydiphenyls, such as p ,p'-dihydroxydiphenyl, 3,3' -dichloro-4, 4' -dihydroxydiphenyl and the like; dihydroxyaryl sulfones, such as bis (4-hydroxyphenyl) sulfone; bis (3,5-methyl
• dihydric phenols are also available to provide carbonate polymers and are disclosed in U.S. 2,999,835; 3,028,365; and 3,153,008.
• aromatic carbonate polymer component (a) are copolymers prepared from any of the above copolymerized with halogen-containing dihydric phenols, such as 2, 2-bis (3,5-dichloro-4-hydroxyphenyl)propane; 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane, and the like.
• dihydric phenols or a copolymer of a dihydric phenol with a glycol or with hydroxy or acid terminated polyester, or with a dibasic acid in the event that a carbonate copolymer or interpolymer rather than a homopolymer is desired for use as component (a).
• blends of any of the above aromatic carbonate polymers are also contemplated for use.
• dihydric phenols are bisphenol-A and 2,2-bis (4-hydroxy-3,5-dimethyIphenyl)propane.
• the carbonate precursor may be either a carbonyl halide, a carbonyl ester or a haloformate.
• the carbonyl halides which may be employed include carbonyl bromide, carbonyl chloride and mixtures thereof.
• Typical of the carbonate esters are diphenyl carbonate, di(halophenyl) carbonates such as di(chlorophenyl) carbonate, di-(bromophenyl) carbonate, di(trichlorophenyl) carbonate, di- (tribromophenyl) carbonate, and the like; di(alkyIphenyl) carbonate, such as di(tolyl) carbonate, di(naphthyl) carbonate, di(chloronaphthyl) carbonate, and the like, or mixtures thereof.
• haloformates of dihydric phenols are (bischloroformates of hydroquinone, etc.), or glycols (bis haloformates of ethylene glycol, neopentyl glycol, polyethylene glycol, etc.). While other carbonate precursors will occur to those skilled in the art, carbonyl chloride, also known as phosgene, is preferred.
• polymeric components (a) comprising units of a dihydric phenol, a dicarboxylic acid and carbonic acid, such as disclosed in U.S. 3,169,121, incorporated herein by reference.
• the aromatic carbonate polymers used as component (a) herein are prepared preferably by employing a molecular weight regulator, an acid acceptor and a catalyst.
• Suitable molecular weight regulators are phenol, cyclohexanol, methanol, p-t-butylphenol, p-bromophenol, and the like.
• a suitable acid acceptor may be either organic or inorganic. Illustrative of the former are tertiary amines, such as pyridine, triethylamine, dimethylaniline, tributylamine, and the like.
• Inorganic acid acceptors can comprise a hydroxide, a carbonate, a bicarbonate, a phosphate, or the like, of an alkali- or an alkaline earth metal.
• component (a) Conventional additives, such as anti-static agents, pigments, mold release agents, thermal stabilizers and the like can be present in component (a).
• the fibrous reinforcing agent (b) can vary widely in nature and type, so long as it is "pristine", that is, essentially free of any sizing materials, as mentioned above.
• suitable fibers e.g., glass fibers
• suitable fibers are all the commercially available kinds and types, such as cut glass filaments (long glass fiber and short glass fiber), rovings and staple fibers.
• the length of the filaments should be between about 60 mm and 6 mm, for long fibers and between about 5 mm and 0.05 mm in the case of short fibers.
• Alkali-free aluminumboron-silicate glass (“E" glass) or alkali containing glass (“C” glass) can be used, as well as others.
• Preferred is a ground short glass fiber.
• Any of the hydrogen polysiloxanes known in the art can serve as component (c). Especially useful are those set forth by formula in the above-mentioned U.S. 3,971,756. The patent also cites U.S.
• an impact modifier can comprise a polyacrylate, or a copolymer of a diene and acrylonitrile and/or vinyl aromatic compound.
• a preferred such modifier is a block copolymer, of the linear or radial type, comprising diene rubber center blocks and vinyl aromatic terminal blocks.
• Illustrative dienes are butadiene or isoprene, and illustrative vinyl aromatics are styrene, vinyl toluene, and the like. Especially suitable are selectivel hydrogenated such compounds.
• any conventional method can be used to formulate the present thermoplastic compositions, and to mold them. The important factor is to insure intimate admixture.
• the amounts of components (a), (b) and (c) and, optionally (d) to be used have been broadly set forth above.
• the siloxane will be present in an amount of from about 0.05 to less than 0.5, and especially preferably, about 0.4 parts, by weight per 100 parts by weight of (a) , (b) and (c) combined.
• the fibrous reinforcing agent will be present in an amount of from about 15 to about 40 parts by weight per 100 parts by weight of (a) , (b) and (c) combined.
• Mixing temperatures and molding temperature will be illustrated in the following examples, but, in any event, will be entirely in harmony with those well known to those skilled in the art of polycarbonate resin technology.
• Polycarbonate compositions are prepared by extruding a hor ⁇ opolymer of 2,2-bis (4-hydroxyphenyl) propane (bisphenol-A) and phosgene (LEXAN ® 125), either short milled glass fibers or short milled rockwoolmineral fibers, both essentially free of any sizing agent, and, where indicated, a polymethyl hydrogen siloxane fluid (DF1040, General Electric Company).
• a polydimethyl siloxane fluid SF-13, General Electric Company
• Extrusion is carried out at 2 ⁇ 5°C., and the extrudate is comminuted into pellets,
• pellets are then injection molded at about 315oC. (cylinder), into standard physical test specimens, so that heat distortion temperature (HDT) can be measured according to standard test methods; Izod impact strength, notched and unnotched can be measured on 1/8" bars according to standard test methods; falling ball impact strength can be measured on a 10 cm round disc according to standard test methods elastic modulus and tensile yield strength and elongation at yield and at break can be measured according to standard test methods.
• HDT heat distortion temperature
• composition(parts by weight) poly(bisphenol-A carbonate a 70 70 70 80 80 80 30 short unsized glass fibers b 30 30 30 20 20 -- -- short unsized rock- wool fibers c -- -- -- -- 20 20 poly(methyl hydrogen) siloxane d 0.4 -- 0.4 — 0.4 — poly(dimethyl) siloxane e -- 0.4 -- -- -- -- --
• EXAMPLE 4 The general procedure of Examples 1-3 is repeated, increasing the amount of hydrogen siloxane fluid, and determining, in addition, Vicat softening temperature, melt viscosity, and gasoline resistance. For comparison purposes, a composition is also made omitting the siloxane fluid. The compositions used and the results obtained are set forth in Table 2.
• composition(parts by weight) poly(bisphenol-A) carbonate a 80 80 short unsized glass fibers 20 20 poly(methyl hydrogen siloxane) 0.5 —
• ** NB did not break a see footnote to Table 1 b see footnote to Table 1 d see footnote to Table 1 The ductile impact strength is again seen to be markedly increased.
• the bisphenol-A polycarbonate can be substituted with a polycarbonate from tetramethylbisphenol-A.
• the poly(methyl hydrogen) siloxane can be substituted with a poly(phenyl hydrogen) siloxane.
• An impact improving amount, e.g.-, 5% by weight, of a selectively hydrogenated block copolymer of styrenebutadiene-styrene, e.g., Shell's Kraton G can be included.in the composition.
• a selectively hydrogenated block copolymer of styrenebutadiene-styrene e.g., Shell's Kraton G
• the polycarbonate there can be substituted polyester carbonate,polycarbonate siloxane copolymers and blends thereof. All such obvious variations are within the full intended scope of the appended claims.

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• Compositions Of Macromolecular Compounds (AREA)

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• 1980
  • 1980-12-08 US US06/214,010 patent/US4358556A/en not_active Expired - Lifetime
• 1981
  • 1981-11-30 WO PCT/US1981/001579 patent/WO1982002051A1/en not_active Ceased
  • 1981-11-30 AU AU79393/82A patent/AU545868B2/en not_active Ceased
  • 1981-11-30 JP JP57500237A patent/JPH0216775B2/ja not_active Expired
  • 1981-12-05 EP EP81110186A patent/EP0053825B1/en not_active Expired
  • 1981-12-05 DE DE8181110186T patent/DE3167656D1/de not_active Expired

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