Classifications

• • 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
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/34—Silicon-containing compounds
• • 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
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/04—Homopolymers or copolymers of ethene
  • C08L23/06—Polyethene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L31/00—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 acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid; Compositions of derivatives of such polymers
  • C08L31/02—Homopolymers or copolymers of esters of monocarboxylic acids
  • C08L31/04—Homopolymers or copolymers of vinyl acetate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
  • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
• • 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

Definitions

• This invention relates to glass reinforced molding compo- sitions which have improved warp resistance, hig h deflection temperature under load (DTUL.) and high impact strength in the molded article. More particularly, it pertains to composi ⁇ tions comprising a thermoplastic resin selected from the groupt consisting of a high molecular weight linear polyester, a ix- ture of high molecular weight linear polyesters, a mixture of a high molecular weight linear polyester and high molecular weight block polyester and a mixture of high molecular weight linear polyesters and high molecular weight block copolyester, fibrous glass reinforcement, phlogopite mica and an impact modifier.
• a thermoplastic resin selected from the groupt consisting of a high molecular weight linear polyester, a ix- ture of high molecular weight linear polyesters, a mixture of a high molecular weight linear polyester and high molecular weight block polyester and a mixture of high molecular weight linear polyesters and high molecular weight block copolyester,
• poly(ethylene terephthalate) has become an important constituent of injection moldable compositions.
• Poly(l, 4-butylene terephthalate) because of its very rapid crystallization from the melt, is uniquely useful as a component in such compositions.
• Workpieces molded from such polyester resins in comparison with other thermoplastics, offer a high degree of surface hardness and abrasion resistance, high gloss, and lower surface friction. it has been previously disclosed in cop ending appli cation ___ ⁇ Serial No.
• glass reinforced thermoplastic compositions of a polycarbonate resin and poly ( 1 , 4-butylene terephthalate) can be molded to articles having greater resis- tance to warpage and/or improved DTTJ.L, in comparison with glass fiber reinforced poly(l, 4-butylene terephthalate) resins. It is further disclosed in co-pending application Serial No.
• compositions of high mole ⁇ cular weight linear polyesters, optionally in admixture with block copolyesters, fibrous glass reinforcement, phlogopite mica and an impact modifier possess very little inherent warpage in the molded article and, in addition, are charac ⁇ terized with good impact strength and high deflection tempera ⁇ ture under load (DTUL).
• DTUL high deflection tempera ⁇ ture under load
• thermoplastic resin s elected from the group consisting of a high molecular weight linear polyester, a mixture of high molecular weight linear polyesters, a mixture of a high mole ⁇ cular weight linear polyester and high molecular weight block copolyester and mixtures of high molecular weight linear polyesters and high molecular weight block copolyester where ⁇ in said block copolyester is derived from blocks of
• X may be alkylene or alkylidene of from 1 to 4 car ⁇ bon atoms, carbonyl, sulfonyl, oxygen or a bond between the benzene rings, and an aliphatic dicarboxylic acid having from 6 to 12 carbon atoms in the chain and one or more straight or branched chain dihydric aliphatic glycols having from 4 to 10 carbon atoms in the chain, said copolyester having at least 10% of aliphatic units being derived from a dicarboxylic acid, or
• the high molecular weight linear polyesters of this invention include, in general, linear saturated condensation products of diols and dicarboxylic acids, or reactive derivatives thereof. Preferably, they will comprise condensation products of aro ⁇ matic dicarboxylic acids and aliphatic diols.
• the diol portion of the polyester can contain from two to ten carbon atoms, it is preferred that it contain from two to four carbon atoms in the form of linear methylene chains . It is to be understood that it is also pos sible to use polyesters such as poly (1, 4-dimethylol cyclohexane dicarboxylates, e. g. , terephtha- lates).
• phthalates small amounts of other aromatic dicarboxylic acids, such as naphthalene dicarboxylic acid, or aliphatic dicarboxylic acids, such as adipic acid, can also be present in preferred compositions.
• the diol constituent can likewise be varied, in the preferred embodiments, by adding small amounts of cyclo aliphatic diols, such as cyclo- hexanedimethanol.
• the preferred polyesters are well known as film and fiber formers, and they are provided
• the preferred polyesters will comprise a poly(alkylene terephthalate), isophthalate or mixed isophthalate-terephthalate, e. g. , up to 30 mole percent isophtha- late, said alkylene groups containing from 2 to 10 carbon atoms, e. g. , poly(ethylene terephthalate) or poly(l, 4-butylene terephtha ⁇ late).
• poly(l, 4-butylene terephthalate) as the linear polyester resin component of the present compositions.
• mixtures of linear polyesters such as a mixture of polyethy ⁇ lene terephthalate) and poly (1, 4-butylene terephthalate).
• poly(ethylene terephthalate) can be used in amounts of from about 1 -40% by weight, preferably 15-30% by weight of the total composition.
• the "block copolyesters” also us eful in the compositions of this invention are prepared by the reaction of terminally- reactive poly(butylene terephthalate), preferably, low molecular weight, and a terminally-reactive copolyester or polyester in the presence of a catalyst for trans esterification, such as zinc acetate, manganese acetate, titanium esters, and the like.
• the terminal groups are hydroxyl , carboxyl, carboalkoxy, and the like, including reactive derivatives thereof.
• the result of reaction between two terminally reactive groups must be an ester linkage.
• polymerization is o carried out under standard conditions, e. g. , 220 to 280 C.
• copolyester designated component (ii), hereinabove, is a copolyester designated component (ii), hereinabove.
• BUREA preferably prepared from terephthalic acid or isophthalic acid or a reactive derivative thereof and a glycol, which may be a straight or branched chain aliphatic glycol.
• the glycol will be 1, 4-butanediol; 1, 5-pentanediol; 1, 6 -hexane- diol; 1, 9-nonanediol; 1, 10-decanediol; neopentyl glycol; 1, 4- cyclohexanediol; 1, 4- cyclohexane dimethanol, a mixture of any of the foregoing, or the like.
• Suitable aliphatic dicarboxylic acids for the mixed aromatic/aliphatic embodiment are suberic, sebacic, azelaic, adipic acids, and the like
• the copolyesters may be prepared by ester interchange in accordance with standard procedures .
• the copolyesters designa ted (ii) are most preferably derived from an aliphatic glycol and a mixture of aromatic and aliphatic dibasic acids in which the mole ratio concentration of aromatic to aliphatic acids is from between 1 to 9 and 9 to 1, with an especially preferred range being from about 3 to 7 to about 7 to 3.
• terminally reactive aliphatic polyesters designated com ⁇ ponent (iii) will contain substantially stoichiometri c amounts of the aliphatic diol and the aliphatic dicarboxylic acid, although hydroxy- containing terminal groups are preferred.
• both the aromatic /aliphatic copolyesters (ii) and the aliphatic polyesters (iii) are commercially available.
• the block copolyesters contemplated herein preferably comprise from 95 to 50 parts byweight of the segments of poly (1, 4-butylene terephthalate).
• the poly( l, 4-butylene tere- phthalate) blocks, before incorporation into the block copoly- - ⁇ ⁇ esters, will preferably have an intrinsic viscosity of above 0. 1 dl/g. and preferably, between 0. 1 and 0. 5 dl/g. , as
• OM measured in a 60:40 mixture of phenol/tetrachloroethane at o 30 c.
• the balance, 5 to 50 parts by weight of the copolyester will comprise blocks of components (ii) or (iii).
• the poly(l, 4-butylene terephthalate) block can be straight chain or branched, e. g. , by use of a branching component, e. g. , 0. 05 to 1 mole %, based on terephthalate units, of a branching component which contains at least three ester-forming groups.
• a branching component e. g. , 0. 05 to 1 mole %, based on terephthalate units
• This can be a glycol, e. g. , pentaerythritol, trimethylolpropane, and the like, or a polybasic acid compound, e. g. , trimethyl trime ⁇ ate, and the like.
• the impact modifiers included within the scope of the present compositions are segmented copolyester-ethers known as Hytrel (duPont), silicone-polycarbonate block copolymer, e. g. , Copel 3320 (G. E. ) and ethylene-vinyl acetate copolymers (Alathon, by duPont).
• Hytrel duePont
• silicone-polycarbonate block copolymer e. g. , Copel 3320 (G. E. )
• ethylene-vinyl acetate copolymers Alathon, by duPont
• a mixture of ethylene-vinyl acetate copolymer and polyethylene homopolymer is useful.
• the impact modifier is present in the composition of this invention in amounts within the range of from about 1 to 20%, by weight, preferably 1-15%, by weight, of the total com ⁇ position.
• segmented copolyester-ethers useful as impact modifiers herein are described in U. S. 3, 023, 182, U. S. 3, 651, 014, U. S. 3, 763, 109 and U. S. 3, 766, 146, which are incorporated herein by reference.
• Typical copolymers of ethylene and vinyl acetate include, for example, Alathon 3152 ( 15% by weight vinyl content), Alathon 3194 (25% by weight vinyl acetate), Alathon 3180 (28% by weight vinyl acetate), Vynathene EY 903, (45% by weight vinyl acetate, sold by U. S. I. Chemicals) and Vynathene EY 904 ( 52% by weight vinyl acetate).
• the fibrous glass employed as component (c) in the present compositions is well known to those skilled in the art and is widely available from a number of manufacturers.
• fibrous glass filaments comprised of lime- aluminum borosilicate glas s that is relatively soda free. This is known as "E" glass .
• other glasses are useful where electrical properties are not so important, e. g. , the low soda glass known as "C” glass .
• the filaments are made by standard processes, e. g. , by steam or air blowing, flame blowing and mechanical pulling.
• the preferred filaments for plastics reinforcement are made by mechanical pulling.
• the filament diameters range from about 0. 00030 to about 0. 0019 cm (about 0. 00012 to 0. 00075 inch), but this is not critical to the present invention.
• the length of the glass filaments and whether or not they are bundled into fibers and the fibers bundled in turn to yarns, ropes or rovings, or woven into mats, and the like, are also not critical to the invention.
• the filamentous glass in the form of chopped strands of from about 0. 29 to about cm (about one-eighth to about 2 inches) long .
• articles molded from the composition s on the other hand, even shorter lengths will be encountered because, during compounding, considerable fragmentation • will occur. This is desirable, however, because the best properties are exhibited by thermo ⁇ plastic injection molded articles in which the filament lengths lie between about 0. 00025 and 0. 32 cm (about 0. 0001 and 0.
• the fibrous glass rein ⁇ forcement and the phlogopite mica are employed in a combined amount of from about 1 to about 60% by weight of the total composition, the preferred range being from about 25 to about 40% by weight.
• the phlogopite mica used in the practice of the present invention has a particle size of from about 10-325 mesh.
• Particularly preferred phlogopite micas are commercially avail ⁇ able from Marietta Resources, Ltd. , Montreal, and are known as Suzorite (20H, 10-20 mesh; 200 H, less than 100 mesh; 200 S, less than 100 mesh; 150 S, less than 100 mesh, 80 S, 99% less than 100 mesh.
• Suzorite 150 S appears to be Suzorite 150 S.
• materials which may also be included in the composi ⁇ tions of the present invention in conjunction with the heretofore identified impact modifiers include polyethylene copolymers, like ethylene -propylene copolymers, ethylene -ethylene acrylate copolymers and ethylene -acrylic acid salt copolymers. Further optional materials include flame retardants like decabromodi- phenyl ether and halogenated aromatic polycarbonates. Illustra ⁇ tive flame - retardant additives are disclosed in U. S. 3, 833, 685, U. S. 3, 195, 926 and U. S. 3, 671, 487, which are incorporated herein by reference. Other flame retardants are disclosed in U. S. 3, 681, 281 and U. S.
• the flame retardants are generally utilized in any flame retardant quantity whereas the other optional ingredients like polyethylene, can be used in amounts of from about 0. 5 to 5% by weight of the total composition or in any conventional amounts for the purposes intended.
• compositions of this invention can be prepared by a number of procedures.
• the fibrous glass rein ⁇ forcement, phlogopite mica and impact modifier are dispersed in a matrix of the resin in the proces s .
• the glas s reinforcement, phlogopite mica and impact modifier are mixed with, for example, the poly( l, 4-butylene terephtha ⁇ late) resin by dry blending, then either fluxed on a mill and comminuted, or they are extruded and chopped.
• the glass reinforcing agent, phlogopite mica and impact modifier can also be mixed with the resin and directly molded, e. g. , by injection or transfer molding techniques.
• Pre-compounded, pelletized and then molded are pre-compounded, pelletized and then molded.
• Pre- compounding can be carried out in conventional equipment. For example, after carefully pre-drying the polyester, e. g. , at 125 C for 4 hours, a single screw extruder is fed with a dry blend of the ingredients, the screw employed having long transition and metering sections to ensure proper melting.
• a twin screw extrusion machine e. g. , a Werner & Pfleiderer machine, can be fed with resins and additives at the feed port and reinforcement downstream. In either case, a generally suitable machine temperature will be about 230 to 300°C. (about 450 to 570°F).
• the pre-compounded composition can be extruded and cut up into molding compounds such as conventional granules , pellets, etc. , by standard techniques .
• compositions can be molded in any equipment conven ⁇ tionally used for glas s -filled thermoplastic compositions, e. g. , Van Dorn type injection molding machine with conventional o o cylinder temperatures, e. g. , 274 C. (525 F), and conventional
• the resistance to warpage of the above compositions is excellent.
• Example s 13-16 The following formulations are mechanically blended then extruded and molded into test pieces in a Van Dorn injection molding machine. The properties are summarized in Table 4.
• Antimony oxide 5.0 5.0 5.0 6.0
• Example 18 The following formulation was mechanically blended, extruded and molded into test pieces in a Van Dorn injection molding machine. The composition and properties are summarized below:
• block copolyester of poly( l, 4-butylene terephthalate) and poly(l, 6-hexylene-(0. 7) azelate-(0. 3) isophthalate molecular weight of block 300 34. 8 fibrous glass reinforcement 11. 0

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• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Compositions Of Macromolecular Compounds (AREA)

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• 1979
  • 1979-06-29 CA CA000330878A patent/CA1148291A/en not_active Expired
  • 1979-07-11 JP JP50116379A patent/JPS55500524A/ja active Pending
  • 1979-07-11 WO PCT/US1979/000486 patent/WO1980000255A1/en unknown
• 1980
  • 1980-02-25 EP EP19790900830 patent/EP0016123A4/de not_active Withdrawn

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