CA2105082A1 - Polymethylpentene compositions - Google Patents
Polymethylpentene compositionsInfo
- Publication number
- CA2105082A1 CA2105082A1 CA002105082A CA2105082A CA2105082A1 CA 2105082 A1 CA2105082 A1 CA 2105082A1 CA 002105082 A CA002105082 A CA 002105082A CA 2105082 A CA2105082 A CA 2105082A CA 2105082 A1 CA2105082 A1 CA 2105082A1
- Authority
- CA
- Canada
- Prior art keywords
- weight percent
- composition
- reinforcer
- weight
- flame retardant
- 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.)
- Abandoned
Links
Classifications
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- 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
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0066—Flame-proofing or flame-retarding additives
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- 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
- C08K7/04—Fibres or whiskers inorganic
-
- 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
- C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
Abstract
A high strength, thermally resistant, fire retardant, composition of matter is provided comprising (A) about 99.5 to about 75 weight percent of unmodified polymethylpentene where the weight percent of polymethylpentene is based on the total weight of A and B;
and (B) about 0.5 to about 25 weight percent of polyphenylene sulfide where the weight percent of polyphenylene sulfide is based on the total weight of A, and B; (C) about 10 to about 67 weight percent of a reinforcer where the weight percent of the reinforcer is based on the total weight of A, B, C, and D; (D) optionally about 5 to about 45 weight percent of a flame retardant where the weight percent of the flame retardant is based on the total weight A, B, C and D. The composition has utility in the molding art.
and (B) about 0.5 to about 25 weight percent of polyphenylene sulfide where the weight percent of polyphenylene sulfide is based on the total weight of A, and B; (C) about 10 to about 67 weight percent of a reinforcer where the weight percent of the reinforcer is based on the total weight of A, B, C, and D; (D) optionally about 5 to about 45 weight percent of a flame retardant where the weight percent of the flame retardant is based on the total weight A, B, C and D. The composition has utility in the molding art.
Description
W O 92/16~86 PC~r/US92102209 21~ ~ ~ 8 2 POLYMETHYLPENTENE COMPOSITIONS
BACKGROUND OF THE INVENTION
This invention relates to high strength, thermally re6istant, fire retardant, polymethylpentene compositions.
Polymethylpentene, also known as PMP, has long been known in the art. Although many methods are known in the art for improving the performance -characteristics of compositions like polyethylene and polypropylene, these same methods tend not to work in the higher alpha olefins, like PMP. Recently, great emphasis has been pIaced upon modi~ying the PMP polymer structure in order to improve the performance characteristics of this polymer. Most of these methods deal with creating a more interactive surface between the PNP polymer structure and the other constituents in the composition. It has been noted though, that the majority of these methods of improving PMP performance characteristics tend to be time consuming and somewhat expensive. Therefore, a method of producing a high strength, thermally resistant, ~ire retardant, PMP
composition, in which the PNP polymer matrix does not have to be substantially altered, would be of great scientific and economic value.
SUMMARY OF IHE INVENTION
It is an object of this invention to provide an improved PNP composition.
SIJBST~T~E SHEE~
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WO~2/16586 PCT/US92/02209 21a a 0~2 It is another object of this invention to provide a PMP composition with improved thermal resistance.
It is still another object of thi~ invention to provide a PMP composition with improved fire retardant capabilities.
It is yet another ob;ect of thi8 invention to provide a PMP composition with high strength and improved thermal resistance.
It is still another object of this invention to provide a PMP composition with high strength and improved fire retardant capabilities.
It is still another ob~ect of this invention to provide a PMP composition with high strength, improved thermal resistance, and improved fire retardant capabilities.
In accordance w~th this invention, a composition of matter i8 provided which comprises (A) about 99.5 to about 75 weight percent of unmodified polymethylpentene where the weight percent of polymethylpentene is based on the total weight of A and B: and tB) about 0.5 to about 25 weight percent of polyphenylene sulfide where the weight percent of polyphenylene sulfide is based on the total weight of A, and B; (C) about l0 to about 67 weight percent of a reinforcer where the weight percent of the reinforcer is based on the total weight of A, B, c, and D; (D) optionally about 5 to about 45 weight percent of a flame retardant where the weight percent of the flame retardant is based on the total weight A, B, C and D.
D~TAILED DESCRIPTION OF THE INVENTION
Polvmethylpentene fPMP~
The polymethylpentene utilized in the present invention is a homopolymer or a copolymer of a methyl-branched pentene, preferably 4-methyl-l-pentene, and SUBSTITUTE SltEET
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WO92/16~86 PCT/US92/02209 ~ S3 another alpha olefin. Generally, applicable comonomers have from about 2 to about 18 carbon atoms and preferably, have from about 8 to about 16 carbon atoms.
Most preferably, the co~onomer or comonomers are linear alpha-olefins. Longer chain linear alpha-olefins are preferred in that they are easier to copolymerize with polymethylpentene and can, in part, increase clarity, stability, and impact strength to the resulting composition. Exemplary comonomers include, but are not limited to, l-octene, l-decene, l-dodecene, l- -tetradecene, l-hexadecene, and other higher alpha-olefins.
Generally the PMP should have a melt viscosity, measured as the melt flow rate, of about 0.5 to 500 grams per l0 minutes according to ASTM Dl238, procedure B, under a load ~f 5 kilograms and a temperature of 260-C., and preferably 5 to 150 grams per lO minutes. ~hese flow rates tend to provide the most desired polymer composition processing rates.
The amount of polymethylpentene to utilize in this invention is from about 75 weight percent to about 99.5 weight percent. More preferably, it is from about 9l weight percent to about 99 weight percent and most preferably it is from about 92 weight percent to about 98 weight percent, based on the total weight of PMP and PPS. Other additives, which do not interfere with the compositions at hand, such as stabilizers, corrosion inhibitors, and colorants, etc., can be added to the PMP composition to provide additional desired variations from the main PMP compositions disclosed herein. If any additives are added then the weight of PMP used in the calculations of the weight percents in this specification is equal to the weight of PMP plus the weight of the additives. However, it should~be noted that the P~2 polymer structure is unmodified. By ~ BS~ E SHE~
., , WO92/16586 PCT/US9~/022 the term ~unmodified~ it is meant that the polymer has no grafting agents acting upon it in order to modify its polymer matrix.
PolY~henylene sul~i~e (PPS~
The polyphenylene sulfides utilized in the present invention are well known in the art and are described in U.S. Patents 3,354,129; 3,396,110;
3,919,177; and 4,025,582; which are hereby incorporated by reference. The polyphenylene sulfide useful in accordance with this invention preferably has a melt flow, when tested in accordance with ASTM D-1238 at 315-C. using a 5 kilogram weight, of 1 to about 2,500 grams per 10 minutes.
The amount of PPS to utilize in this invention is from about 0.5 weight percent to about 25 weight percent where the weight percent of PPS is based on the weight of PMP and PPS. More preferably, it is from about 1 to about 9 weight percent and most preferably it i5 from about 2 to about 8 weight percent. The rationale for these ranges is that, while increasing the amount of polyphenylene sulfide in the composition tends to increase the thermal resistance of the polymethylpentene composition, the benefit of adding additional large increments of polyphenylene sulfide does not outweigh the cost. Indeed, practically speaking, small amounts of PPS can be used to obtain large increments of thermal resistance 80 that further additions of PPS do not bring cost effective advantages.
Rein~oxcing Aaents The reinforcing agents usable in the present invention include, for example, glass fiber, carbon fiber, boron fiber, and other inorganic substances, etc. Glass fiber reinforcements are available i~ a variety of compositions, filament diameters, sizings, SU8STlTlJTE SHEET
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WO92/1~86 PCT/US92/02209 2 ~ ;3 and forms. The most commonly used composition for reinforced thermoplastics is E Glass, a boroaluminosilicate.
The diameter of the glass fiber i8 preferably less than 20 micrometers, but may vary from about 3 to about 30 micrometers. Glass fiber diameters are usually given a letter designation between A and Z.
The most common diameters encountered in glass reinforced thermoplast~cs are G-f~lament (about 9 micrometers) and K-filament (about 13 micrometers).
Several types of glass fiber products can be used for reinforcing thermoplastics. These include yarn, woven fabrics, chopped strands, mats, etc. Continuous filament strands are generally cut into lengths of 1/8, 3/16, 1/4, 1/2, 3/4, and 1 inch or longer for compounding efficiency in various processes and products.
The glass fiber products are usually sized during the fiber ~ormation process or in a post treatment. Sizing compositions usually contain a lubricant, which provides protection for the glass `
fiber strand; a film former or binder that gives the glass fiber strand integrity and wor~ability; and a coupling agent that provides better adhesion between the glass fiber strand and the polymeric materials that are reinforced with the glass fiber strand. Additional agents that may be used in sizing compositions include emulsifiers, wetting agents, nucleating agents, and the like.
The amount of sizing on the glass fiber product typically ranges from about O.2 to 1.5 weight percent based on the weight of the glass, although loadings up to lO percent may be added to mat products.
Examples of film formers include polyesters, ep~xy resins, polyurethanes, polyacrylates, polyvinyl TITUTE SHE~T
wos2/16s86 PcT/us92/o22o9 ~ 6 -acetates, polyvinyl alcohols, starchs, a~d the like.
Usually the coupling agent is a silane coupling agent that has a hydrolyzable moiety for bonding to the glass and a reactive organic moiety that is compat~ble with the polymeric ~aterial that i6 to be reinforced with the glass fibers.
Preferably the amount of reinforcers used are present in about 10 to about 67 weight percent, based on the weight of PMP, PPS, the reinforcer and the lo optional flame retardant. Preferably, the glass fibers are present in the range of about 10 to about 55 weight percent, and most preferably in the range of about 10 to about 45 weight percent. Not enough glass fiber does not improve the polymer properties and too much glass fiber results in not enough polymer to coat the glass fiber, i.e., the $ibers are not wetted ~ut.
El~m~ Retardants Fla~e retardants utilized in the present invention include, but are not limited to, phosphate acid esters such as tricresyl phosphate, tributyl phosphate, tris(dichloropropyl)phosphate, and tris(2,3-dibromopropyl)phosphate; halogenated hydrocarbons such as chlorinated or brominated, ethane, propane, butane, and cyclodecane; halogenated polymers such as chlorinated or brominated, polyethylene, polypropylene, polystyrene, and polycarbonates; brominated or chlorinated diphenyl oxides such as octabromodiphenyl oxide, and decabromodiphenyl oxide; antimony type compounds such as antimony trioxide, antimony potassium tartarate; boron type compound such as borax, zinc borate, barium metaborate: and metallic hydroxides such as magnesium hydroxide, aluminum hydroxide, calcium hydroxide, barium hydroxide, etc. Most preferably the flame retardant is selected from the group consi~tin~
of antimo~y type compounds, boron type compounds, SUBSTITUTE SHEET
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WO92/16586 PCT~US92/022~9 polybrominated diphenyl oxides, brominated polystyrenes, polydibromophenylene oxides, brominated polycarbonate derivatives, or mixtures thereof.
Preferably the amount of flame retardant used is between about 5 weight percent to about 45 weight percent based on the weight of PMP, PPS, reinforcer, and flame retardant. More preferably, the amount used is between about 10 weight percent to about 40 weight percent, and most preferably is from about 15 to about 36 weight percent.
EXAMP~ES
~ hese examples are provided to further assist a person skilled in the art with understanding this invention. The particular reactants, conditions, and the like, are intended to be generally illustrative of this invention and are not meant to be construed a8 unduly lim~ting the reasonable scope of thi6 invention.
The following ASTM test procedures were utilized in the testing.
Analysis ASTM Method No.
Tensile Strength at Break D638, at 5 mm/min.
Elongation at Break D638, at 5 mm/min.
Flexural Strength D790, 2 inch span, 1 mm/min. crosshead speed Flexural Modulus D790, 2 inch span, 1 mm/min. crosshead speed Izod Impact Strength, D256 Notched and Unnotched Heat Deflection Temperature D648, at 264 psi (HDT) (-C.) Experiment~ ials Dry blends of polymethylpentene (PM~) ~nd polypropylene (PP~ were prepared, respectively, by drum ~BSTITUTE SHEET
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tumbling 10 Xilograms of resin with 5 grams of Mg4A12(OH)12CO3 3H2O (DHT-4A), 50 grams of Irganox 1010, 50 grams of Anoxsyn 442 and 10 grams of Weston 619 for 30 minutes. Since the total mass of each mix amounted to 10115 grams, a 101.15 gram portion was equivalent, respectively, to 100 parts PMP or PP, 0.05 phr DHT-4A, 0.5 phr Irganox 1010, 0.5 phr Anoxsyn 442 and 0.1 phr Weston 619.
The PMP/PPS formulations were compounded in a Werner & Pfleiderer ZSX-30 twin screw extruder (general purpose compounding screw/barrel configuration) at 250 rpm and 260-290-C. temperature profile. The compositions were stranded, pelletized and dried overnight at 110-C. The PP/PPS formulations were compounded in a Werner & Pfleiderer zsX-30 twin screw extruder at 250 rpm and 200-230 C. profile. These compositions were also stranded, pelletized and dried overnight at 110-C.
The pelletized compositions were molded into ASTM test samples on a Engel Model EC88 injection molding machine with a 55 ton clamp force. The PMP/PPS
blends were molded with a 136-C. mold temperature, 280-295-C. barrel temperature and 30 second cycle time.
The PP/PPS blends were molded with a 90-C. mold temperature, 220-240-C. barrel temperature and 30 second cycle time. Molded parts were annealed for one hour at 150-C. be~ore testing.
The formulations of the PMP and PP are illustrated along with the other materials in Table EM.
STIT~ TE SH~E~
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Wo92~6s86 PCT/US92/02209 TABLE EM .
A. Polymethvlmentene Base Formulation 100.00 phr PMP PMP Homopolymer, ~18 MFR) 0.05 phr DHT-4A hydrotalcite, available Srom Mitsui Petrochemicals, Inc.
0.50 phr Irganox 1010 tetrakis (methylene 3-(3,5-di-t-butyl-4-hydroxyphenyl)-propionate)methane, available from Ciba-Geigy 0.50 phr Anoxsyn 442 aliphatic thio compound, available from Atochem 0.10 phr Weston 619 distearyl pentaerythritol :
diphosphite, available from General Electric ~. Polypromvlene 100.00 phr PP PP Homopolymer, (12 MFR) O.05 phr DHT-4A hydrotalcite, a~ailable from Mitsui Petrochemicals, Inc.
0.50 phr Irganox 1010 tetrakis (methylene 3-(3,5-di-t-butyl-4-hydroxyphenyl)-propionate)methane, available from Ciba-Geigy 0.50 phr Anoxsyn 442 aliphatic thio compound, available from Atochem 0.10 phr Weston 619 distearyl pentaerythritol diphosphite, available from General Electric S~iBSrlTUrE SHEET
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o~2 - 10 -C. PolyDhenvlene Sulfide Approximate Grade Flow Rate Type Wash A 2500 uncured water B 900 cured water C 120 cured water D 300 uncured acid E 160 uncured water lASTM D1238 at 315-C. and 5 kg load, modified with a 5 minut~ preheat instead of a 6 minute preheat.
D. Glas~s ~ein~orcemen~ P~o~cts Manu-facturer Product Sizingl Diameter2 Length (in) L0I3 oCF4 457BA6 pp K 3/16 0.90 OCF 408BC PBT K 3/16 0.70 OCF 492AA Nylon/PET G 1/8 1.10 OCF 497DC PPS X 1/8 0.35 CertainTeed5 930 PB~ K 3/16 0.80 CertainTeed 93B Nylon/PET G 1/8 1.00 lIndicates the resin for which the sizing package was optimized: PP represents polypropylene, PBT represents polybutylene terephthalate and PET
repre~ents polyethylene terephthalate.
2G-filament nominal diameter is 9 ~m.
K-filament nominal dizmeter is 13 ~m.
3LOI is ~he nominal ignition loss of the product. This is the percent organic solids of the sizing package.
4Owens Corning FiberglasTM Corp 5CertainTeed Glass Corporation i ?!~BSTITUTE SHEET
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21~3~w 6All examples used OCF 457BA unless specified otherwise.
~xa~le I
~his example i8 provided to illustrate that the effect observed in polymethylpentene compositions does not occur in polypropylene compositions.
Referring to the data in Table I it is evident that relatively small amounts of PPS did not enhance the HDT
values in Runs 12, 13, and 14. Furthermore, it appears that PPS functions only as a filler in the polypropylene compositions.
TABLE I
pP and PPS Blends:
Pro~erti~s as a Function o$ Polv~henylene Sulfide Level (30% Glass Reinforced~
Run Number 11 12 13 14 Percent PPS ~Grade B) 0 5 10 25 Tensile Strength, Break (ksi) 7.77.5 7.36.7 Flexural Strength (ksi)10.8 10.7 10.4 9.8 Flexural Modulus (ksi) 806 821 803 849 Unnotched Izod Impact (ft-lb/in) 2.62.5 2.22.2 HDT ~ 264 psi (-C.) 150.1149.9 150.0149.8 ~HDT/wt~ PPS -0.04 -0.01-0.01 ~xam~le II
This example is provided to illustrate the effect observed in polymethylpentene/polyphenylene culfide/reinforced compositions. It is evident from the data below that relative small amounts of PPS
enhanced the HDT values in PMP/PPS resins. For SUBSTITUTE SHEE T
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WO92/16~86 PCTIUS92/02209 2 ~ 2 example, in Run 22, at a 5 weight percent PPS level, the HDT value was approximately 56% greater than the HDT value in Run 21 which contained no PPS.
Furthermore, it can be seen from the data below, in the ~HDT/weight percent PPS row, that increasing the weight percent of PPS does not proportionally increase the change in the heat deflection temperature.
PMP and PpS ~lends:
Pro~ç~ies a~ ly~ ig~_oo_,~lyphçnylene Sulfide Level (3Q~Gl~ss Reinforced~
Run Number 21 22 23 24 25 Percent PPS (Grade B) 0 5 1025 50 Tensile Strength, Break (~si) 6.3 6.2 6.1 6.36.3 Flexural Strength (~si) 9.7 9.1 9.1 9.3 9.6 Flexural Modulus (ksi) 674 738 804 890 1,020 Unnotched Izod Impact (ft-lb/in) 2.1 2.2 2.5 2.31.4 HDT ~ 264 psi (-C.)111.0 173.3 176.2 195.1217.7 ~HDT/wt% PPS12.5 6.5 3.4 2.1 Example III
Additional data was gathered to confirm the findings observed in Example II. This data is illustrated in Table III. It is apparent from the data, that at very low levels of PPS, a significant amount of thermal resistance can be attained.
Further~ore, it can be seen from the data below, in the ~HDT/wt% PPS row, that increasing the weight percent of PPS does not proportionally increase the change ~in the heat deflection temperature. This is illustrated by S~IBSTITUTE SttEE ~
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WO 92/16586 PCr/US92/02209 ~ l a ~'~t~
the ~HDT/weight percent PPs row whic:h shows a dra~natic decline from a 2.5 wsight percent loading to a 20 weight percent loading.
TA~E III
R~P and PPS ~e~ls:
~e~ties as a E~on of Polv~lene ~lfide Level r30% Gla~ Reinfor~
R~n No. 31 32 33 34 35 36 .
P~.t PPS (OE~e 8) 0 2.5 5.0 7.510.0 20.0 . .
qensile Strer~h ~ksi) 6.7 6.9 6.76.9 7.0 7.3 El~n (S) 3.1 3.1 3.1 3.03.0 3.1 Fle~ral StL~Ul ~ksi) 9.3 8.9 8.8 8.58.9 9.1 Ele~al ~ulus (ksi) 815 809 822 805856 891 Notd~ed Izod (ft-lb/in) 0.9 1.0 0.90.9 o.9 0.8 ~t~ Izcd (~t-lb/in) 2.S 2.7 2.6 2.72.9 2.2 HDr at 264 psi (-C.) 104.7 156.1 165.1 163.2 167.2 184.1 /wtS E~ 20.6 12.1 7.8 6.3 4.0 Exam~le IV
This example shows the properties of injection molded sample~ prepared from PMP/PPS molding compositions containing different grades of PPS at the 5 weight percent PPS level. The different grades of PPS are identified in Table EM. Results are sl~mmarized in Table IV.
Referring to the HDT values in Runs 41-45, it can be seen that this property varied over a range 157.3 to 164.2-C. This is a dramatic enhancement of HDT relative to the HDT value of 104.7-C. exhibited by the sample in Control ~un 31 which contain no ~S. The general enhancement of HDT values in Runs 41-45 SU~S~ITUTE SHE~
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, . . ' " , WO92/16586 PCT/US92tO2209 indicate that any of the five different types of PPS
are suitable for use in the inventive composition.
TABLE IV
PMP and PPS Blends:
5Effe~t of PPS Variant on Pro~erties ~0% Glass Reinforced) Run No. 41 42 43 44 45 PPS Grade A B C D E
Tensile Strength ~ksi) 7.1 6.9 6.6 6.8 7.1 Elongation (%) 3.2 3.2 3.2 3.2 3.2 Flexural Strength (ksi) 9.1 8.8 9.o 9.1 9.1 Flexural ~odulus (ksi) 831 826 821 842 832 Notched Izod (ft-lb/in) 0.9 1.0 1.0 1.0 0.9 Unnotched Izod (ft-lb/in~ 2.4 4.5 3.1 3.1 2.5 HDT at 264 p8i (-C.) 158.~ 157.3 160.9 157.5 164.2 ~xample V
This example ~hows the properties of injection molded samples prep red from 30% glass reinforced PMP/PPS molding compositions containing six different types of glasæ reinforcement. The different types of glass reinforcements are identified in Table EM. The polyphenylene 8Ul fide was Grade B at the 5 weight percent level. The results are ~ummarizsd in Table V.
Referring to Runs 53 and 56 in Table V, it is evident that the ~ystems containing, respectively, OCF
492AA and Certainteed 93B gave the highest HDT values of 184.5 and 17SØ These glass reinforcements are - sized for compatibility with Nylon/PET resins. The smaller filament diameters of these glass reinfo~ce-ments perhaps accounted for the superior HDT values SU13STITU~E SXEET
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exhibited by the molded samples in Runs 53 and 56. The glass reinforcements sized for compatibility with polypropylene, polybutylene terephthalate and Nylon/PET
resins imparted comparable mechanical properties to molded samples, respectively, in Runs 51, 52, 53, 55, and 56. Surprisingly, the glass reinforcement sized for compatibility with PPS (Run 54) providsd molding samples which exhibited the lowest HDT values of the series.
~t is noteworthy that all of the HDT values in Table V (regardless of the type of glass reinforcement) were significantly greater than that of control run 31.
q~E V
~P and P$S Elends:
Effec~ Of Glass Reinfor~E~t cn Pnox~ties t30% Gl s Reinfo~d) Run No. 5152 53 54 55 56 Glass Reinfon#~ænt 457B~408EC 492AA 497DC 93093B
-Tens;le Stn~th (ksi) 6.5 6.8 6.8 5.8 7.1 6.4 Elongation (%) 1.6 1.6 1.4 1.5 1.6 1.6 25 Flex~ S~U-(ksi) 8.7 8.6 8.7 7.7 9.3 8.2 Flex~ Moh~us (ksi) 800 789 832 789 83~ 789 No~d Izod tft-lb/in) 0.9 1.1 1.2 1.0 1.2 1.0 UnnJ3~{d Izod (ft-Ib/in) 2.9 2.9 3.6 3.0 3.1 3.4 HDT at 264 p6i t 'C.)164.1 165.7 184.5 lS5.9 169.8 175.0 ExamDle VI
This example shows the properties of injection molded samples prepared from 30% glass reinforced PMP/PPS molding compositions under somewhat varied processing conditions. The polyphenylene ~BSTITUT~ SH~ET
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W092/16586 PCT~US92/02209 sulfide was Grade B at a 5S by weight level. The results are summarized in Table VI.
In Runs 61 and 62 samples were molded at the higher temperature of 136-C. The sample in Run 62 was annealed for two hours at 150-C. whereas the sample in Run 61 was not annealed. Since the HDT values in Runs 61 and 62 were essentially the same (162 V8. 167), there appeared to be no annealing effect perhaps indicating that both PMP and PPS, especially the PPS, attained maximum crystallization at the 136-F. mold temperature.
In Runs 63 and 64 samplec were molded at the lower temperature of 38-C. The sample in Run 64 was annealed for two hours at 150-C. whereas the sample in Run 63 was not annealed. Since the HDT values in Runs 63 and 64 were not comparable (147 vs. 165), there appeared to be an annealing effect in the sample of Run 64. Although the properties of molded samples at the lower mold temperature were comparable, it is noteworthy that the HDT value of the sample in Run 64 was significantly greater than that of the non-annealed sample in Run 63. Perhaps this indicates that the PPS
did not completely crystallize at the lower mold temperature of 38-C. It should be noted, however, that even at the lower mold temperature the HDT value of the non-annealed 6ample in Run 63 tl47) was significantly greater than that of the sample in Control Run 31.
The results in Table VI indicate that higher mold temperatures should be used on the inventive molding compositions to realize maximum enhancement of HDT values in the injection molded samples.
SUBS~ITU~ S~ET
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W0 92/16~86 PCT~US92/02209 ~LE VI
Eff~ of E~x~essina Conditions on Properties (30% Glass Reinforced) R~n No. 61 62 63 64 Mbld Tecperature ('C.) 136 136 38 38 Arnealing No Yes No Yes Tensile Strength (ksi) 6.8 7.1 6.8 7.0 Elongation (%) 3.4 3.2 3.2 3.0 FlexLral SI~U. (ksi) 8.4 8.7 8.1 8.6 Flex~ral Mbdulus tksi) 741 752 720 729 N~ Izod (~t-lb/in) 0.9 0.9 1.0 1.0 Il~LJbdh d Izod (ft-Ib/in) 2.6 2.6 2.6 2.8 HDr at 264 pd (-C.) 162.1 166.7 147.1 165.3 GENERAL NOTES FOR ALL FLAME RETARDANT EXAMPLES
The weight ratio of the flame retardant to the antimony oxide 6ynergist in each formulation was 3:1. The samples, in each of the following examples, were tested according to ANSI/UL94 Standard for tests for flamability of plastic materials for parts and devices and appliances. The speciman thickness was 1/8 of an inch. In these UL94 tests a result of V-o is better than a V-l and both of these results are better than a fail.
~xample VII
This example describes flame retarded glass reinforced PMP molding compositions containing 2.5 to 10 weight percsnt PPS and 18 to 27 weight percent of decabromodiphenyloxide, a commercial flame retardant available as DE-83R from Great Lzkes Chemical ~J~S~ITl~E SHtET
W092/16~86 PCT~US92/OZ209 2 1 ~
Corporation. Table VIIA shows the properties of injection molded samples prepared from compositions containing 18 weight percent DE-83R and 0, 2.5, 5 and 10 weight percent PPS. Table VII8 shows the properties of injection molded samples prepared from compositions containing 22. 5 weight percent DE-83R and 0, 2. 5, 5 and 10 weight percent PPS. Table VIIC shows the properties of injection molded samples prepared from compositions containing 27 weight percent DE-83R and 0, 2.5, 5 and 10 weight percent PPS.
Part A
Referring to runs 71A and 72A in Table VIIA, neither of which contained PPS, it is evident that the glass reinforced PMP sample without flame retardant (run 72~) exhibited higher property values (except for îlexural modulus) than did the sample of run 71A which contained 18 we~ght percent flame retardant ~DE-83R).
It is noteworthy that the samples of runs 71A and 72A
failed to obtain V-O (self extinguishing) ratings in the UL94 flammability test. Thus, the presence of a flame retardant in a glass reinforced PMP formulation was detrimental to the physical properties of the molded sample and did not render the composition flame resistant. Inventive runs 74A and 75A in Table VIIA
show that the PPS at 5 and 10 weight percent levels enhanced flexural modulus and HDT values as well as flame retardancy. The samples of runs 74A and 75A
rated V-O in the UL94 test. Run 73A is noteworthy because it shows that 2. 5 weight percent PPS is insufficient to enhance flame retardancy to a V-O
rating with only an 18 weight percent flame retardant loading. The HDT value in run 73A, however, was significantly greater than the observed values in runs 71A and 72A . Therefore it can be concluded that the addition of this flame retardant lowers the mechanical SUBSmlJT~ SH~ET
. .
.
..
,.' .' ' : , . .: ' -WO92/16~B6 PCT/US92/02209 2 1~
performance of the polymethylpentene composition.
However, the addition of PPS restores both the mechanical performa~ce as well as improving the ,lame retardancy of t~e co~bined composition.
~ VIIA
~action with Flame Retu~brt Dooi~nT~d1~henyloxide 18 Wt% Flame Ret~ebrt (30 Wk~ Glass Reinfoxxd~
_ Run 71A 72A 73A 74A 75A
% nE-83~a 18.0 Oo~x~ 18.0 18.018.0 % PFS (Gra~e B) o o 2.5 5.010.0 lensile Stn~h, B~k (ksi) 5.4 6.1 6.2 6.9 6.7 Fle~n~l Sbn~h (ksi) 7.4 8.6 8.3 8.4 8.6 Fle~n~l ~Y~US (ksi) 920 710 ggo 995 1,080 No~d Izod ~p~ (ft-lb/in) 0.5 0.8 0.5 0.6 0.6 Unn*l~cd Izcd ~xwk (ft-Ib/in) 1.3 2.2 1.5 1.7 1.5 HDT ~ 264 p6i ~ C.) 122.5 124.3 157.3 165.2 161.7 UL94 V-l ~1 V-1 V-0 V-0 Limiting ~ n ~x (LDI)b (%) 31.5 25.5 29.2 30.0 31.5 a DE-83R represents decabromodiphenyloxide (DBDP0) (83% Br), available from Great Lakes Chemical Corporation.
b The limiting oxygen index (LOI) is expressed as the minimum volume percent of oxygen necessary in an oxygen/nitrogen mixture to sustain combustion of a burning sample. The magnitude of LOI numbers i8 directly proportional to flame retardant effectiveness.
aUBSTlTI JTE SHEET
- , . .
W O 92/16S86 PC~r~US92/02209 2 ~ 2 Part B
Referring to runs 71B and 72B in Table VII8, neither of which contained PPS, it can be seen that the flame retardant reduced the property values (except for modulus) in run 71B but the sample rated V-0 in the UL94 flammability test. Control run 72B without flame retardant failQd the UL94 test. Inventive runs 73B, 74B and 75B in Table VIIB show that the PPS at 2.5, 5 and 10 weight percent levels enhanced flame retardancy (~ee higher LOI values compared to the LOI values of runs 71B and 72B), modulus values and ~DT values.
Thus, at the 22.5 vQight percent loading of flame retardant, the PPS enhanced both the flame retardancy to the point of being self-extinguishing and the physical properties of the injection molded samples.
S!JBSTITU~E SttEET
.. . . . ~ . .
.. ... , ... . -.
. . ` . . ~.... . . : ~
.` - . ~
, ` . . . .
.
W o 92/16~86 PCTtUS92/02209 ~ ~ ,J ~
DecabrcmLdi~henvloxide 2~.5 Wk% Flame Frtard3nt (30 Wk% Glass ReinfcrGed) : `
R~n 71B 72B 73B 74B 75B
S DE n3R 22.5Ccntrol 22.5 22.5 22.5 S PæS (Gra~e B) 0 2.5 5.0 10.0 Tens~le ~ , Ereak (ksi) 5.4 6.1 6.0 6.4 6.4 FlexLral Strength ~ksi) 7.4 8.6 8.2 8.3 7.6 FlexLral McdLlus (ksi) 1,100 710 1,100 1,060 1,160 Nbkched Izod l~pact (ft-Ib/in)0.5 0.8 0.5 0.5 0.5 13~YJldho~ Izod Impact~ft-lb/in) 1.2 2.2 1.6 1.6 1.1 H~ ~ 264 Fsi (-C.) 120.0 124.3 160.0 159.4 165.3 U~4 V-0 Fail V~ V-0 V-0 Limitir~ Qx~en ~c (LOI) (%)29.2 25.5 30.8 32.1 33.6 .
Part C
Referring to runs 71C and 72C in Table VIIC, neither of which contained PPS, it is evident that properties (except for flexural modulus) were reduced by the flame retardant (run 71C) but the sample did rate V-0 in the UL94 test and possessed a desirably high LOI value of 33. The glass reinforced PMP sample (run 72C) without flame retardant failed the UL94 test.
Inventive runs 73C, 74C and 75C in Table VIIC show that the PPS additive at 2.5, 5 and 10 weight percent levels maintained fla~e retardancy and enhanced HDT values of camples containing 27 weight percent :Elame retardant.
SUBSTITLJTE SHE~T
WO 92/16S86 P~US92/02209 210'~ 82 ,q~E VlIC
;~actia~ with Fq# Eb~
DecobrorLdi~henvloxide 27 Wk% Flame PeeDrd~nt (30 Wk% Gl~e Reinforced~ ~
:
Run 71C 72C 73C 74C 75C
% DE-83R 27.0 Cbnkrcl27.0 27.027.0 % PFS (Grade B) 0 2.5 5.010.0 ~, lersile Strength, Ereak (ksi) 5.1 6.1 5.8 5.9 6.4 FlexLral SLLe~Uh (ksi) 7.2 8.6 7.4 6.7 7.2 Flo^~n~al M~dulus (ksi) 1,190 7101,200 1,1601,300 Nbtdhed Izod Impact (ft-Ib/in) 0.5 0.8 0.5 0.4 0.5 ~rr~h~ 3a Impact (ft-Ib/in) 0.9 2.2 1.0 0.9 0.9 HDr 0 264 p6i (-C.) 120.3 124.3160.0 171.2177.8 UI94 V-0 F~l V-0 V-0 V-0 L~miting a~n ~Y~X -:
(LDI) (%) 33.0 25.5 33.6 34.935.4 Example.YIII
This example describes flame retardant glass reinforced PMP molding compositions containing 2.5 to 10 weight percent PPS and 18 to 27 weight percent o~
brominated polystyrene, a commercial flame retardant available as Pyro-Chek 68PB (68S bromine) ~rom Ferro Corporation. Table VIIIA shows the properties of injection ~olded samples prepared from compositions containing 18 weight percent Pyro-Chek 68PB and 0, 2.5, 5 and 10 weight percent PPS. Table VIIIB shows the properties of injection molded samples prepared from compositions containing 22.5 weight percent Pyro-Chek 68PB and 0, 2.5, 5 and 10 weight percent PPS. Table SUBSmUTE SH~ET
j ~. .
.
.. . . . . . ~ . . .. . . . . .
- : : . . . ..
WO92/16~6 PCT~US92/02209 ~a~2 VIIIC shows the properties of in~ection molded samples prepared from compositions containing 27 weight percent Pyro-Chek 68PB and 0, 2.5, 5 and 10 weight percent PPS.
Part A
Referring to runs 81A and 82A in Table VIII, neither of which contained PPS, it can be seen that the glass reinforced PMP sample without flame retardant (run 82A) had higher property values in general than did the sample of run RlA which contained 18 weight percent flame retardant (Pyro-Chek 68PB). Sa~ples of both run 81A and 82A failed the UL94 flammability test.
It is noteworthy that the samples in runs 83A and 84A
at the 2.5 and 5 weight % PPS levels failed to enhance flame retardancy to a V-0 rating but HDT values were increased to about 155. Inventive run 85A shows that the PPS at the 10 weight percent levels enhanced ~lexural modulus and HDT ~alues as well as flame retardancy. The injection molded sample in run 85A
rated V-0 in the UL94 test. The data in Table VII
suggest that between 5 and 10 weight percent PPS at the 18 wt% loading of flame retardant is required to obtain maximum enhancement of physical properties.
SUBSTITUTE SHEET
.
, ' W o 92/16586 PCT~US92/02209 2 1 ~ 2 - 24 - ~
.q~E VmA ' PMP and PPS Blends:
Erominated P~lystvrene 18 Wt% Flame ~eearC3nt ~30 Wk% Glass Reinforced~
~n 81A 82A 83A 84A 85A
% Fyro-Chek 68P~a 18.0 Control 18.0 18.0 18.0 % PPS (Grade B) 0 0 2.5 5.0 10.0 lens;le Strength, Ereak (ksi) 5.46.1 5.9 6.3 6.6 FlexLral Strength (ksi) 7.98.6 8.4 8.6 8.9 Flexural M~dLlus (ksi) 900 710 930 970 1,050 Nbkched Izod Impact (ft-Ib/in) 0.50.8 0.6 0.6 0.7 UCrr~dh d Izod I~pact (ft-Ib/in) 1.4 2.2 1.9 1.7 1.9 264 psi (-C.) 130.8124.3154.3156.9156.8 U~4 FailFail V-l V-l V-0 I1miting Qx~en :~c (LO~) (%) 27.625.5 29.2 30.0 31.5 a Pyro-Chek 68PB represents a brominated polystyrene (68% bromine) available from Ferro Corporation. `
Part B
Referring to runs 81B and 82B in Table VIIIEI, neither of which contained PPS, it is evident that the presence of flame retardant at a 22.5 weight percent loading (run 81B) compromised the physical properties of a molded sample and the sample failed to rate V-0 in the UL94 flammability test. Run 82B is a glass rein-forced PMP sample without flame retardant (control).
Inventive samples 83B, 84B and 85B in Table VIIIB show that the PPS at the 2.5, 5 and 10 weight percent levels SUBS~ITIJTE SH~E~
. . . . . ..
2 ~ 8 `~
snhanced physical properties, particularly HDT values, and enhanced flame retardancy as evidenced by the higher L~I values and a V-0 rating in the UL94 flammability test. It is noteworthy that in Table VIIIB PPS was effective at 2.5 weight percent in runs wherein the flame retardant was at the 22.5 weight percent loading. As noted previously, the PPS was required at the 10 weight percent level to be fully effective in the presence of only 18 weight percent flame retardant (see Table VIIIA).
Table VIIIB
PMP and FP5 Elends:
b~ ction with Flame R-t~brt Broyhxeed P~lYs~n~e 22.S Wt% Flame Rct~brt (30 Wk% Glass Reinf~xæd~
Run 81B 82B 83B 84B 85B
% Pyn~C~Y~ 68PB 22.5 O~ol 22.5 22.5 22.5 % PPS (G~e B) o o 2.5 5.0 10.0 _ _ _ _ Tensile Sbn~h, B~k (ksi) 5.4 6.1 5.6 5.8 6.4 Flex~21 Stna~h (ksi) 7.7 8.6 8.7 8.5 9.1 Fle~n~l Mo~us (ksi) 940 7101,030 1,050 1,140 N~x~ed Izod ~ t (ft-lb/in) 0.5 0.80.5 0.6 0.6 U~JI~Yd Izcd ~x~ (ft-Ib/in)1.2 2.21.3 1.5 1.5 HDT ~ 264 p6i (-C.) 138.0 124.3 153.9 155.9 159.9 . .
UI~4 V~ 1 V-0 V-0 V-0 T .;mi ting Q~n ~Y~X
(LDI) (%) 28.4 25.5 31.5 31.5 33.0 Part C
Referring to runs &lC and 82C in Table VIIIC, neither of which contained PPS, it can be seen in run 81C that a 27 weight percent loading of flame retardant ~'JBSTlTUTE SHEET
WO 92tl 6~86 PCT/US92/~2209 h ~ ~ ~ 9 8 2 reduced properties except for modest increases in modulus and HDT values. This sample rated V-0 in the UL94 test. A contrc~l run (No. 82C) with a glass reinforced PMP composition without flame retardant failed the UL94 flammability test.
Inventive runs 83C, 84C and 85C in Table VIIIC, show that the PPS at the 2.5, 5 and 10 weight percent levels dramatically enhanced modulus and HDT
values. The enhanced flame retardancy of the sample was evidenced by the higher values of the L0I.
~E vmc FMP and PP5 E4ends:
~açticn with Flame ~etosbrt B~x~s~ted P~lv5~n~ne 27 Wk% Fla~e RYt~nbrt ~30 Wk% Gl~C~ Reinf~xd) Run 81C 82C 83C 84C 85C
% PynrC~Yk 68PB 27.00o~ol 27.0 27.027.0 % PFS (Grade B) 0 0 2.5 5.010.0 Tensile Stn~th, Bn~k (ksi) 5.1 6.1 5.6 5.8 6.3 Fle~n~l S~n~Ul(ksi) 7.3 8.6 8.4 8.6 9.1 Flex~ Moh~us (Xsi) 980 7101,100 1,160 1,230 Nou~d Izcd ~x~t (ft-lb/in) 0.4 0.8 0.5 0.5 0.5 unn~=tn~ Izcd ~x~t (ft-lb/in) 1.12.2 1.5 1.2 1.0 HDT ~ 264 p6i (-C.) 138.3 124.3152.1 1~.8 158.9 -UI94 V-0 F~l V-0 V-0 V-o T;miting Q~n ~x (LDI) (%)30.8 25.5 33.0 33.6 35.4 _ Exam~le 1~
This example describes a flame retarded reinforced PMP molding composition containing 10 weight percent PPS and 22.5 weight percent of a SUBSTITUTE SH~E-~
, .
WO92~16586 PCr~US92102209 2 ~ f ~
polydibromophenylene oxide, a commercial flame retardant available as PO-64P from Great Lakes Chemical ~ -Corporation. Table IX shows the properties of injection molded samples.
s Referring to runs 91 and 92 in Table IX, neither of which contained PPS, it is evident in run 92 that a 22.5 weight percent loading of fla~e retardant reduced properties except for ~ome increase in modulus and HDT values. This sample rated V-0 in the UL94 test. A control run (No. 91) with a glass reinforced PMP composition without flame retardant failed the UL94 flammability test. Inventive run 93 in Table IX, shows that the PPS additive at the lO weight percent level enhanced modulus and HDT values. ~he enhanced flame retardancy of the sample was reflected by the higher L~I value (34.9).
TITUTE S~ET
. .
, . ~
WO 92/16~86 PCllUS92/02209 2 ~ 2 28 -~ l:X ' Interactial wi~h Plame 8 (30 W~% Glass R~in~or~) Rl~n 91 92 93 % ~64pa C~trol 22.522.5 ~ EeS O O 10.0 _ _ Tensile St~th, B~ealc (ksi)6.1 5.8 6.7 E~e~ral Sl~ (ksi) 8.6 8.3 8.2 ~ i) 710 1,0301,200 No~ Izod ~c (~-~b/in) 0.8 0.5 0-5 W~ Izod ~ (~-~b/in) 2.2 1.2 .8 Hl~ 0 264 pgi (-C.) 124.3 150.0160.2 UL94 Eail V~~O V-O
T.im~~ axygen ~c (IDI) (%)25.5 30.034.9 a PO-64P represents polydibromophenylene oxide (64% Br) available from Great Lakes Chemical Corporation.
2S ;~xamDle X
This example describes flame retarded glass reinforced PMP molding compositions conta~ning 5 and 10 weight percent PPS and 22.5 weight percent of a tetrabromobisphenol A carbonate oligomer, a commercial flame retardant available as BC-58 from Great Lalces Chemical Corporation. Table X shows the properties of injection molded samples.
Referring to runs 101 and 105 in Table X, none of which contained PPS, it can be seen that the SUBSTITUTE S~t'ET
. . ~ .
. . . :: . -., . ~. . , ... ` ~ .
~as~sS2 flame retardant in the sample of run lOl and 104 reduced properties except for modulus and rated V-O in the UL94 flammability test. The control sample in run 105 without rlame retardant failed the UL94 flammability test. Inventive runs 102 and 103 in Table X show that the PPS at the 5 and 10 weight percent l~vels enhanced modulus and HDr values. These samples rated V-O in the UL94 flammability test and possessed LOI values of about 32-q~ X
~P a~ PPS ~e~s:
~ elon with Fla~e Rct~bnt Iet~n~lb~q*~rol A CE~xnate OlioD~r ~30 WC% Glas~s Reinfc ~ d) Rlm lOl 102 103 104 105 % BC-58a 22.5 22.5 æ.5 27.0 Control % PPS O 5.0 lO.0 0 O
Tensile Str ~ h, Brealc (Xsi) 4.9 6.0 6.4 4-9 6.1 FlexLral ~ (Xsi) 7-2 8.0 ~.0 7.2 8.6 ~e~ral ~ lus (ksi) 1,030 1,020 1,110 1,060 710 ed Izcd ~ act (ft-lb/in) 0.4 0.6 0.6 O.S 0-8 13 tdled T7~ ~ t (ft--lb/in) 1.4 1.3 1.4 .9 2.2 E ~ ~! 264 psi (C) lO9.9 148.1 158.6 114.1 124-3 Ul~4 V-O V-O V-O V-O Fail Limiting Q~æn ~K~X
(IDI) (%)31-5 31.5 33.0 31.5 25.5 a BC-58 represents tetrabromobisphenol A
carbonate oligomer (58~ Br), a~aila~le from Great Lakes C~emical Corporation.
.SU~ST~UTE SH~_ i ... . ~
BACKGROUND OF THE INVENTION
This invention relates to high strength, thermally re6istant, fire retardant, polymethylpentene compositions.
Polymethylpentene, also known as PMP, has long been known in the art. Although many methods are known in the art for improving the performance -characteristics of compositions like polyethylene and polypropylene, these same methods tend not to work in the higher alpha olefins, like PMP. Recently, great emphasis has been pIaced upon modi~ying the PMP polymer structure in order to improve the performance characteristics of this polymer. Most of these methods deal with creating a more interactive surface between the PNP polymer structure and the other constituents in the composition. It has been noted though, that the majority of these methods of improving PMP performance characteristics tend to be time consuming and somewhat expensive. Therefore, a method of producing a high strength, thermally resistant, ~ire retardant, PMP
composition, in which the PNP polymer matrix does not have to be substantially altered, would be of great scientific and economic value.
SUMMARY OF IHE INVENTION
It is an object of this invention to provide an improved PNP composition.
SIJBST~T~E SHEE~
- . ,- - ~ . . . : .
.. : ........ ... ~ - ~, .-- . :
.
.
WO~2/16586 PCT/US92/02209 21a a 0~2 It is another object of this invention to provide a PMP composition with improved thermal resistance.
It is still another object of thi~ invention to provide a PMP composition with improved fire retardant capabilities.
It is yet another ob;ect of thi8 invention to provide a PMP composition with high strength and improved thermal resistance.
It is still another object of this invention to provide a PMP composition with high strength and improved fire retardant capabilities.
It is still another ob~ect of this invention to provide a PMP composition with high strength, improved thermal resistance, and improved fire retardant capabilities.
In accordance w~th this invention, a composition of matter i8 provided which comprises (A) about 99.5 to about 75 weight percent of unmodified polymethylpentene where the weight percent of polymethylpentene is based on the total weight of A and B: and tB) about 0.5 to about 25 weight percent of polyphenylene sulfide where the weight percent of polyphenylene sulfide is based on the total weight of A, and B; (C) about l0 to about 67 weight percent of a reinforcer where the weight percent of the reinforcer is based on the total weight of A, B, c, and D; (D) optionally about 5 to about 45 weight percent of a flame retardant where the weight percent of the flame retardant is based on the total weight A, B, C and D.
D~TAILED DESCRIPTION OF THE INVENTION
Polvmethylpentene fPMP~
The polymethylpentene utilized in the present invention is a homopolymer or a copolymer of a methyl-branched pentene, preferably 4-methyl-l-pentene, and SUBSTITUTE SltEET
.
.
...
WO92/16~86 PCT/US92/02209 ~ S3 another alpha olefin. Generally, applicable comonomers have from about 2 to about 18 carbon atoms and preferably, have from about 8 to about 16 carbon atoms.
Most preferably, the co~onomer or comonomers are linear alpha-olefins. Longer chain linear alpha-olefins are preferred in that they are easier to copolymerize with polymethylpentene and can, in part, increase clarity, stability, and impact strength to the resulting composition. Exemplary comonomers include, but are not limited to, l-octene, l-decene, l-dodecene, l- -tetradecene, l-hexadecene, and other higher alpha-olefins.
Generally the PMP should have a melt viscosity, measured as the melt flow rate, of about 0.5 to 500 grams per l0 minutes according to ASTM Dl238, procedure B, under a load ~f 5 kilograms and a temperature of 260-C., and preferably 5 to 150 grams per lO minutes. ~hese flow rates tend to provide the most desired polymer composition processing rates.
The amount of polymethylpentene to utilize in this invention is from about 75 weight percent to about 99.5 weight percent. More preferably, it is from about 9l weight percent to about 99 weight percent and most preferably it is from about 92 weight percent to about 98 weight percent, based on the total weight of PMP and PPS. Other additives, which do not interfere with the compositions at hand, such as stabilizers, corrosion inhibitors, and colorants, etc., can be added to the PMP composition to provide additional desired variations from the main PMP compositions disclosed herein. If any additives are added then the weight of PMP used in the calculations of the weight percents in this specification is equal to the weight of PMP plus the weight of the additives. However, it should~be noted that the P~2 polymer structure is unmodified. By ~ BS~ E SHE~
., , WO92/16586 PCT/US9~/022 the term ~unmodified~ it is meant that the polymer has no grafting agents acting upon it in order to modify its polymer matrix.
PolY~henylene sul~i~e (PPS~
The polyphenylene sulfides utilized in the present invention are well known in the art and are described in U.S. Patents 3,354,129; 3,396,110;
3,919,177; and 4,025,582; which are hereby incorporated by reference. The polyphenylene sulfide useful in accordance with this invention preferably has a melt flow, when tested in accordance with ASTM D-1238 at 315-C. using a 5 kilogram weight, of 1 to about 2,500 grams per 10 minutes.
The amount of PPS to utilize in this invention is from about 0.5 weight percent to about 25 weight percent where the weight percent of PPS is based on the weight of PMP and PPS. More preferably, it is from about 1 to about 9 weight percent and most preferably it i5 from about 2 to about 8 weight percent. The rationale for these ranges is that, while increasing the amount of polyphenylene sulfide in the composition tends to increase the thermal resistance of the polymethylpentene composition, the benefit of adding additional large increments of polyphenylene sulfide does not outweigh the cost. Indeed, practically speaking, small amounts of PPS can be used to obtain large increments of thermal resistance 80 that further additions of PPS do not bring cost effective advantages.
Rein~oxcing Aaents The reinforcing agents usable in the present invention include, for example, glass fiber, carbon fiber, boron fiber, and other inorganic substances, etc. Glass fiber reinforcements are available i~ a variety of compositions, filament diameters, sizings, SU8STlTlJTE SHEET
.
WO92/1~86 PCT/US92/02209 2 ~ ;3 and forms. The most commonly used composition for reinforced thermoplastics is E Glass, a boroaluminosilicate.
The diameter of the glass fiber i8 preferably less than 20 micrometers, but may vary from about 3 to about 30 micrometers. Glass fiber diameters are usually given a letter designation between A and Z.
The most common diameters encountered in glass reinforced thermoplast~cs are G-f~lament (about 9 micrometers) and K-filament (about 13 micrometers).
Several types of glass fiber products can be used for reinforcing thermoplastics. These include yarn, woven fabrics, chopped strands, mats, etc. Continuous filament strands are generally cut into lengths of 1/8, 3/16, 1/4, 1/2, 3/4, and 1 inch or longer for compounding efficiency in various processes and products.
The glass fiber products are usually sized during the fiber ~ormation process or in a post treatment. Sizing compositions usually contain a lubricant, which provides protection for the glass `
fiber strand; a film former or binder that gives the glass fiber strand integrity and wor~ability; and a coupling agent that provides better adhesion between the glass fiber strand and the polymeric materials that are reinforced with the glass fiber strand. Additional agents that may be used in sizing compositions include emulsifiers, wetting agents, nucleating agents, and the like.
The amount of sizing on the glass fiber product typically ranges from about O.2 to 1.5 weight percent based on the weight of the glass, although loadings up to lO percent may be added to mat products.
Examples of film formers include polyesters, ep~xy resins, polyurethanes, polyacrylates, polyvinyl TITUTE SHE~T
wos2/16s86 PcT/us92/o22o9 ~ 6 -acetates, polyvinyl alcohols, starchs, a~d the like.
Usually the coupling agent is a silane coupling agent that has a hydrolyzable moiety for bonding to the glass and a reactive organic moiety that is compat~ble with the polymeric ~aterial that i6 to be reinforced with the glass fibers.
Preferably the amount of reinforcers used are present in about 10 to about 67 weight percent, based on the weight of PMP, PPS, the reinforcer and the lo optional flame retardant. Preferably, the glass fibers are present in the range of about 10 to about 55 weight percent, and most preferably in the range of about 10 to about 45 weight percent. Not enough glass fiber does not improve the polymer properties and too much glass fiber results in not enough polymer to coat the glass fiber, i.e., the $ibers are not wetted ~ut.
El~m~ Retardants Fla~e retardants utilized in the present invention include, but are not limited to, phosphate acid esters such as tricresyl phosphate, tributyl phosphate, tris(dichloropropyl)phosphate, and tris(2,3-dibromopropyl)phosphate; halogenated hydrocarbons such as chlorinated or brominated, ethane, propane, butane, and cyclodecane; halogenated polymers such as chlorinated or brominated, polyethylene, polypropylene, polystyrene, and polycarbonates; brominated or chlorinated diphenyl oxides such as octabromodiphenyl oxide, and decabromodiphenyl oxide; antimony type compounds such as antimony trioxide, antimony potassium tartarate; boron type compound such as borax, zinc borate, barium metaborate: and metallic hydroxides such as magnesium hydroxide, aluminum hydroxide, calcium hydroxide, barium hydroxide, etc. Most preferably the flame retardant is selected from the group consi~tin~
of antimo~y type compounds, boron type compounds, SUBSTITUTE SHEET
.
.
.
WO92/16586 PCT~US92/022~9 polybrominated diphenyl oxides, brominated polystyrenes, polydibromophenylene oxides, brominated polycarbonate derivatives, or mixtures thereof.
Preferably the amount of flame retardant used is between about 5 weight percent to about 45 weight percent based on the weight of PMP, PPS, reinforcer, and flame retardant. More preferably, the amount used is between about 10 weight percent to about 40 weight percent, and most preferably is from about 15 to about 36 weight percent.
EXAMP~ES
~ hese examples are provided to further assist a person skilled in the art with understanding this invention. The particular reactants, conditions, and the like, are intended to be generally illustrative of this invention and are not meant to be construed a8 unduly lim~ting the reasonable scope of thi6 invention.
The following ASTM test procedures were utilized in the testing.
Analysis ASTM Method No.
Tensile Strength at Break D638, at 5 mm/min.
Elongation at Break D638, at 5 mm/min.
Flexural Strength D790, 2 inch span, 1 mm/min. crosshead speed Flexural Modulus D790, 2 inch span, 1 mm/min. crosshead speed Izod Impact Strength, D256 Notched and Unnotched Heat Deflection Temperature D648, at 264 psi (HDT) (-C.) Experiment~ ials Dry blends of polymethylpentene (PM~) ~nd polypropylene (PP~ were prepared, respectively, by drum ~BSTITUTE SHEET
. ~ ~ . . .
... .
. .
5~8~
tumbling 10 Xilograms of resin with 5 grams of Mg4A12(OH)12CO3 3H2O (DHT-4A), 50 grams of Irganox 1010, 50 grams of Anoxsyn 442 and 10 grams of Weston 619 for 30 minutes. Since the total mass of each mix amounted to 10115 grams, a 101.15 gram portion was equivalent, respectively, to 100 parts PMP or PP, 0.05 phr DHT-4A, 0.5 phr Irganox 1010, 0.5 phr Anoxsyn 442 and 0.1 phr Weston 619.
The PMP/PPS formulations were compounded in a Werner & Pfleiderer ZSX-30 twin screw extruder (general purpose compounding screw/barrel configuration) at 250 rpm and 260-290-C. temperature profile. The compositions were stranded, pelletized and dried overnight at 110-C. The PP/PPS formulations were compounded in a Werner & Pfleiderer zsX-30 twin screw extruder at 250 rpm and 200-230 C. profile. These compositions were also stranded, pelletized and dried overnight at 110-C.
The pelletized compositions were molded into ASTM test samples on a Engel Model EC88 injection molding machine with a 55 ton clamp force. The PMP/PPS
blends were molded with a 136-C. mold temperature, 280-295-C. barrel temperature and 30 second cycle time.
The PP/PPS blends were molded with a 90-C. mold temperature, 220-240-C. barrel temperature and 30 second cycle time. Molded parts were annealed for one hour at 150-C. be~ore testing.
The formulations of the PMP and PP are illustrated along with the other materials in Table EM.
STIT~ TE SH~E~
.
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.~ . -~ . ;.. ~. . ; ....... . -.
Wo92~6s86 PCT/US92/02209 TABLE EM .
A. Polymethvlmentene Base Formulation 100.00 phr PMP PMP Homopolymer, ~18 MFR) 0.05 phr DHT-4A hydrotalcite, available Srom Mitsui Petrochemicals, Inc.
0.50 phr Irganox 1010 tetrakis (methylene 3-(3,5-di-t-butyl-4-hydroxyphenyl)-propionate)methane, available from Ciba-Geigy 0.50 phr Anoxsyn 442 aliphatic thio compound, available from Atochem 0.10 phr Weston 619 distearyl pentaerythritol :
diphosphite, available from General Electric ~. Polypromvlene 100.00 phr PP PP Homopolymer, (12 MFR) O.05 phr DHT-4A hydrotalcite, a~ailable from Mitsui Petrochemicals, Inc.
0.50 phr Irganox 1010 tetrakis (methylene 3-(3,5-di-t-butyl-4-hydroxyphenyl)-propionate)methane, available from Ciba-Geigy 0.50 phr Anoxsyn 442 aliphatic thio compound, available from Atochem 0.10 phr Weston 619 distearyl pentaerythritol diphosphite, available from General Electric S~iBSrlTUrE SHEET
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: . .
- . . . . - . . .,:
:. . .
: , , . :
~ . . .
.
o~2 - 10 -C. PolyDhenvlene Sulfide Approximate Grade Flow Rate Type Wash A 2500 uncured water B 900 cured water C 120 cured water D 300 uncured acid E 160 uncured water lASTM D1238 at 315-C. and 5 kg load, modified with a 5 minut~ preheat instead of a 6 minute preheat.
D. Glas~s ~ein~orcemen~ P~o~cts Manu-facturer Product Sizingl Diameter2 Length (in) L0I3 oCF4 457BA6 pp K 3/16 0.90 OCF 408BC PBT K 3/16 0.70 OCF 492AA Nylon/PET G 1/8 1.10 OCF 497DC PPS X 1/8 0.35 CertainTeed5 930 PB~ K 3/16 0.80 CertainTeed 93B Nylon/PET G 1/8 1.00 lIndicates the resin for which the sizing package was optimized: PP represents polypropylene, PBT represents polybutylene terephthalate and PET
repre~ents polyethylene terephthalate.
2G-filament nominal diameter is 9 ~m.
K-filament nominal dizmeter is 13 ~m.
3LOI is ~he nominal ignition loss of the product. This is the percent organic solids of the sizing package.
4Owens Corning FiberglasTM Corp 5CertainTeed Glass Corporation i ?!~BSTITUTE SHEET
~.. ... . ~ . .. . - : . .
- . . . . .. ~ . - .
. ~ . .
.. ~ . :. ..
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.
21~3~w 6All examples used OCF 457BA unless specified otherwise.
~xa~le I
~his example i8 provided to illustrate that the effect observed in polymethylpentene compositions does not occur in polypropylene compositions.
Referring to the data in Table I it is evident that relatively small amounts of PPS did not enhance the HDT
values in Runs 12, 13, and 14. Furthermore, it appears that PPS functions only as a filler in the polypropylene compositions.
TABLE I
pP and PPS Blends:
Pro~erti~s as a Function o$ Polv~henylene Sulfide Level (30% Glass Reinforced~
Run Number 11 12 13 14 Percent PPS ~Grade B) 0 5 10 25 Tensile Strength, Break (ksi) 7.77.5 7.36.7 Flexural Strength (ksi)10.8 10.7 10.4 9.8 Flexural Modulus (ksi) 806 821 803 849 Unnotched Izod Impact (ft-lb/in) 2.62.5 2.22.2 HDT ~ 264 psi (-C.) 150.1149.9 150.0149.8 ~HDT/wt~ PPS -0.04 -0.01-0.01 ~xam~le II
This example is provided to illustrate the effect observed in polymethylpentene/polyphenylene culfide/reinforced compositions. It is evident from the data below that relative small amounts of PPS
enhanced the HDT values in PMP/PPS resins. For SUBSTITUTE SHEE T
.: . . .
~ .
WO92/16~86 PCTIUS92/02209 2 ~ 2 example, in Run 22, at a 5 weight percent PPS level, the HDT value was approximately 56% greater than the HDT value in Run 21 which contained no PPS.
Furthermore, it can be seen from the data below, in the ~HDT/weight percent PPS row, that increasing the weight percent of PPS does not proportionally increase the change in the heat deflection temperature.
PMP and PpS ~lends:
Pro~ç~ies a~ ly~ ig~_oo_,~lyphçnylene Sulfide Level (3Q~Gl~ss Reinforced~
Run Number 21 22 23 24 25 Percent PPS (Grade B) 0 5 1025 50 Tensile Strength, Break (~si) 6.3 6.2 6.1 6.36.3 Flexural Strength (~si) 9.7 9.1 9.1 9.3 9.6 Flexural Modulus (ksi) 674 738 804 890 1,020 Unnotched Izod Impact (ft-lb/in) 2.1 2.2 2.5 2.31.4 HDT ~ 264 psi (-C.)111.0 173.3 176.2 195.1217.7 ~HDT/wt% PPS12.5 6.5 3.4 2.1 Example III
Additional data was gathered to confirm the findings observed in Example II. This data is illustrated in Table III. It is apparent from the data, that at very low levels of PPS, a significant amount of thermal resistance can be attained.
Further~ore, it can be seen from the data below, in the ~HDT/wt% PPS row, that increasing the weight percent of PPS does not proportionally increase the change ~in the heat deflection temperature. This is illustrated by S~IBSTITUTE SttEE ~
.. . , : .
:
.: : . - . . `.
,:
WO 92/16586 PCr/US92/02209 ~ l a ~'~t~
the ~HDT/weight percent PPs row whic:h shows a dra~natic decline from a 2.5 wsight percent loading to a 20 weight percent loading.
TA~E III
R~P and PPS ~e~ls:
~e~ties as a E~on of Polv~lene ~lfide Level r30% Gla~ Reinfor~
R~n No. 31 32 33 34 35 36 .
P~.t PPS (OE~e 8) 0 2.5 5.0 7.510.0 20.0 . .
qensile Strer~h ~ksi) 6.7 6.9 6.76.9 7.0 7.3 El~n (S) 3.1 3.1 3.1 3.03.0 3.1 Fle~ral StL~Ul ~ksi) 9.3 8.9 8.8 8.58.9 9.1 Ele~al ~ulus (ksi) 815 809 822 805856 891 Notd~ed Izod (ft-lb/in) 0.9 1.0 0.90.9 o.9 0.8 ~t~ Izcd (~t-lb/in) 2.S 2.7 2.6 2.72.9 2.2 HDr at 264 psi (-C.) 104.7 156.1 165.1 163.2 167.2 184.1 /wtS E~ 20.6 12.1 7.8 6.3 4.0 Exam~le IV
This example shows the properties of injection molded sample~ prepared from PMP/PPS molding compositions containing different grades of PPS at the 5 weight percent PPS level. The different grades of PPS are identified in Table EM. Results are sl~mmarized in Table IV.
Referring to the HDT values in Runs 41-45, it can be seen that this property varied over a range 157.3 to 164.2-C. This is a dramatic enhancement of HDT relative to the HDT value of 104.7-C. exhibited by the sample in Control ~un 31 which contain no ~S. The general enhancement of HDT values in Runs 41-45 SU~S~ITUTE SHE~
' .' ' . ~, : ' ~ !
, . . ' " , WO92/16586 PCT/US92tO2209 indicate that any of the five different types of PPS
are suitable for use in the inventive composition.
TABLE IV
PMP and PPS Blends:
5Effe~t of PPS Variant on Pro~erties ~0% Glass Reinforced) Run No. 41 42 43 44 45 PPS Grade A B C D E
Tensile Strength ~ksi) 7.1 6.9 6.6 6.8 7.1 Elongation (%) 3.2 3.2 3.2 3.2 3.2 Flexural Strength (ksi) 9.1 8.8 9.o 9.1 9.1 Flexural ~odulus (ksi) 831 826 821 842 832 Notched Izod (ft-lb/in) 0.9 1.0 1.0 1.0 0.9 Unnotched Izod (ft-lb/in~ 2.4 4.5 3.1 3.1 2.5 HDT at 264 p8i (-C.) 158.~ 157.3 160.9 157.5 164.2 ~xample V
This example ~hows the properties of injection molded samples prep red from 30% glass reinforced PMP/PPS molding compositions containing six different types of glasæ reinforcement. The different types of glass reinforcements are identified in Table EM. The polyphenylene 8Ul fide was Grade B at the 5 weight percent level. The results are ~ummarizsd in Table V.
Referring to Runs 53 and 56 in Table V, it is evident that the ~ystems containing, respectively, OCF
492AA and Certainteed 93B gave the highest HDT values of 184.5 and 17SØ These glass reinforcements are - sized for compatibility with Nylon/PET resins. The smaller filament diameters of these glass reinfo~ce-ments perhaps accounted for the superior HDT values SU13STITU~E SXEET
~: . . . . .. . . . ..
.. .
: :. -- .
; : :. ~.: , .~ .. , ., . ' . . , 21 V.5{1~ `
exhibited by the molded samples in Runs 53 and 56. The glass reinforcements sized for compatibility with polypropylene, polybutylene terephthalate and Nylon/PET
resins imparted comparable mechanical properties to molded samples, respectively, in Runs 51, 52, 53, 55, and 56. Surprisingly, the glass reinforcement sized for compatibility with PPS (Run 54) providsd molding samples which exhibited the lowest HDT values of the series.
~t is noteworthy that all of the HDT values in Table V (regardless of the type of glass reinforcement) were significantly greater than that of control run 31.
q~E V
~P and P$S Elends:
Effec~ Of Glass Reinfor~E~t cn Pnox~ties t30% Gl s Reinfo~d) Run No. 5152 53 54 55 56 Glass Reinfon#~ænt 457B~408EC 492AA 497DC 93093B
-Tens;le Stn~th (ksi) 6.5 6.8 6.8 5.8 7.1 6.4 Elongation (%) 1.6 1.6 1.4 1.5 1.6 1.6 25 Flex~ S~U-(ksi) 8.7 8.6 8.7 7.7 9.3 8.2 Flex~ Moh~us (ksi) 800 789 832 789 83~ 789 No~d Izod tft-lb/in) 0.9 1.1 1.2 1.0 1.2 1.0 UnnJ3~{d Izod (ft-Ib/in) 2.9 2.9 3.6 3.0 3.1 3.4 HDT at 264 p6i t 'C.)164.1 165.7 184.5 lS5.9 169.8 175.0 ExamDle VI
This example shows the properties of injection molded samples prepared from 30% glass reinforced PMP/PPS molding compositions under somewhat varied processing conditions. The polyphenylene ~BSTITUT~ SH~ET
.. . .
.
.
W092/16586 PCT~US92/02209 sulfide was Grade B at a 5S by weight level. The results are summarized in Table VI.
In Runs 61 and 62 samples were molded at the higher temperature of 136-C. The sample in Run 62 was annealed for two hours at 150-C. whereas the sample in Run 61 was not annealed. Since the HDT values in Runs 61 and 62 were essentially the same (162 V8. 167), there appeared to be no annealing effect perhaps indicating that both PMP and PPS, especially the PPS, attained maximum crystallization at the 136-F. mold temperature.
In Runs 63 and 64 samplec were molded at the lower temperature of 38-C. The sample in Run 64 was annealed for two hours at 150-C. whereas the sample in Run 63 was not annealed. Since the HDT values in Runs 63 and 64 were not comparable (147 vs. 165), there appeared to be an annealing effect in the sample of Run 64. Although the properties of molded samples at the lower mold temperature were comparable, it is noteworthy that the HDT value of the sample in Run 64 was significantly greater than that of the non-annealed sample in Run 63. Perhaps this indicates that the PPS
did not completely crystallize at the lower mold temperature of 38-C. It should be noted, however, that even at the lower mold temperature the HDT value of the non-annealed 6ample in Run 63 tl47) was significantly greater than that of the sample in Control Run 31.
The results in Table VI indicate that higher mold temperatures should be used on the inventive molding compositions to realize maximum enhancement of HDT values in the injection molded samples.
SUBS~ITU~ S~ET
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.
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W0 92/16~86 PCT~US92/02209 ~LE VI
Eff~ of E~x~essina Conditions on Properties (30% Glass Reinforced) R~n No. 61 62 63 64 Mbld Tecperature ('C.) 136 136 38 38 Arnealing No Yes No Yes Tensile Strength (ksi) 6.8 7.1 6.8 7.0 Elongation (%) 3.4 3.2 3.2 3.0 FlexLral SI~U. (ksi) 8.4 8.7 8.1 8.6 Flex~ral Mbdulus tksi) 741 752 720 729 N~ Izod (~t-lb/in) 0.9 0.9 1.0 1.0 Il~LJbdh d Izod (ft-Ib/in) 2.6 2.6 2.6 2.8 HDr at 264 pd (-C.) 162.1 166.7 147.1 165.3 GENERAL NOTES FOR ALL FLAME RETARDANT EXAMPLES
The weight ratio of the flame retardant to the antimony oxide 6ynergist in each formulation was 3:1. The samples, in each of the following examples, were tested according to ANSI/UL94 Standard for tests for flamability of plastic materials for parts and devices and appliances. The speciman thickness was 1/8 of an inch. In these UL94 tests a result of V-o is better than a V-l and both of these results are better than a fail.
~xample VII
This example describes flame retarded glass reinforced PMP molding compositions containing 2.5 to 10 weight percsnt PPS and 18 to 27 weight percent of decabromodiphenyloxide, a commercial flame retardant available as DE-83R from Great Lzkes Chemical ~J~S~ITl~E SHtET
W092/16~86 PCT~US92/OZ209 2 1 ~
Corporation. Table VIIA shows the properties of injection molded samples prepared from compositions containing 18 weight percent DE-83R and 0, 2.5, 5 and 10 weight percent PPS. Table VII8 shows the properties of injection molded samples prepared from compositions containing 22. 5 weight percent DE-83R and 0, 2. 5, 5 and 10 weight percent PPS. Table VIIC shows the properties of injection molded samples prepared from compositions containing 27 weight percent DE-83R and 0, 2.5, 5 and 10 weight percent PPS.
Part A
Referring to runs 71A and 72A in Table VIIA, neither of which contained PPS, it is evident that the glass reinforced PMP sample without flame retardant (run 72~) exhibited higher property values (except for îlexural modulus) than did the sample of run 71A which contained 18 we~ght percent flame retardant ~DE-83R).
It is noteworthy that the samples of runs 71A and 72A
failed to obtain V-O (self extinguishing) ratings in the UL94 flammability test. Thus, the presence of a flame retardant in a glass reinforced PMP formulation was detrimental to the physical properties of the molded sample and did not render the composition flame resistant. Inventive runs 74A and 75A in Table VIIA
show that the PPS at 5 and 10 weight percent levels enhanced flexural modulus and HDT values as well as flame retardancy. The samples of runs 74A and 75A
rated V-O in the UL94 test. Run 73A is noteworthy because it shows that 2. 5 weight percent PPS is insufficient to enhance flame retardancy to a V-O
rating with only an 18 weight percent flame retardant loading. The HDT value in run 73A, however, was significantly greater than the observed values in runs 71A and 72A . Therefore it can be concluded that the addition of this flame retardant lowers the mechanical SUBSmlJT~ SH~ET
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,.' .' ' : , . .: ' -WO92/16~B6 PCT/US92/02209 2 1~
performance of the polymethylpentene composition.
However, the addition of PPS restores both the mechanical performa~ce as well as improving the ,lame retardancy of t~e co~bined composition.
~ VIIA
~action with Flame Retu~brt Dooi~nT~d1~henyloxide 18 Wt% Flame Ret~ebrt (30 Wk~ Glass Reinfoxxd~
_ Run 71A 72A 73A 74A 75A
% nE-83~a 18.0 Oo~x~ 18.0 18.018.0 % PFS (Gra~e B) o o 2.5 5.010.0 lensile Stn~h, B~k (ksi) 5.4 6.1 6.2 6.9 6.7 Fle~n~l Sbn~h (ksi) 7.4 8.6 8.3 8.4 8.6 Fle~n~l ~Y~US (ksi) 920 710 ggo 995 1,080 No~d Izod ~p~ (ft-lb/in) 0.5 0.8 0.5 0.6 0.6 Unn*l~cd Izcd ~xwk (ft-Ib/in) 1.3 2.2 1.5 1.7 1.5 HDT ~ 264 p6i ~ C.) 122.5 124.3 157.3 165.2 161.7 UL94 V-l ~1 V-1 V-0 V-0 Limiting ~ n ~x (LDI)b (%) 31.5 25.5 29.2 30.0 31.5 a DE-83R represents decabromodiphenyloxide (DBDP0) (83% Br), available from Great Lakes Chemical Corporation.
b The limiting oxygen index (LOI) is expressed as the minimum volume percent of oxygen necessary in an oxygen/nitrogen mixture to sustain combustion of a burning sample. The magnitude of LOI numbers i8 directly proportional to flame retardant effectiveness.
aUBSTlTI JTE SHEET
- , . .
W O 92/16S86 PC~r~US92/02209 2 ~ 2 Part B
Referring to runs 71B and 72B in Table VII8, neither of which contained PPS, it can be seen that the flame retardant reduced the property values (except for modulus) in run 71B but the sample rated V-0 in the UL94 flammability test. Control run 72B without flame retardant failQd the UL94 test. Inventive runs 73B, 74B and 75B in Table VIIB show that the PPS at 2.5, 5 and 10 weight percent levels enhanced flame retardancy (~ee higher LOI values compared to the LOI values of runs 71B and 72B), modulus values and ~DT values.
Thus, at the 22.5 vQight percent loading of flame retardant, the PPS enhanced both the flame retardancy to the point of being self-extinguishing and the physical properties of the injection molded samples.
S!JBSTITU~E SttEET
.. . . . ~ . .
.. ... , ... . -.
. . ` . . ~.... . . : ~
.` - . ~
, ` . . . .
.
W o 92/16~86 PCTtUS92/02209 ~ ~ ,J ~
DecabrcmLdi~henvloxide 2~.5 Wk% Flame Frtard3nt (30 Wk% Glass ReinfcrGed) : `
R~n 71B 72B 73B 74B 75B
S DE n3R 22.5Ccntrol 22.5 22.5 22.5 S PæS (Gra~e B) 0 2.5 5.0 10.0 Tens~le ~ , Ereak (ksi) 5.4 6.1 6.0 6.4 6.4 FlexLral Strength ~ksi) 7.4 8.6 8.2 8.3 7.6 FlexLral McdLlus (ksi) 1,100 710 1,100 1,060 1,160 Nbkched Izod l~pact (ft-Ib/in)0.5 0.8 0.5 0.5 0.5 13~YJldho~ Izod Impact~ft-lb/in) 1.2 2.2 1.6 1.6 1.1 H~ ~ 264 Fsi (-C.) 120.0 124.3 160.0 159.4 165.3 U~4 V-0 Fail V~ V-0 V-0 Limitir~ Qx~en ~c (LOI) (%)29.2 25.5 30.8 32.1 33.6 .
Part C
Referring to runs 71C and 72C in Table VIIC, neither of which contained PPS, it is evident that properties (except for flexural modulus) were reduced by the flame retardant (run 71C) but the sample did rate V-0 in the UL94 test and possessed a desirably high LOI value of 33. The glass reinforced PMP sample (run 72C) without flame retardant failed the UL94 test.
Inventive runs 73C, 74C and 75C in Table VIIC show that the PPS additive at 2.5, 5 and 10 weight percent levels maintained fla~e retardancy and enhanced HDT values of camples containing 27 weight percent :Elame retardant.
SUBSTITLJTE SHE~T
WO 92/16S86 P~US92/02209 210'~ 82 ,q~E VlIC
;~actia~ with Fq# Eb~
DecobrorLdi~henvloxide 27 Wk% Flame PeeDrd~nt (30 Wk% Gl~e Reinforced~ ~
:
Run 71C 72C 73C 74C 75C
% DE-83R 27.0 Cbnkrcl27.0 27.027.0 % PFS (Grade B) 0 2.5 5.010.0 ~, lersile Strength, Ereak (ksi) 5.1 6.1 5.8 5.9 6.4 FlexLral SLLe~Uh (ksi) 7.2 8.6 7.4 6.7 7.2 Flo^~n~al M~dulus (ksi) 1,190 7101,200 1,1601,300 Nbtdhed Izod Impact (ft-Ib/in) 0.5 0.8 0.5 0.4 0.5 ~rr~h~ 3a Impact (ft-Ib/in) 0.9 2.2 1.0 0.9 0.9 HDr 0 264 p6i (-C.) 120.3 124.3160.0 171.2177.8 UI94 V-0 F~l V-0 V-0 V-0 L~miting a~n ~Y~X -:
(LDI) (%) 33.0 25.5 33.6 34.935.4 Example.YIII
This example describes flame retardant glass reinforced PMP molding compositions containing 2.5 to 10 weight percent PPS and 18 to 27 weight percent o~
brominated polystyrene, a commercial flame retardant available as Pyro-Chek 68PB (68S bromine) ~rom Ferro Corporation. Table VIIIA shows the properties of injection ~olded samples prepared from compositions containing 18 weight percent Pyro-Chek 68PB and 0, 2.5, 5 and 10 weight percent PPS. Table VIIIB shows the properties of injection molded samples prepared from compositions containing 22.5 weight percent Pyro-Chek 68PB and 0, 2.5, 5 and 10 weight percent PPS. Table SUBSmUTE SH~ET
j ~. .
.
.. . . . . . ~ . . .. . . . . .
- : : . . . ..
WO92/16~6 PCT~US92/02209 ~a~2 VIIIC shows the properties of in~ection molded samples prepared from compositions containing 27 weight percent Pyro-Chek 68PB and 0, 2.5, 5 and 10 weight percent PPS.
Part A
Referring to runs 81A and 82A in Table VIII, neither of which contained PPS, it can be seen that the glass reinforced PMP sample without flame retardant (run 82A) had higher property values in general than did the sample of run RlA which contained 18 weight percent flame retardant (Pyro-Chek 68PB). Sa~ples of both run 81A and 82A failed the UL94 flammability test.
It is noteworthy that the samples in runs 83A and 84A
at the 2.5 and 5 weight % PPS levels failed to enhance flame retardancy to a V-0 rating but HDT values were increased to about 155. Inventive run 85A shows that the PPS at the 10 weight percent levels enhanced ~lexural modulus and HDT ~alues as well as flame retardancy. The injection molded sample in run 85A
rated V-0 in the UL94 test. The data in Table VII
suggest that between 5 and 10 weight percent PPS at the 18 wt% loading of flame retardant is required to obtain maximum enhancement of physical properties.
SUBSTITUTE SHEET
.
, ' W o 92/16586 PCT~US92/02209 2 1 ~ 2 - 24 - ~
.q~E VmA ' PMP and PPS Blends:
Erominated P~lystvrene 18 Wt% Flame ~eearC3nt ~30 Wk% Glass Reinforced~
~n 81A 82A 83A 84A 85A
% Fyro-Chek 68P~a 18.0 Control 18.0 18.0 18.0 % PPS (Grade B) 0 0 2.5 5.0 10.0 lens;le Strength, Ereak (ksi) 5.46.1 5.9 6.3 6.6 FlexLral Strength (ksi) 7.98.6 8.4 8.6 8.9 Flexural M~dLlus (ksi) 900 710 930 970 1,050 Nbkched Izod Impact (ft-Ib/in) 0.50.8 0.6 0.6 0.7 UCrr~dh d Izod I~pact (ft-Ib/in) 1.4 2.2 1.9 1.7 1.9 264 psi (-C.) 130.8124.3154.3156.9156.8 U~4 FailFail V-l V-l V-0 I1miting Qx~en :~c (LO~) (%) 27.625.5 29.2 30.0 31.5 a Pyro-Chek 68PB represents a brominated polystyrene (68% bromine) available from Ferro Corporation. `
Part B
Referring to runs 81B and 82B in Table VIIIEI, neither of which contained PPS, it is evident that the presence of flame retardant at a 22.5 weight percent loading (run 81B) compromised the physical properties of a molded sample and the sample failed to rate V-0 in the UL94 flammability test. Run 82B is a glass rein-forced PMP sample without flame retardant (control).
Inventive samples 83B, 84B and 85B in Table VIIIB show that the PPS at the 2.5, 5 and 10 weight percent levels SUBS~ITIJTE SH~E~
. . . . . ..
2 ~ 8 `~
snhanced physical properties, particularly HDT values, and enhanced flame retardancy as evidenced by the higher L~I values and a V-0 rating in the UL94 flammability test. It is noteworthy that in Table VIIIB PPS was effective at 2.5 weight percent in runs wherein the flame retardant was at the 22.5 weight percent loading. As noted previously, the PPS was required at the 10 weight percent level to be fully effective in the presence of only 18 weight percent flame retardant (see Table VIIIA).
Table VIIIB
PMP and FP5 Elends:
b~ ction with Flame R-t~brt Broyhxeed P~lYs~n~e 22.S Wt% Flame Rct~brt (30 Wk% Glass Reinf~xæd~
Run 81B 82B 83B 84B 85B
% Pyn~C~Y~ 68PB 22.5 O~ol 22.5 22.5 22.5 % PPS (G~e B) o o 2.5 5.0 10.0 _ _ _ _ Tensile Sbn~h, B~k (ksi) 5.4 6.1 5.6 5.8 6.4 Flex~21 Stna~h (ksi) 7.7 8.6 8.7 8.5 9.1 Fle~n~l Mo~us (ksi) 940 7101,030 1,050 1,140 N~x~ed Izod ~ t (ft-lb/in) 0.5 0.80.5 0.6 0.6 U~JI~Yd Izcd ~x~ (ft-Ib/in)1.2 2.21.3 1.5 1.5 HDT ~ 264 p6i (-C.) 138.0 124.3 153.9 155.9 159.9 . .
UI~4 V~ 1 V-0 V-0 V-0 T .;mi ting Q~n ~Y~X
(LDI) (%) 28.4 25.5 31.5 31.5 33.0 Part C
Referring to runs &lC and 82C in Table VIIIC, neither of which contained PPS, it can be seen in run 81C that a 27 weight percent loading of flame retardant ~'JBSTlTUTE SHEET
WO 92tl 6~86 PCT/US92/~2209 h ~ ~ ~ 9 8 2 reduced properties except for modest increases in modulus and HDT values. This sample rated V-0 in the UL94 test. A contrc~l run (No. 82C) with a glass reinforced PMP composition without flame retardant failed the UL94 flammability test.
Inventive runs 83C, 84C and 85C in Table VIIIC, show that the PPS at the 2.5, 5 and 10 weight percent levels dramatically enhanced modulus and HDT
values. The enhanced flame retardancy of the sample was evidenced by the higher values of the L0I.
~E vmc FMP and PP5 E4ends:
~açticn with Flame ~etosbrt B~x~s~ted P~lv5~n~ne 27 Wk% Fla~e RYt~nbrt ~30 Wk% Gl~C~ Reinf~xd) Run 81C 82C 83C 84C 85C
% PynrC~Yk 68PB 27.00o~ol 27.0 27.027.0 % PFS (Grade B) 0 0 2.5 5.010.0 Tensile Stn~th, Bn~k (ksi) 5.1 6.1 5.6 5.8 6.3 Fle~n~l S~n~Ul(ksi) 7.3 8.6 8.4 8.6 9.1 Flex~ Moh~us (Xsi) 980 7101,100 1,160 1,230 Nou~d Izcd ~x~t (ft-lb/in) 0.4 0.8 0.5 0.5 0.5 unn~=tn~ Izcd ~x~t (ft-lb/in) 1.12.2 1.5 1.2 1.0 HDT ~ 264 p6i (-C.) 138.3 124.3152.1 1~.8 158.9 -UI94 V-0 F~l V-0 V-0 V-o T;miting Q~n ~x (LDI) (%)30.8 25.5 33.0 33.6 35.4 _ Exam~le 1~
This example describes a flame retarded reinforced PMP molding composition containing 10 weight percent PPS and 22.5 weight percent of a SUBSTITUTE SH~E-~
, .
WO92~16586 PCr~US92102209 2 ~ f ~
polydibromophenylene oxide, a commercial flame retardant available as PO-64P from Great Lakes Chemical ~ -Corporation. Table IX shows the properties of injection molded samples.
s Referring to runs 91 and 92 in Table IX, neither of which contained PPS, it is evident in run 92 that a 22.5 weight percent loading of fla~e retardant reduced properties except for ~ome increase in modulus and HDT values. This sample rated V-0 in the UL94 test. A control run (No. 91) with a glass reinforced PMP composition without flame retardant failed the UL94 flammability test. Inventive run 93 in Table IX, shows that the PPS additive at the lO weight percent level enhanced modulus and HDT values. ~he enhanced flame retardancy of the sample was reflected by the higher L~I value (34.9).
TITUTE S~ET
. .
, . ~
WO 92/16~86 PCllUS92/02209 2 ~ 2 28 -~ l:X ' Interactial wi~h Plame 8 (30 W~% Glass R~in~or~) Rl~n 91 92 93 % ~64pa C~trol 22.522.5 ~ EeS O O 10.0 _ _ Tensile St~th, B~ealc (ksi)6.1 5.8 6.7 E~e~ral Sl~ (ksi) 8.6 8.3 8.2 ~ i) 710 1,0301,200 No~ Izod ~c (~-~b/in) 0.8 0.5 0-5 W~ Izod ~ (~-~b/in) 2.2 1.2 .8 Hl~ 0 264 pgi (-C.) 124.3 150.0160.2 UL94 Eail V~~O V-O
T.im~~ axygen ~c (IDI) (%)25.5 30.034.9 a PO-64P represents polydibromophenylene oxide (64% Br) available from Great Lakes Chemical Corporation.
2S ;~xamDle X
This example describes flame retarded glass reinforced PMP molding compositions conta~ning 5 and 10 weight percent PPS and 22.5 weight percent of a tetrabromobisphenol A carbonate oligomer, a commercial flame retardant available as BC-58 from Great Lalces Chemical Corporation. Table X shows the properties of injection molded samples.
Referring to runs 101 and 105 in Table X, none of which contained PPS, it can be seen that the SUBSTITUTE S~t'ET
. . ~ .
. . . :: . -., . ~. . , ... ` ~ .
~as~sS2 flame retardant in the sample of run lOl and 104 reduced properties except for modulus and rated V-O in the UL94 flammability test. The control sample in run 105 without rlame retardant failed the UL94 flammability test. Inventive runs 102 and 103 in Table X show that the PPS at the 5 and 10 weight percent l~vels enhanced modulus and HDr values. These samples rated V-O in the UL94 flammability test and possessed LOI values of about 32-q~ X
~P a~ PPS ~e~s:
~ elon with Fla~e Rct~bnt Iet~n~lb~q*~rol A CE~xnate OlioD~r ~30 WC% Glas~s Reinfc ~ d) Rlm lOl 102 103 104 105 % BC-58a 22.5 22.5 æ.5 27.0 Control % PPS O 5.0 lO.0 0 O
Tensile Str ~ h, Brealc (Xsi) 4.9 6.0 6.4 4-9 6.1 FlexLral ~ (Xsi) 7-2 8.0 ~.0 7.2 8.6 ~e~ral ~ lus (ksi) 1,030 1,020 1,110 1,060 710 ed Izcd ~ act (ft-lb/in) 0.4 0.6 0.6 O.S 0-8 13 tdled T7~ ~ t (ft--lb/in) 1.4 1.3 1.4 .9 2.2 E ~ ~! 264 psi (C) lO9.9 148.1 158.6 114.1 124-3 Ul~4 V-O V-O V-O V-O Fail Limiting Q~æn ~K~X
(IDI) (%)31-5 31.5 33.0 31.5 25.5 a BC-58 represents tetrabromobisphenol A
carbonate oligomer (58~ Br), a~aila~le from Great Lakes C~emical Corporation.
.SU~ST~UTE SH~_ i ... . ~
Claims (39)
1. A composition of matter comprising:
(A) about 99.5 to about 75 weight percent of unmodified polymethylpentene where the weight percent of polymethylpentene is based on the total weight of A
and B; and (B) about 0.5 to about 25 weight percent of polyphenylene sulfide where the weight percent of polyphenylene sulfide is based on the total weight of A
and B; and (C) about 10 to about 67 weight percent of a reinforcer where the weight percent of the reinforcer is based on the total weight of A, B and C.
(A) about 99.5 to about 75 weight percent of unmodified polymethylpentene where the weight percent of polymethylpentene is based on the total weight of A
and B; and (B) about 0.5 to about 25 weight percent of polyphenylene sulfide where the weight percent of polyphenylene sulfide is based on the total weight of A
and B; and (C) about 10 to about 67 weight percent of a reinforcer where the weight percent of the reinforcer is based on the total weight of A, B and C.
2. A composition of matter according to claim 1, wherein said polymethylpentene is a homopolymer of 4-methyl-1-pentene.
3. A composition of matter according to claim 1, wherein said polymethylpentene is a copolymer of 4-methyl-1-pentene and another alpha-olefin.
4. A composition of matter according to claim 1, wherein the amount of said polyphenylene sulfide is about 1 to about 9 weight percent.
5. A composition of matter according to claim 1, wherein the amount of said polyphenylene sulfide is from about 2 to about 8 weight percent.
6. A composition of matter according to claim 1, wherein the amount of said reinforcer is from about 10 to about 55 weight percent.
7. A composition of matter according to claim 1, wherein the amount of said reinforcer is from about 10 to about 45 weight percent.
8. A composition according to claim 1, wherein said reinforcer is a glass fiber reinforcer.
9. A composition according to claim 8, wherein said glass fiber reinforcer has a diameter of about 9 micrometers to about 13 micrometers.
10. A composition of matter according to claim 8, wherein said glass fiber reinforcer has a length of about 1/8 of an inch to about 1/2 of an inch.
11. A composition of matter comprising:
(A) about 99.5 to about 75 weight percent of unmodified polymethylpentene where the weight percent of polymethylpentene is based on the total weight of A
and B; and (B) about 0.5 to about 25 weight percent of polyphenylene sulfide where the weight percent of polyphenylene sulfide is based on the total weight of A
and B; and (C) about 10 to about 67 weight percent of a reinforcer where the weight percent of the reinforcer is based on the total weight of A, B, C, and D; and (D) about 5 to about 45 weight percent of a flame retardant where the weight percent of the flame retardant is based on the total weight of A, B, C, and D.
(A) about 99.5 to about 75 weight percent of unmodified polymethylpentene where the weight percent of polymethylpentene is based on the total weight of A
and B; and (B) about 0.5 to about 25 weight percent of polyphenylene sulfide where the weight percent of polyphenylene sulfide is based on the total weight of A
and B; and (C) about 10 to about 67 weight percent of a reinforcer where the weight percent of the reinforcer is based on the total weight of A, B, C, and D; and (D) about 5 to about 45 weight percent of a flame retardant where the weight percent of the flame retardant is based on the total weight of A, B, C, and D.
12. A composition of matter according to claim 11, wherein said polymethylpentene is a homopolymer of 4-methyl-1-pentene.
13. A composition of matter according to claim 11, wherein said polymethylpentene is a copolymer of 4-metyl-1-pentene and another alpha-olefin.
14. A composition of matter according to claim 11, wherein the amount of said polyphenylene sulfide is about 1 to about 9 weight percent.
15. A composition of matter according to claim 11, wherein the amount of said polyphenylene sulfide is from about 2 to about 8 weight percent.
16. A composition of matter according to claim 11, wherein the amount of said reinforcer is from about 10 to about 55 weight percent.
17. A composition of matter according to claim 11, wherein the amount of said reinforcer is from about 10 to about 45 weight percent.
18. A composition according to claim 11, wherein said reinforcer is a glass fiber reinforcer.
19. A composition according to claim 18, wherein said glass fiber reinforcer has a diameter of about 9 micrometers to about 13 micrometers.
20. A composition of matter according to claim 18, wherein said glass fiber reinforcer has a length of about 1/8 of an inch to about 1/2 of an inch.
21. A composition of matter according to claim 11, wherein said flame retardant is selected from the group consisting of antimony type compounds, boron type compounds, brominated diphenyl oxides, brominated polystyrenes, polydibromophenylene oxides, brominated polycarbonate derivatives, or mixtures thereof.
22. A composition of matter according to claim 11, wherein said flame retardant is antimony trioxide.
23. A composition of matter according to claim 11, wherein said flame retardant is zinc borate.
24. A composition of matter according to claim 11, wherein said flame retardant is decabromodiphenyloxide.
25. A composition of matter according to claim 11, wherein said flame retardant is a brominated polystyrene.
26. A composition of matter according to claim 11, wherein said flame retardant is a polydibromophenylene oxide.
27. A composition of matter according to claim 11, wherein said flame retardant is a brominated polycarbonate derivative.
28. A composition of matter according to claim 11, wherein the amount of said flame retardant is from about 10 to about 40 weight percent.
29. A composition of matter according to claim 11, wherein the amount of said flame retardant is from about 15 to about 36 weight percent.
30. A composition of matter comprising:
(A) about 99 to about 91 weight percent of unmodified poly(4-methyl-1-pentene) where the weight percent of poly(4-methyl-1-pentene) is based on the total weight of A and B: and (B) about 1 to about 9 weight percent of polyphenylene sulfide where the weight percent of polyphenylene sulfide is based on the total weight of A
and B; and (C) about 10 to about 45 weight percent of a reinforcer where the weight percent of the reinforcer is based on the total weight of A, B, and C.
(A) about 99 to about 91 weight percent of unmodified poly(4-methyl-1-pentene) where the weight percent of poly(4-methyl-1-pentene) is based on the total weight of A and B: and (B) about 1 to about 9 weight percent of polyphenylene sulfide where the weight percent of polyphenylene sulfide is based on the total weight of A
and B; and (C) about 10 to about 45 weight percent of a reinforcer where the weight percent of the reinforcer is based on the total weight of A, B, and C.
31. A composition of matter comprising:
(A) about 99 to about 91 weight percent of unmodified poly(4-methyl-1-pentene) where the weight percent of poly(4-methyl-1-pentene) is based on the total weight of A and B; and (B) about 1 to about 9 weight percent of polyphenylene sulfide where the weight percent of polyphenylene sulfide is based on the total weight of A
and B; and (C) about 10 to about 45 weight percent of a reinforcer where the weight percent of the reinforcer is based on the total weight of A, B, C, and D; and (D) about 15 to about 36 weight percent of a flame retardant selected from the group consisting of antimony trioxide, decabromodiphenyl oxide, a brominated polystyrene, a polydibromophenylene oxide, a tetrabromobisphenol A carbonate oligomer, or mixtures thereof, where the weight percent of the flame retardant is based on the total weight of A, B, C, and D.
(A) about 99 to about 91 weight percent of unmodified poly(4-methyl-1-pentene) where the weight percent of poly(4-methyl-1-pentene) is based on the total weight of A and B; and (B) about 1 to about 9 weight percent of polyphenylene sulfide where the weight percent of polyphenylene sulfide is based on the total weight of A
and B; and (C) about 10 to about 45 weight percent of a reinforcer where the weight percent of the reinforcer is based on the total weight of A, B, C, and D; and (D) about 15 to about 36 weight percent of a flame retardant selected from the group consisting of antimony trioxide, decabromodiphenyl oxide, a brominated polystyrene, a polydibromophenylene oxide, a tetrabromobisphenol A carbonate oligomer, or mixtures thereof, where the weight percent of the flame retardant is based on the total weight of A, B, C, and D.
32. A composition of matter consisting essentially of:
(A) about 99.5 to about 75 weight percent of unmodified polymethylpentene where the weight percent of polymethylpentene is based on the total weight of A
and B; and (B) about 0.5 to about 25 weight percent of polyphenylene sulfide where the weight percent of polyphenylene sulfide is based on the total weight of A
and B; and (C) about 10 to about 67 weight percent of a reinforcer where the weight percent of the reinforcer is based on the total weight of A, B and C.
(A) about 99.5 to about 75 weight percent of unmodified polymethylpentene where the weight percent of polymethylpentene is based on the total weight of A
and B; and (B) about 0.5 to about 25 weight percent of polyphenylene sulfide where the weight percent of polyphenylene sulfide is based on the total weight of A
and B; and (C) about 10 to about 67 weight percent of a reinforcer where the weight percent of the reinforcer is based on the total weight of A, B and C.
33. A composition of matter according to claim 32, wherein said polymethylpentene is a homopolymer of 4-methyl-1-pentene.
34. A composition of matter according to claim 32, wherein said polymethylpentene is a copolymer of 4-methyl-1-pentene and another alpha-olefin.
35. A composition of matter consisting essentially of:
(A) about 99.5 to about 75 weight percent of unmodified polymethylpentene where the weight percent of polymethylpentene is based on the total weight of A
and B; and (B) about 0.5 to about 25 weight percent of polyphenylene sulfide where the weight percent of polyphenylene sulfide is based on the total weight of A
and B; and (C) about 10 to about 67 weight percent of a reinforcer where the weight percent of the reinforcer is based on the total weight of A, B, C, and D; and (D) about 5 to about 40 weight percent of a flame retardant where the weight percent of the flame retardant is based on the total weight of A, B, C, and D.
(A) about 99.5 to about 75 weight percent of unmodified polymethylpentene where the weight percent of polymethylpentene is based on the total weight of A
and B; and (B) about 0.5 to about 25 weight percent of polyphenylene sulfide where the weight percent of polyphenylene sulfide is based on the total weight of A
and B; and (C) about 10 to about 67 weight percent of a reinforcer where the weight percent of the reinforcer is based on the total weight of A, B, C, and D; and (D) about 5 to about 40 weight percent of a flame retardant where the weight percent of the flame retardant is based on the total weight of A, B, C, and D.
36. A composition of matter according to claim 35, wherein said polymethylpentene is a homopolymer of 4-methyl-1-pentene.
37. A composition of matter according to claim 35, wherein said polymethylpentene is a copolymer of 4-methyl-1-pentene and another alpha-olefin.
38. A composition of matter consisting essentially of:
(A) about 99 to about 91 weight percent of unmodified poly(4-methyl-1-pentene) where the weight percent of poly(4-methyl-1-pentene) is based on the total weight of A and B: and (B) about 1 to about 9 weight percent of polyphenylene sulfide where the weight percent of polyphenylene sulfide is based on the total weight of A
and B; and (C) about 10 to about 4 weight percent of a reinforcer where the weight percent of the reinforcer is based on the total weight of A, B, and C.
(A) about 99 to about 91 weight percent of unmodified poly(4-methyl-1-pentene) where the weight percent of poly(4-methyl-1-pentene) is based on the total weight of A and B: and (B) about 1 to about 9 weight percent of polyphenylene sulfide where the weight percent of polyphenylene sulfide is based on the total weight of A
and B; and (C) about 10 to about 4 weight percent of a reinforcer where the weight percent of the reinforcer is based on the total weight of A, B, and C.
39. A composition of matter consisting essentially of:
(A) about 99 to about 91 weight percent of unmodified poly(4-methyl-1-pentene) where the weight percent of poly(4-methyl-1-pentene) is based on the total weight of A and B; and (B) about 1 to about 9 weight percent of polyphenylene sulfide where the weight percent of polyphenylene sulfide is based on the total weight of A
and B; and (C) about 10 to about 45 weight percent of a reinforcer where the weight percent of the reinforcer is based on the total weight of A, B, C, and D; and (D) about 15 to about 36 weight percent of a flame retardant selected from the group consisting of antimony trioxide, decabromodiphenyl oxide, a brominated polystyrene, a polydibromophenylene oxide, a tetrabromobisphenol A carbonate oligomer or mixtures thereof, where the weight percent of the flame retardant is based on the total weight of A, B, C, and D.
(A) about 99 to about 91 weight percent of unmodified poly(4-methyl-1-pentene) where the weight percent of poly(4-methyl-1-pentene) is based on the total weight of A and B; and (B) about 1 to about 9 weight percent of polyphenylene sulfide where the weight percent of polyphenylene sulfide is based on the total weight of A
and B; and (C) about 10 to about 45 weight percent of a reinforcer where the weight percent of the reinforcer is based on the total weight of A, B, C, and D; and (D) about 15 to about 36 weight percent of a flame retardant selected from the group consisting of antimony trioxide, decabromodiphenyl oxide, a brominated polystyrene, a polydibromophenylene oxide, a tetrabromobisphenol A carbonate oligomer or mixtures thereof, where the weight percent of the flame retardant is based on the total weight of A, B, C, and D.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US67360291A | 1991-03-21 | 1991-03-21 | |
| US673,602 | 1991-03-21 | ||
| PCT/US1992/002209 WO1992016586A1 (en) | 1991-03-21 | 1992-03-19 | Polymethylpentene compositions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2105082A1 true CA2105082A1 (en) | 1992-09-22 |
Family
ID=24703332
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002105082A Abandoned CA2105082A1 (en) | 1991-03-21 | 1992-03-19 | Polymethylpentene compositions |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0576573A4 (en) |
| JP (1) | JPH06507431A (en) |
| CA (1) | CA2105082A1 (en) |
| WO (1) | WO1992016586A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7115677B2 (en) | 2001-11-30 | 2006-10-03 | Polyplastics Co., Ltd. | Flame-retardant resin composition |
| CN114196126B (en) * | 2022-01-13 | 2023-03-10 | 宁夏清研高分子新材料有限公司 | Preparation method of poly 4-methyl-1-pentene flame retardant material |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4025582A (en) * | 1975-07-03 | 1977-05-24 | Phillips Petroleum Company | Ultraviolet-stabilized polyolefin compositions |
| JPS63213562A (en) * | 1987-03-03 | 1988-09-06 | Mitsui Petrochem Ind Ltd | Fiber-reinforced and heat-resistant polyolefin composition |
| MY104182A (en) * | 1988-09-02 | 1994-02-28 | Mitsui Petrochemical Ind | Heat resistant poly-4-methyl-1-pentene resin composition and shaped article thereof. |
-
1992
- 1992-03-19 JP JP4508356A patent/JPH06507431A/en active Pending
- 1992-03-19 EP EP92908871A patent/EP0576573A4/en not_active Withdrawn
- 1992-03-19 WO PCT/US1992/002209 patent/WO1992016586A1/en not_active Application Discontinuation
- 1992-03-19 CA CA002105082A patent/CA2105082A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| EP0576573A4 (en) | 1995-02-22 |
| EP0576573A1 (en) | 1994-01-05 |
| WO1992016586A1 (en) | 1992-10-01 |
| JPH06507431A (en) | 1994-08-25 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Discontinued | ||
| FZDE | Discontinued |
Effective date: 19980319 |