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
  • C08K5/00—Use of organic ingredients
  • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
  • C08K5/41—Compounds containing sulfur bound to oxygen
  • C08K5/42—Sulfonic acids; Derivatives thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L27/00—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 a halogen; Compositions of derivatives of such polymers
  • C08L27/02—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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L27/12—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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
  • C08L27/18—Homopolymers or copolymers or tetrafluoroethene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
  • C08L83/10—Block- or graft-copolymers containing polysiloxane sequences

Definitions

• This invention relates to ductile and solvent resistant aromatic polycarbonate compositions that also have improved flame retardance.
• Polycarbonate polymers are known as being excellent molding materials since products made therefrom exhibit such properties as high impact strength, toughness, high transparen ⁇ cy, wide temperature limits (high impact resistance below -60o C and a UL thermal endurance rating of 115o C with impact), good dimensional stability, good creep resistance, good flame re ⁇ tardance, and the like. It would be desirable to add to this list of properties those of ductility and solvent resistance en ⁇ abling these polycarbonate compositions to be employed to form molded articles that can be used in such applications as air ⁇ craft tray tables and seat backg, aircraft ducting, ski boots, and the like wherein the articles will be required to exhibit high tensile properties and resistance to the corrosive effects of commercial cleaning compounds and other organic chemicals. Summary of the Invention
• aromatic polycarbonate resins by mixing the polycarbonate resin with block copolymers consisting of alterna ⁇ ting segments of polybisphenol carbonates and polyorganosiloxane in amounts of about 1-30% by weight, preferably about 4-10% by weight, of the polycarbonate resin.
• block copolymers consisting of alterna ⁇ ting segments of polybisphenol carbonates and polyorganosiloxane in amounts of about 1-30% by weight, preferably about 4-10% by weight, of the polycarbonate resin.
• any of the aromatic poly ⁇ carbonates can be empolyed that are prepared by reacting a diphenol with a carbonate precursor.
• Typical of some of the diphenols that can be employed are bisphenol-A (2, 2 -bis (4-hydroxy-phenyl)propane), bis(4-hydroxphenyl)methane, 2, 2-bis(4-hydroxy-3-methylphenyl)propane, 4, 4'-bis(4-hydroxphenyl) heptane, 2, 2-(3, 5-3', 5'-tetrachloro-4, 4'-dihydroxydiphenyl) propane, ?, 2-(3, 5, 3', 5' -tetrabromo-4, 4'-dihydroxydiphenyl) propane, (3, 3' -dichloro-4, 4' -dihydroxyphenyl)methane.
• Other halogenated and non-halogenated diphenols of the bisphenol type can also be used such as are disclosed in U. S. Patents 2 2, 999, 835, 3, 028, 365 and 3, 334, 154.
• the carbonate precursor used can be either a carbonyl halide, a carbonate ester or a haloformate.
• the carbonyl halides can be carbonyl bromide, carbonyl chloride and mixtures thereof.
• the carbonate esters can be diphenyl car ⁇ bonate, di-(halophenyl) carbonates such as di-(chlorophenyl) carbonate, di-(bromophenyl) carbonate, di-(trichlorophenyl) carbonate, di-(tribromophenyl) carbonate, etc. di-(alkylphenyl) carbonate such as di(tolyl) carbonate, etc. , di-(naphthyl) carbonate, di-(chloronaphthyl) carbonate, phenyl tolyl carbo ⁇ nate, chlorophenyl chloronaphthyl carbonate, etc. , or mixtures thereof.
• di-(halophenyl) carbonates such as di-(chlorophenyl) carbonate, di-(bromophenyl) carbonate, di-(trichlorophenyl) carbonate, di-(tribromophenyl) carbonate, etc.
• haloformates that can be used include bis ⁇ haloformates of dihydric phenols (bischloroformates of hydroquinone, etc. ) or glycols (bishaloformates 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 derivatives of a dihydric phenol, a dicarboxylic acid and carbonic acid such as are disclosed in U. S. Patent 3, 169, 121 which is incorporated herein by reference, and which are particularly preferred.
• This class of compounds is generally referred to as copolyestercarbonates.
• Molecular weight regulators, acid acceptors and catalysts can also be used in obtaining the aromatic polycarbonates of this invention.
• the useful molecular weight regulators include monohydric phenols such as phenol, chroman- I, paratertiarybutylphenol, parabromophenol, primary and secondary amines, etc.
• phenol is employed as the molecular weight regulator.
• a suitable acid acceptor can be either an organic or an inorganic acid acceptor,
• a suitable organic acid acceptor is a tertiary amine such as pyridine, triethylamine, dimethylaniline, tributylamine, etc.
• the inorganic acid acceptor can be either a hydroxide, a carbonate, a bicarbonate, or a phosphate of an alkali or alkaline earth metal.
• the catalysts which can be employed are those that typically aid the polymerization of the diphenol with phosgene.
• Suitable catalysts include tertiary amines such as triethyl ⁇ amine, tripropylamine, N, N-dimethylaniline, quaternary ammonium compounds such as, for example, tetraethyl-ammonium bromide, cetyl triethyl ammonium bromide, tetra-n-heptylammonium iodide, tetra-n-propyl ammonium bromide, tetramethylammonium chloride, tetramethyl ammonium hydroxide, tetra-n-butyl ammonium iodide, benzyltrimethyl ammonium chloride and quaternary phospho -nium compounds such as, for example, n-butyltriphenyl phosphonium bromide and methyltriphenyl phosphonium bromide.
• branched polycarbonates wherein a polyfunctional aromatic compound is reacted with the diphenol and carbonate precursor to provide a thermoplastic randomly branched polycarbonate.
• These polyfunctional aromatic compounds contain at least three functional groups which are carboxyl, carboxylic anhydride, haloformyl, or mixtures thereof.
• the preferred polyfunctional aromatic compounds are trimellitic anhydride and trimellitic acid of their acid halide derivatives. Blends of linear and branched aromatic polycarbonates are also included within the scope of this invention.
• block copolymers that can be employed in the practice of this invention can be prepared by methods known to those skilled in the art, such as are disclosed in U. S Patents 3, 189, 622 and 3, 189, 634 which are incorporated herein by reference.
• block copolymers typically comprise alternating segments of polycarbonate and polyorganosiloxane; i. e. , block A and block B, as represented by the general formula
• R 1 -R 8 can each be independently selected from the group consisting of hydrogen, halogen, alkyl having 1 to 6carbon atoms and aryl; R 9 and R 1 0 can each be independently selected from the group consisting of hydrogen, alkyl having
• the polycarbonate segment of the block copolymer is derived from the same diphenol homopolymer as is the polycarbonate resin with which the block copolymer is to be blended.
• the polycarbonate resin is derived from the diphenol, bisphenol-A; i. e.
• the polycarbonate segment of the block copolymer is preferably derived from the same diphenol; i. e. , BPA.
• the polycarbonate resin is derived from the diphenol 2, 2-bis(4-hydroxy-3-methylphenyl) propane, then the polycarbonate segment of the block copolymer is derived from the same diphenol; i. e. , 2, 2-bis(4-hydroxy- 3-methylphenyl)propane, and so forth.
• the polyorganosiloxane segment of the block copolymer is preferably polydimethylsiloxane (PDMS).
• PDMS polydimethylsiloxane
• One hundred (100) parts of an aromatic polycarbonate was prepared by reacting BPA (2, 2-bis(4-hydroxyphenyl) propane) and phosgene in the presence of an acid acceptor and a molecular weight regulator.
• the resultant high molecular weight aromatic polycarbonate had an intrinsic viscosity (IV) of 0. 50.
• This aromatic polycarbonate was subsequently mixed with the various block copolymers described in the ensuing examples by tumbling the ingredients together in a laboratory tumbler. In each instance, the resulting mixture was then fed through an extruder which was operated at about 285o C and the extrudate was comminuted into pellets.
• the pellets were then injection molded at about 315o C into test bars of about (5 in. ) 12. 7cm by 1 ⁇ 2 in. by about (1/ 16- 1/8 in. ) 0. 16 -0. 32cm thick and into test squares of about 5x5cm (2 in. by 2 in. ) by about (1/8 in. ) 0. 32cm thick.
• a block copolymer consisting of a polycarbonate segment derived from BPA and polydimethylsiloxane (PDMS) in the polyorganosiloxane segment was prepared in accordance with the method disclosed in U. S. Patent 3, 189, 622. That is the block copolymer was prepared by forming a mixture of
• the resultant block copolymer consisted of 50% by weight polycarbonate segments and 50% by weight PDMS segments.
• Example 2 The block copolymer of Example 2 was mixed with the aromatic polycarbonate of Example 1 at the weight percentages shown below and each of the mixtures was then extruded into pellets which were then molded into test bars and test squares following the procedure described in Example 1.
• Example 2 Following the procedure of Example 2, a block copolymer was obtained consisting of 35% by weight polycarbonate segments and 65% by weight PDMS segments.
• Example 8 Following the procedure of Example 1, 5% by weight of the block copolymer of Example 7 was mixed with 95% by weight of the aromatic polycarbonate of Example 1 whereupon the mixture was extruded into pellets and the pellets molded into test bars and test squares as described in Example 1.
• Example 9 The procedure of Example 2 was used to prepare a block copolymer consisting of 95% by weight polycarbonate segments and 5% by weight PDMS segments. This block copolymer was then extruded into pellets and the pellets molded into test bars and test squares as described in Example 1.
• Example 10 A mixture of 97% by weight of the polycarbonate of Example 1 and 3% by weight PDMS was prepared, which was then extruded into pellets and the pellets molded into test bars and test squares following the proceedu of Example 1.
• test bars and test squares obtained from mixtures of the aromatic polycarbonate of Example 1 with the block copolymers of Examples 3-6 and 8 had a mottled, laminar appearance which could not be used as a commercially acceptable product.
• test bars and test squares of Examples 1, 3-6 and 8-10 were subject to various tests to determine various properties of the compositions.
• the test results wherein 5 tests bars and 5 test squares were used for each test are set forth in Tables. I and II below wherein the various tests were determined in accordance with the following methods:
• V-O Average flaming and/or glowing after removal of the igniting flame shall not exceed 5 seconds and none of the specimens shall drip flaming particles which ignite absorbent cotton.
• V-I Average flaming and/or glowing after removal of the igniting flame shall not exceed 25 seconds and the glowing does not travel vertically for more than 1/8" of the specimen after flaming ceases and glowing is incapable of igniting absorbent cotton.
• V-II Average flame and or glowing after removal of the igniting flame shall not exceed 25 seconds and the speciments drip flaming particles which ignite absorbent cotton.
• a test bar which continues to burn for more than 25 seconds after removal of the igniting flame is classified, not by UL-94, but by the standards of the instant invention, as "burns".
• Flexural modulus was determined in accordance with ASTM D-790; flexural yield was determined in accordance with ASTM D-790; unnotched and notched Izod impact strengths were determined in accordance with ASTM D-256; flammability oxygen ratio (Fenimore/Martin) was determined in accordance with ASTM D-2863; solvent resistance was evaluated by measuring the percent strain necessary to cause crazing in test samples exposed to one drop of solvent for a period of 3 minutes; and RDT (Retention of Ductility Time) denotes the maximum number of hours for which a test bar can be aged at a temperature before the mode of failure in the notched Izod impact test (ASTM-256) changes from ductile to brittle, Unless otherwise specified, the KDT refers to heat aging at 125°C of test bars
• Example 4 block copolymer
• Example 5 raised the resistance to 1% strain, which is about the maximum generally encountered in most practical situations.
• Table -I also reveals that, at higher levels of block copolymer, oxygen index and UL-94 ratings are improved (for instance Example 1 vs. Example 6). From Table II it can be seen that use of the block copolymers of the invention results in a larger positive effect on ductility and a smaller negative effect on molded properties of the test samples as shown by Examples 3-6 and 8.
• Example 6 consisting of the aromatic polycarbonate-block copolymer mixture retained its impact strength and ductility after two weeks of aging at 125°C whereas Example 9, consisting of only the block copolymer, did not.
• Example 11 The procedure of Example 1 was repeated except that 0,5% by weight of the sodium salt of trichlorobenzene sulfonic acid (STB) and 0.1% by weight polytetrafluoroethylene (PTFE) were mixed with the aromatic polycarbonate. The mixture was extruded into pellets as in Example 1, but instead of injection molding the pellets into test bars and test squares, the pellets were extruded into sheets measuring 4 feet square by 0.318 cm (0.125”) thick.
• STB trichlorobenzene sulfonic acid
• PTFE polytetrafluoroethylene
• Example 12 The procedure of Example 2 was repeated to obtain a block copolymer consisting of 57% by weight polycarbonate segments and 43% by weight PDMS.
• Example 13 The procedure of Example 2 was repeated to obtain a block copolymer consisting of 57% by weight polycarbonate segments and 43% by weight PDMS.
• Example 11 The procedure of Example 11 was repeated except that 4% by weight of the block copolymer of Example 12 was mixed with the other ingredients of Example 11 to obtain the aromatic polycarbonate sheets.
• Example 13 containing the additional 4% by weight of the block copolymer required higher stress levels to induce stress-crazing than did Example 11.
• Example 13 was also more durable than Example 11 when exposed to carbon tetrachloride as shown in Table IV.
• Tables III and IV indicate that improved solvent resistance is obtained when the aromatic polycarbonate is further modified with the block copolymer.
• Example 1 The procedure of Example 1 was followed to prepare aromatic polycarbonate test bars and test squares comprising 70% by weight of the polycarbonate of Example 1 and 30% by weight of the block copolymer of Example 12.
• the properties of Example 1 were compared with those of this example (14) and the results are set forth in Table V below wherein tensile strength (psi), elongation (%), and modulus (psi) results were determined in accordance with ASTM D-638.

Landscapes

• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Polyesters Or Polycarbonates (AREA)

Applications Claiming Priority (2)

Publications (2)

Family

ID=25439439

Family Applications (1)

Country Status (3)

Families Citing this family (23)

Family Cites Families (3)

• 1979
  • 1979-06-19 JP JP50106079A patent/JPS55500687A/ja active Pending
  • 1979-06-19 WO PCT/US1979/000428 patent/WO1980000084A1/en unknown
• 1980
  • 1980-01-29 EP EP79900751A patent/EP0016791A1/de not_active Withdrawn

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events