EP0140885A1 - Durch fasern verstärkte polymere mit hoher schlagzähigkeit - Google Patents
Durch fasern verstärkte polymere mit hoher schlagzähigkeitInfo
- Publication number
- EP0140885A1 EP0140885A1 EP83901687A EP83901687A EP0140885A1 EP 0140885 A1 EP0140885 A1 EP 0140885A1 EP 83901687 A EP83901687 A EP 83901687A EP 83901687 A EP83901687 A EP 83901687A EP 0140885 A1 EP0140885 A1 EP 0140885A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- composition
- weight
- parts
- bis
- fibers
- 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- Withdrawn
Links
Classifications
-
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
-
- 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
- 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
- C08L83/04—Polysiloxanes
Definitions
- This invention is directed to an improved polycarbonate composition of an aromatic carbonate polymer and a linear polyester in intimate admixture with an unsized fibrous reinforcing agent 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 ductiie impact with such specific hydrogen polysiloxanes is, as will be illustrated later, more than ten times greater than TUTE SHEET "BU E- with the dimethyl-polysiloxanes 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 per- cent of a polysiloxane having silicon-bonded hy ⁇ drogens can be used to prevent dripping in flame retardant polycarbonate compositions.
- the amounts and types of hydrogen siloxanes sug ⁇ gested in the '756 patent are within the limits employed herein, and the inclusion of fibrous glass is suggested, the need for sizing-free fi ⁇ bers to enhance ductile impact is not at all evi ⁇ dent.
- sizing agents on the fibrous reinforce ⁇ ment or separately added must be absent because these either evoke adhesive bonds between the matrix and fiber, or they prevent reactions between the hy- drogen 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 hydro ⁇ gen silicon bonds.
- thermoplastic compositions comprising per 100 parts by weight (a) , (b) , (c) and (d) , an intimate admixture of:
- n plus m is at least 4, and, for example, up to about 200.
- aromatic carbonate polymer or co- polymer 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.
- the aromatic carbonate polymers are homopolymers and copolymers that are prepared by re ⁇ acting a dihydric phenol with a carbonote precursor.
- Suitable dihydric phenols are bis(4-hydroxyphenyl)methane; 2,2-bis(4-hydroxyphenyl)propane (hereinafter referred to as bisphenbl-A) ; 2,2-bis(4-hydroxy-3-methylphenyl) propane; 4,4-bis(4-hydroxyphenyl)heptane; 2,2-bis (4- hydroxy-3,5-dichlorophenyl)propane; 2,2-bis(4-hydroxy- 3,5-dibromophenyl) ropane; 2,2-bis (4-hydroxy-3,5-dimethyl- phenyl)propane, * and the like; dihydric phenol ethers such as bis(4-hydroxy- ⁇ henyl)ether, and the like; dihydroxy- diphenyls, such as p,p'-dihydroxydi ⁇ henyl; 3,3'-dichloro- 4,4'-dihydroxydiphenyl, and the like, dihydroxyaryl sul- fones, such as bis
- dihydric phenols are also avail ⁇ able 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 copolymerize with halogen-containing•dihydric phenols, such as 2,2- bis(3,5-dichloro-4-hydroxyphenyl)propane; 2,2-bis(3,5- dibromo-4-hydroxyphenyl) ropane, and the like. It is contemplated to employ two or more different dihydric phenols or a copolymers of a dihydric phenol with a glycol
- E SHEET OMPI or with hydroxy or acid terminated polyester, or with a dibasic acid in the eventthat a carbonate copolymer or interpolymer rather than a homopolymer is desired for use as component (a) .
- a carbonate copolymer or interpolymer rather than a homopolymer is desired for use as component (a) .
- blends of any of the above aromatic carbonate poly ⁇ mers are also contemplated for use.
- dihydric phenols are bis- phenol-A and 2,2-bis(4-hydroxy-3,5-dimethylphenyl) ropane.
- the carbonate precursor may be either a car- bonyl halide, a carbonyl ester or a haloformate.
- the carbonyl halides which may be employed include carbonyl bromide, carbonyl chloride and mixtures thereof.
- Typi ⁇ cal of the carbonate esters are diphenyl carbonate, di- (halophenyl)-carbonate such as di(chlorophenyl)carbonate, di(bromophenyl)-carbonate, di (trichlorophenyl) car- bonate, di(tribromophenyl)-carbonate, and the like; di(alkylphenyl)carbonate, such as di(tolyl)carbonate, di(naphthyl)carbonate, di(chloronaphthyl)carbonate, and the like, or mixtures thereof.
- haloformates of di ⁇ hydric phenols are (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.
- a molecular weight regulator is 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
- SUBSTITUTE SHEET 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.
- the linear polyesters (b) used in the practice of the present invention are polymeric glycol esters of terephthalic and isophthalic acids. They are available commercially or can be prepared by known techniques such as by the alcoholysis of esters of the phthalic acid with a glycol and subsequent polymerization, by heating glycols with the free acids or with ' halide derivatives thereof, and similar processes. These are described in U.S. 2,465,319 and 3,047,539. Although the glycol 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.
- polyesters will be of the family con- sisting of high molecular weight, polymeric glycol tere- phthalates or isophthalates having repeat general formula:
- n is a whole number from two to four, and mixtures of such esters, including copolyester of terephthalic and isophthalic acids.
- polyesters are poly(ethylene terephthalate) and poly(1,4-butylene terephthalate) .
- 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
- SUBSTITUTE SHEET 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 (d) combined.
- Mixing temperatures and molding tem ⁇ peratures will be illustrated in the following examples but, in any event, they will correspond entirely to those well known to those skilled in the art of resin technology.
- DESCRIPTION OF THE PREFERRED EMBODIMENTS The following examples illustrate the composi ⁇ tions of the present invention. They are not to be con ⁇ strued as limiting the claims in any manner whatsoever.
- Resin compositions are prepared by extruding a mixture of a homopolymer of 2,2-bis(4-hydroxyphenyl) propane (Bisphenol-A) and phosgene (LEXA _- ⁇ 125) , a linear polyester, short milled glass fibers, essentially free of any sizing agent, and, where indicated, a poly- methyl hydrogen siloxane fluid (DF 1040, General Electric Company) . Extrusion is carried out at 265°C. and the extrudate is comminuted into pellets.
- pellets are then injection molded at about 300°C. (cylinder) for Examples A and B and 270°C. for Examples C, D, E and F into standard physical test speci- mens 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 disk according to standard test methods; elastic modulus and tensile yield strength and elongation at yield and at break can be measured by standard test methods.
- HDT heat distortion temperature
- 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, i.e., 5% by weight, of a selectively hydrogenated block copolymer of styrene- butadiene-styrene, such as Shell's Kraton G can be in ⁇ cluded in the composition.
- a selectively hydrogenated block copolymer of styrene- butadiene-styrene such as Shell's Kraton G
- the polycarbonate there can be substituted polyester ' carbonate, polycarbonate siloxane copolymers and blends thereof. All such ob ⁇ vious variations are within the full intended scope of the appended claims.
- 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 (c) 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 avail ⁇ able 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.
- C ' ⁇ gUREA taining glass
- Preferred is a ground short glass fiber.
- any of the hydrogen polysiloxanes known in the art can serve as component (d) .
- Especially useful are those set forth by formula in the above-mentioned U.S. 3,971,756.
- the patent also cites U.S. 2,445,794; 2,448,756; 2,484,595 and 3,514,424 as showing ways of making such siloxanes. To save unnecessarily detailed description, these are all incorporated herein by ref- erence.
- Most important members of the family are those in which R is methyl, or phenyl, or a mixture thereof. These are commercially available.
- poly(methyl hydrogen) siloxane a fluid which is available commercially from General Electric Company under the trade designation DF-1040.
- an impact modifier e
- This 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 illus- trative vinyl aromatics are styrene, vinyl toluene, and the like. Especially suitable are selectively hydrogenated such compounds.
- thermoplastic compositions Any conventional method can be used to formulate the present thermoplastic compositions, and to mold them. The important factor is to insure intimate admixture.
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)
- Reinforced Plastic Materials (AREA)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/US1983/000637 WO1984004318A1 (en) | 1983-05-04 | 1983-05-04 | High impact, high modulus fiber reinforced polymers |
Publications (1)
Publication Number | Publication Date |
---|---|
EP0140885A1 true EP0140885A1 (de) | 1985-05-15 |
Family
ID=22175072
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP83901687A Withdrawn EP0140885A1 (de) | 1983-05-04 | 1983-05-04 | Durch fasern verstärkte polymere mit hoher schlagzähigkeit |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0140885A1 (de) |
JP (1) | JPS60501211A (de) |
AU (1) | AU569469B2 (de) |
WO (1) | WO1984004318A1 (de) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL8601128A (nl) * | 1986-05-02 | 1987-12-01 | Gen Electric | Polymeermengsel met polyfenyleenether en versterkende vezels. |
WO1989010382A1 (en) * | 1988-04-27 | 1989-11-02 | Signworld International Pty. Ltd. | Method and means for forming moulded products |
CA2103414A1 (en) * | 1992-12-03 | 1994-06-04 | Douglas G. Hamilton | Stabilized polyester-polycarbonate compositions |
US8871858B2 (en) * | 2006-05-31 | 2014-10-28 | Sabic Global Technologies B.V. | Thermoplastic polycarbonate compositions |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2518287C2 (de) * | 1975-04-24 | 1982-04-22 | Bayer Ag, 5090 Leverkusen | Glasfaserverstärkte Polycarbonate mit verbesserten mechanischen Eigenschaften |
US4221728A (en) * | 1977-12-28 | 1980-09-09 | General Electric Company | Stabilized polycarbonate compositions |
US4161469A (en) * | 1978-01-09 | 1979-07-17 | General Electric Company | Polyalkylene terephthalate and organopolysiloxane-polycarbonate block copolymer blends |
JPS60501213A (ja) * | 1983-05-04 | 1985-08-01 | ゼネラル エレクトリツク カンパニイ | 高耐衝撃性、高モジユラス繊維強化線状ポリエステル |
AU565558B2 (en) * | 1983-05-04 | 1987-09-17 | General Electric Company | High impact, high modulus reinforced aromatic carbonate polymeric mixtures |
-
1983
- 1983-05-04 AU AU15200/83A patent/AU569469B2/en not_active Ceased
- 1983-05-04 JP JP58501656A patent/JPS60501211A/ja active Pending
- 1983-05-04 EP EP83901687A patent/EP0140885A1/de not_active Withdrawn
- 1983-05-04 WO PCT/US1983/000637 patent/WO1984004318A1/en not_active Application Discontinuation
Non-Patent Citations (1)
Title |
---|
See references of WO8404318A1 * |
Also Published As
Publication number | Publication date |
---|---|
AU569469B2 (en) | 1988-02-04 |
JPS60501211A (ja) | 1985-08-01 |
WO1984004318A1 (en) | 1984-11-08 |
AU1520083A (en) | 1984-11-19 |
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Legal Events
Date | Code | Title | Description |
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PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
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AK | Designated contracting states |
Designated state(s): DE FR GB NL Kind code of ref document: A1 Designated state(s): DE FR GB NL |
|
17P | Request for examination filed |
Effective date: 19850425 |
|
17Q | First examination report despatched |
Effective date: 19860327 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN |
|
18W | Application withdrawn |
Withdrawal date: 19861128 |
|
RIN1 | Information on inventor provided before grant (corrected) |
Inventor name: HEUSCHEN, JEAN, MARIE, HUBERT Inventor name: BUSSINK, JAN Inventor name: VAN ABEELEN, PETRUS, CORNELIS, ALOYSIUS, MARIA |