EP0576573A1 - Polymethylpentene compositions - Google Patents

Polymethylpentene compositions

Info

Publication number
EP0576573A1
EP0576573A1 EP92908871A EP92908871A EP0576573A1 EP 0576573 A1 EP0576573 A1 EP 0576573A1 EP 92908871 A EP92908871 A EP 92908871A EP 92908871 A EP92908871 A EP 92908871A EP 0576573 A1 EP0576573 A1 EP 0576573A1
Authority
EP
European Patent Office
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.)
Withdrawn
Application number
EP92908871A
Other languages
German (de)
French (fr)
Other versions
EP0576573A4 (en
Inventor
Edwin Boudreaux, Jr.
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Phillips Petroleum Co
Original Assignee
Phillips Petroleum Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Phillips Petroleum Co filed Critical Phillips Petroleum Co
Publication of EP0576573A1 publication Critical patent/EP0576573A1/en
Publication of EP0576573A4 publication Critical patent/EP0576573A4/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • 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
    • 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

Definitions

  • Polymethylpentene also known as PMP, has long been known in the art. Although many methods are known in the art for improving the performance
  • compositions like polyethylene and polypropylene these same methods tend not to work in the higher alpha olefins, like PMP.
  • great emphasis has been placed upon modifying the PMP polymer structure in order to improve the performance
  • composition of matter 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 (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 polymethylpentene utilized in the present invention is a homopolymer or a copolymer of a methyl-branched pentene, preferably 4-methyl-1-pentene, and another alpha olefin.
  • applicable comonomers have from about 2 to about 18 carbon atoms and
  • the comonomer 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, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, and other higher alpha-olefins.
  • 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 91 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
  • 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.
  • the PMP polymer structure is unmodified. By the term “unmodified” it is meant that the polymer has no grafting agents acting upon it in order to modify its polymer matrix.
  • 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;
  • the polyphenylene sulfide useful in accordance with this invention preferably has a melt flow, when tested in accordance with ASTM D-1238 at 315oC. using a 5 kilogram weight, of 1 to about 2,500 grams per 10 minutes.
  • 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 in a variety of compositions, filament diameters, sizings, and forms.
  • the most commonly used composition for reinforced thermoplastics is E Glass, a
  • the diameter of the glass fiber is 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
  • the glass fiber products are usually sized during the fiber formation process or in a post
  • 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 workability; 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 0.2 to 1.5 weight percent based on the weight of the glass, although loadings up to 10 percent may be added to mat products.
  • film formers include polyesters, epoxy resins, polyurethanes, polyacrylates, polyvinyl acetates, polyvinyl alcohols, starchs, and the like.
  • 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 compatible with the polymeric material that is to be reinforced with the glass fibers.
  • chlorinated or brominated polyethylene, polypropylene, polystyrene, and polycarbonates; brominated or
  • 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.
  • 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 136oC. mold temperature, 280- 295oC. barrel temperature and 30 second cycle time.
  • the PP/PPS blends were molded with a 90oC. mold
  • PP represents polypropylene
  • PBT represents polybutylene terephthaiate
  • PET represents polyethylene terephthalate
  • K-filament nominal diameter is 13 ⁇ m.
  • 3LOI is the nominal ignition loss of the product. This is the percent organic solids of the sizing package.
  • This example shows the properties of injection molded samples 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 summarized in Table IV.
  • This example shows the properties of injection molded samples prepared from 30% glass reinforced PMP/PPS molding compositions containing six different types of glass reinforcement.
  • the different types of glass reinforcements are identified in Table EM.
  • the polyphenylene sulfide was Grade B at the 5 weight percent level. The results are summarized in Table V.
  • the weight ratio of the flame retardant to the antimony oxide synergist 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-0 is better than a V-1 and both of these results are better than a fail.
  • This example describes flame retarded glass reinforced PMP molding compositions containing 2.5 to 10 weight percent PPS and 18 to 27 weight percent of decabromodiphenyloxide, a commercial flame retardant available as DE-83R from Great Lakes Chemical 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 VIIB 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.
  • LOI limiting oxygen index
  • the PPS enhanced both the flame retardancy to the point of being self-extinguishing and the physical properties of the injection molded samples.
  • Notched Izod Impact (ft-lb/in) 0.5 0.8 0.5 0.4 0.5 Unnotched Impact (ft-lb/in) 0.9 2.2 1.0 0.9 0.9
  • This example describes flame retardant glass reinforced PMP molding compositions containing 2.5 to 10 weight percent PPS and 18 to 27 weight percent of brominated polystyrene, a commercial flame retardant available as Pyro-Chek 68PB (68% bromine) from Ferro Corporation.
  • Table VIIIA shows the properties of injection molded samples prepared from compositions containing 18 weight percent Pyro-Chek 68PB ⁇ md 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 VIIIC shows the properties of injection molded samples prepared from compositions containing 27 weight percent Pyro-Chek 68PB and 0, 2.5, 5 and 10 weight percent PPS .
  • This example describes a flame retarded reinforced PMP molding composition containing 10 weight percent PPS and 22.5 weight percent of a polydibromophenylene oxide, a commercial flame
  • PO-64P represents polydibromophenylene oxide (64% Br) available from Great Lakes Chemical Corporation.
  • This example describes flame retarded glass reinforced PMP molding compositions containing 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 Lakes Chemical Corporation.
  • Table X shows the properties of injection molded samples.
  • Notched Izod Inpact (ft-lb/in) 0.4 0.6 0.6 0.5 0.8
  • BC-58 represents tetrabromobisphenol A carbonate oligomer (58% Br), available from Great Lakes Chemical Corporation.

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

Abstract

Composition à haute résistance mécanique et thermique, inhibitrice de combustion, comprenant: (A) environ 99,5 à environ 75 pour cent en poids d'un polyméthylpentène non modifié, ledit pourcentage en poids étant basé sur le poids total de A et B; et (B) environ 0,5 à environ 25 pour cent en poids de sulfure de polyphénylène, ledit pourcentage en poids étant basé sur le poids total de A et B; (C) environ 10 à environ 67 pour cent en poids d'un agent de renforcement, ledit pourcentage en poids étant basé sur le poids total de A, B, C et D; (D) éventuellement environ 5 à environ 45 pour cent en poids d'un inhibiteur de combustion, ledit pourcentage en poids étant basé sur le poids total de A, B, C et D. Cette composition est utilisée dans la technique du moulage.A composition with high mechanical and thermal resistance, combustion inhibitor, comprising: (A) about 99.5 to about 75 percent by weight of an unmodified polymethylpentene, said percent by weight being based on the total weight of A and B; and (B) about 0.5 to about 25 percent by weight of polyphenylene sulfide, said percent by weight being based on the total weight of A and B; (C) about 10 to about 67 percent by weight of a reinforcing agent, said weight percent being based on the total weight of A, B, C and D; (D) optionally about 5 to about 45 percent by weight of a combustion inhibitor, said percent by weight being based on the total weight of A, B, C and D. This composition is used in the molding technique.

Description

POLYMETHYLPENTENE COMPOSITIONS
BACKGROUND OF THE INVENTION
This invention relates to high strength, thermally resistant, 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 placed upon modifying 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 PMP 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, fire retardant, PMP composition, in which the PMP polymer matrix does not have to be substantially altered, would be of great scientific and economic value.
SUMMARY OF THE INVENTION
It is an object of this invention to provide an improved PMP composition. It is another object of this invention to provide a PMP composition with improved thermal resistance.
It is still another object of this invention to provide a PMP composition with improved fire retardant capabilities.
It is yet another object of this 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 object of this invention to provide a PMP composition with high strength, improved thermal resistance, and improved fire
retardant capabilities.
In accordance with this invention, a composition of matter is 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 (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.
DETAILED DESCRIPTION OF THE INVENTION
Polymethylpentene (PMP)
The polymethylpentene utilized in the present invention is a homopolymer or a copolymer of a methyl-branched pentene, preferably 4-methyl-1-pentene, and 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 comonomer 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, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-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 10 minutes according to ASTM D1238, procedure B, under a load of 5 kilograms and a
temperature of 260ºC., and preferably 5 to 150 grams per 10 minutes. These 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 91 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 PMP polymer structure is unmodified. By the term "unmodified" it is meant that the polymer has no grafting agents acting upon it in order to modify its polymer matrix.
Polyphenylene sulfide (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 315ºC. 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 is 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 so that further additions of PPS do not bring cost
effective advantages.
Reinforcing Agents
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 in a variety of compositions, filament diameters, sizings, and forms. The most commonly used composition for reinforced thermoplastics is E Glass, a
boroaluminosilicate.
The diameter of the glass fiber is 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 thermoplastics are G-filament (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 formation 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 workability; 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 0.2 to 1.5 weight percent based on the weight of the glass, although loadings up to 10 percent may be added to mat products. Examples of film formers include polyesters, epoxy resins, polyurethanes, polyacrylates, polyvinyl acetates, polyvinyl alcohols, starchs, and 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 compatible with the polymeric material that is 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 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 fibers are not wetted out.
Flame Retardants
Flame 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 consisting of antimony type compounds, boron type compounds, 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.
EXAMPLES
These 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 as unduly limiting the reasonable scope of this 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) (ºC.)
Experimental Materials
Dry blends of polymethylpentene (PMP) and polypropylene (PP) were prepared, respectively, by drum tumbling 10 kilograms of resin with 5 grams of
Mg4Al2(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 ZSK-30 twin screw extruder (general purpose compounding screw/barrel configuration) at 250 rpm and 260-290ºC. temperature profile. The
compositions were stranded, pelletized and dried overnight at 110ºC. The PP/PPS formulations were compounded in a Werner & Pfleiderer ZSK-30 twin screw extruder at 250 rpm and 200-230ºC. profile. These compositions were also stranded, pelletized and dried overnight at 110ºC.
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 136ºC. mold temperature, 280- 295ºC. barrel temperature and 30 second cycle time.
The PP/PPS blends were molded with a 90ºC. mold
temperature, 220-240ºC. barrel temperature and 30 second cycle time. Molded parts were annealed for one hour at 150ºC. before testing.
The formulations of the PMP and PP are illustrated along with the other materials in Table EM. TABLE EM
A. Polymethylpentene Base Formulation
100.00 phr PMP PMP Homopolymer, (18 MFR) 0.05 phr DHT-4A hydrotalcite, available 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
B. Polypropylene
100.00 phr PP PP Homopolymer, (12 MFR) 0.05 phr DHT-4A hydrotalcite, available 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 C. Polyphenylene Sulfide
Approximate1
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
1ASTM D1238 at 315ºC. and 5 kg load, modified with a 5 minute preheat instead of a 6 minute preheat.
D. Glass Reinforcement Products Manufacturer Product Sizing1 Diameter2 Length (in) LOI3
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 K 1/8 0.35
CertainTeed5 930 PBT K 3/16 0.80
CertainTeed 93B Nylon/PET G 1/8 1.00
1Indicates the resin for which the sizing package was optimized: PP represents polypropylene, PBT represents polybutylene terephthaiate and PET represents polyethylene terephthalate.
2G-filament nominal diameter is 9 μm.
K-filament nominal diameter is 13 μm.
3LOI is the nominal ignition loss of the product. This is the percent organic solids of the sizing package.
4Owens Corning Fiberglas™ Corp
5CertainTeed Glass Corporation 6All examples used OCF 457BA unless specified otherwise.
Example I
This example is 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:
Properties as a Function of Polyphenylene Sulfide Level
(30% Glass Reinforced)
Run Number 11 12 13 14
Percent PPS (Grade B) 0 5 10 25
Tensile Strength,
Break (ksi) 7.7 7.5 7.3 6.7 Flexural Strength (ksi) 10.8 10.7 10.4 9.8 Flexural Modulus (ksi) 806 821 803 849 Unnotched Izod
Impact (ft-lb/in) 2.6 2.5 2.2 2.2 HDT @ 264 psi (ºC) 150.1 149.9 150.0 149.8 ΔHDT/Wt% PPS -0.04 -0.01 -0.01 Example II
This example is provided to illustrate the effect observed in polymethylpentene/polyphenylene sulfide/reinforced compositions. It is evident from the data below that relative small amounts of PPS enhanced the HDT values in PMP/PPS resins. For 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 ΔHDT/weight percent PPS row, that increasing the weight percent of PPS does not proportionally increase the change in the heat deflection temperature.
TABLE II PMP and PPS Blends:
Properties as a Function of Polyphenylene Sulfide Level
(30% Glass Reinforced)
Run Number 21 22 23 24 25 Percent PPS (Grade B) 0 5 10 25 50
Tensile Strength,
Break (ksi) 6.3 6.2 6.1 6.3 6.3
Flexural Strength (ksi) 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 2.3 1.4 HDT @ 264 psi (ºC.) 111.0 173.3 176.2 195.1 217.7 ΔHDT/Wt% PPS 12.5 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.
Furthermore, it can be seen from the data below, in the ΔHDT/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 the ΔHDT/weight percent PPS row which shows a dramatic decline from a 2.5 weight percent loading to a 20 weight percent loading.
TABLE III
PMP and PPS Blends;
Properties as a Function of Polyphenylene
Sulf ide Level Two
(30% Glass Reinforced)
Run No. 31 32 33 34 35 36
Percent PPS (Grade B) 0 2.5 5.0 7.5 10.0 20.0
Tensile Strength (ksi) 6.7 6.9 6.7 6.9 7.0 7.3 Elongation (%) 3.1 3.1 3.1 3.0 3.0 3.1
Flexural Strength (ksi) 9.3 8.9 8.8 8.5 8.9 9.1 Flexural Modulus (ksi) 815 809 822 805 856 891 Notched Izod (ft-lb/in) 0.9 1.0 0.9 0.9 0.9 0.8 Unnotched Izod (ft-lb/in) 2.5 2.7 2.6 2.7 2.9 2.2 HDT at 264 psi (ºC.) 104.7 156.1 165.1 163.2 167.2 184.1
ΔHDT/wt% PPS — 20.6 12.1 7.8 6.3 4.0
Example IV
This example shows the properties of injection molded samples 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 summarized 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 164.2ºC. This is a dramatic enhancement of HDT relative to the HDT value of 104.7ºC. exhibited by the sample in Control Run 31 which contain no PPS. The general enhancement of HDT values in Runs 41-45 indicate that any of the five different types of PPS are suitable for use in the inventive composition.
TABLE IV
PMP and PPS Blends:
Effect of PPS Variant on Properties
(30% 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 9.0 9.1 9.1 Flexural Modulus (ksi) 831 826 821 842 832 Notched Izod (ft-lb/in) 0.9 1.0 1.0 1.0 0.9 Unnotσhed Izod (ft-lb/in) 22..44 4.5 3.1 3.1 2.5 HDT at 264 psi (ºC.) 158.1 157.3 160.9 157.5 164.2 Example V
This example shows the properties of injection molded samples prepared from 30% glass reinforced PMP/PPS molding compositions containing six different types of glass reinforcement. The different types of glass reinforcements are identified in Table EM. The polyphenylene sulfide was Grade B at the 5 weight percent level. The results are summarized in Table V.
Referring to Runs 53 and 56 in Table V, it is evident that the systems containing, respectively, OCF 492AA and Certainteed 93B gave the highest HDT values of 184.5 and 175.0. These glass reinforcements are sized for compatibility with Nylon/PET resins. The smaller filament diameters of these glass reinfoucements perhaps accounted for the superior HDT values 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) provided molding samples which exhibited the lowest HDT values of the series.
It 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.
TABLE V
PMP and PPS Blends:
Effect of PPS Variant on Properties
(30% Glass Reinforced)
Run No. 51 52 53 54 55 56
Glass Reinforcement 457BA 408BC 492AA 497DC 930 93B
Tensile Strength (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 Flexural Strength (ksi) 8.7 8.6 8.7 7.7 9.3 8.2 Flexural Modulus (ksi) 800 789 832 789 834 789 Notched Izod (ft-lb/in) 0.9 1.1 1.2 1.0 1.2 1.0 Unnotched Izod (ft-lb/in) 2.9 2.9 3.6 3.0 3.1 3.4 HOT at 264 psi (ºC.) 164.1 165.7 184.5 155.9 169.8 175
Example 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 sulfide was Grade B at a 5% by weight level. The results are summarized in Table VI.
In Runs 61 and 62 samples were molded at the higher temperature of 136ºC. The sample in Run 62 was annealed for two hours at 150ºC. whereas the sample in Run 61 was not annealed. Since the HDT values in Runs 61 and 62 were essentially the same (162 vs. 167), there appeared to be no annealing effect perhaps indicating that both PMP and PPS, especially the PPS, attained maximum crystallization at the 136ºF. mold temperature.
In Runs 63 and 64 samples were molded at the lower temperature of 38ºC. The sample in Run 64 was annealed for two hours at 150ºC. 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 38ºC. It should be noted, however, that even at the lower mold temperature the HDT value of the non-annealed sample in Run 63 (147) 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. TABLE VI
PMP and PPS Blends:
Effect of Processing Conditions on Properties
(30% Glass Reinforced)
Run No. 61 62 63 64
Mold Tamperature (ºC.) 136 136 38 38
Annealing No Yes No Yes
Tensile strength (ksi) 6.8 7.1 6.8 7.0 Elongation (%) 3.4 3.2 3.2 3.0 Flexural Strength (ksi) 8.4 8.7 8.1 8.6 Flexural Madulus (ksi) 741 752 720 729 Notched Izod (ft-lb/in) 0.9 0.9 1.0 1.0 Unnotched Izod (ft-lb/in) 2.6 2.6 2.6 2.8 HOT at 264 psi (ºC.) 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 synergist 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-0 is better than a V-1 and both of these results are better than a fail.
Example VII
This example describes flame retarded glass reinforced PMP molding compositions containing 2.5 to 10 weight percent PPS and 18 to 27 weight percent of decabromodiphenyloxide, a commercial flame retardant available as DE-83R from Great Lakes Chemical 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 VIIB 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 72A) exhibited higher property values (except for flexural modulus) than did the sample of run 71A which contained 18 weight percent flame retardant (DE-83R). It is noteworthy that the samples of runs 71A and 72A failed to obtain V-0 (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-0 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-0 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 performance of the polymethylpentene composition.
However, the addition of PPS restores both the
mechanical performance as well as improving the flame retardancy of the combined composition.
TABLE VIIA PMP ana PPS Blends:
Interaction with Flame Retardant
Decabromodiphenyloxide 18 Wt% Fl ame Retardant
(30 Wt% glass Reinforced)
Run 71A 72A 73A 74A 75A
% EE-83Ra 18.0 Control 18.0 18.0 18.0
% PPS (Grade B) 0 0 2.5 5.0 10.0
Tensile Strength, Break (ksi) 5.4 6.1 6.2 6.9 6.7
Flexural Strength (ksi) 7.4 8.6 8.3 8.4 8.6
Flexural Modulus (ksi) 920 710 990 995 1,080
Notched Izod Impact (ft-lb/in) 0.5 0.8 0.5 0.6 0.6
Unnotched Tzod Impact (ft-lb/in) 1 .3 2.2 1.5 1.7 1.5
HDT @ 264 psi (ºC.) 122.5 124.3 157.3 165.2 161.7
UL94 V-1 Fail V-1 V-0 V-0
Limiting Oxygen Index
(LOI)b (%) 31.5 25.5 29.2 30.0 31.5 a DE-83R represents decabromodiphenyloxide (DBDPO) (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 is directly proportional to flame retardant effectiveness. Part B
Referring to runs 71B and 72B in Table VIIB, neither of which contained PPS, it can be seen that the flame retardant reduced the property values (except for modulus) in run 7IB but the sample rated V-0 in the
UL94 flammability test. Control run 72B without flame retardant failed 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 (see higher LOI values compared to the LOI values of runs 7IB and 72B), modulus values and HDT values.
Thus, at the 22.5 weight 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.
TABLE VIIB
PMP ana PPS Blend:
Interaction with Flame Retardant
Decabromodiphenyloxide 22.5 Wt% Flame Retardant
(30 Wt% Glass Reinforced)
Run 71B 72B 73B 74B 75B
% EE-83R 22.5 Control 22.5 22.5 22.5
% PPS (Grade B) 0 2.5 5.0 10.0
Tensile Strength, Break (ksi) 5.4 6.1 6.0 6.4 6.4 Flexural Strength (ksi) 7.4 8.6 8.2 8.3 7.6 Flexural Modulus (ksi) 1,100 710 1,100 1,060 1,160 Notched Izod Impact (ft-lb/in) 0.5 0.8 0.5 0.5 0.5
Unnotched Izod Impact (ft-lb/in) 1.2 2.2 1.6 1.6 1.1
HOT @ 264 psi ( ºC.) 120.0 124.3 160.0 159.4 165.3
UL94 V-0 Fail V-0 V-0 V-0
Limiting Oxygen Index
(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 flame retardancy and enhanced HDT values of samples containing 27 weight percent flame retardant. TABLE VIIC
PMP and PPS Blends:
Interaction with Flame Retardant
Decabromodiphenyloxide 27 Wt% Flame Retardant
(30 Wt% Glass Reinforced)
Run 71C 72C 73C 74C 75C
% EE-83R 27.0 Control 27.0 27.0 27.0
% PPS (Grade B) 0 2.5 5.0 10.0
Tensile Strength, Break (ksi) 5.1 6.1 5.8 5.9 6.4 Flexural Strength (ksi) 7.2 8.6 7.4 6.7 7.2
Flexural Modulus (ksi) 1,190 710 1,200 1,160 1,300
Notched Izod Impact (ft-lb/in) 0.5 0.8 0.5 0.4 0.5 Unnotched Impact (ft-lb/in) 0.9 2.2 1.0 0.9 0.9
HOT @ 264 psi (ºC. ) 120.3 124.3 160.0 171.2 177.8
UL94 V-0 Fail V-0 V-0 V-0
Limiting Oxygen Index
(LOI) (%) 33.0 25.5 33.6 34.9 35.4
Example VIII
This example describes flame retardant glass reinforced PMP molding compositions containing 2.5 to 10 weight percent PPS and 18 to 27 weight percent of brominated polystyrene, a commercial flame retardant available as Pyro-Chek 68PB (68% bromine) from Ferro Corporation. Table VIIIA shows the properties of injection molded samples prepared from compositions containing 18 weight percent Pyro-Chek 68PB εmd 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 VIIIC shows the properties of injection 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 81A which contained 18 weight percent flame retardant (Pyro-Chek 68PB). Samples 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 flexural modulus and HDT values 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.
TABLE VIIIA
PMP and PPS Blends:
Interaction with Flame Retardant
Brominated Polystyrene 18 Wt% Flame Retardant
(30 Wt% Glass Reinforced)
Run 81A 82A 83A 84A 85A
% Pyro-Chek 68PBa 18.0 Control 18.0 18.0 18.0
% PPS (Grade B) 0 0 2.5 5.0 10.0
Tensile Strength, Break (ksi) 5.4 6.1 5.9 6.3 6.6
Flexural Strength (ksi) 7.9 8.6 8.4 8.6 8.9
Flexural Modulus (ksi) 900 710 930 970 1,050
Notched Izod Impact (ft-lb/in) 0.5 0.8 0.6 0.6 0.7
Uhnotched Izod Impact (ft-lb/in) 1.4 2.2 1.9 1.7 1.9
HOT @ 264 psi (ºC.) 130.8 124.3 154.3 156.9 156.8
UL94 Fail Fail V-1 V-1 V-0 limiting Oxygen Index
(LOI) (%) 27.6 25.5 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 VIIIB, 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 reinforced 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 enhanced physical properties, particularly HDT values, and enhanced flame retardancy as evidenced by the higher LOI 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 ana PPS Blends :
Interaction with Flame Retardant
Brominated Polystyrene 22.5 Wt% Flame Retardant
(30 Wt% Glass Reinforced)
Run 81B 82B 83B 84B 85B
% Pyro-Chek 68PB 22.5 Control 22.5 22.5 22.5
% PPS (Grade B) 0 0 2.5 5.0 10.0
Tensile Strength, Break (ksi) 5.4 6.1 5.6 5.8 6.4
Flexural Strength (ksi) 7.7 8.6 8.7 8.5 9.1
Flexural Modulus (ksi) 940 710 1,030 1,050 1,140
Notched Izod Impact (ft-lb/in) 0.5 0.8 0.5 0.6 0.6
Unnotched Izod Impact (ft-lb/in) 1.2 2.2 1.3 1.5 1.5
HOT @ 264 psi (*C.) 138.0 124.3 153.9 155.9 159.9
UL94 V-1 Fail V-0 V-0 V-0
Limiting Oxygen Index
(LOI) (%) 28.4 25.5 31.5 31.5 33.0
Part C
Referring to runs 81C 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 reduced properties except for modest increases in modulus and HDT values. This sample rated V-0 in the UL94 test. A control 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 LOI.
TABLE VIIIC
PMP and PPS Blends:
Interaction with Flame Retardant
Brominated Polystyrene 27 Wt% Flame Retardant
(30 Wt% Glass Reinforced)
Run 81C 82C 83C 84C 85C
% Pyro-Chek 68PB 27.0 Control 27.0 27.0 27.0
% PPS (Grade B) 0 0 2.5 5.0 10.0
Tensile Strength, Break (ksi) 5.1 6.1 5.6 5.8 6.3
Flexural Strength (ksi) 7.3 8.6 8.4 8.6 9.1
Flexural Modulus (ksi) 980 710 1,100 1,160 1,230
Notched Izod Impact (ft-lb/in) 0.4 0.8 0.5 0.5 0.5
Unnotched Izod Impact (ft-lb/in) 1 .1 2.2 1.5 1.2 1.0
HOT 8 264 psi ( ºC.) 138.3 124.3 152.1 154.8 158.9
UL94 V-0 Fail V-0 V-0 V-0 Limiting Oxygen Index
(LOI) (%) 30.8 25.5 33.0 33.6 35.4
Example IX
This example describes a flame retarded reinforced PMP molding composition containing 10 weight percent PPS and 22.5 weight percent of a polydibromophenylene oxide, a commercial flame
retardant available as PO-64P from Great Lakes Chemical Corporation. Table IX shows the properties of
injection molded samples.
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 flame retardant reduced properties except for some 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 10 weight percent level enhanced modulus and HDT values. The enhanced flame retardancy of the sample was reflected by the higher LOI value (34.9).
TABLE IX
PMP and PPS Blends:
Interaction with Flame Retardant
polydibromophenylene Oxide Flame Retardant
(30 Wt% Glass Reinforced)
Run 91 92 93
% 10-64Pa Control 22.5 22.5
% PPS 0 0 10.0
Tensile Strength, Break (ksi) 6.1 5.8 6.7
Flexural Strength (ksi) 8.6 8.3 8.2
Flexural Modulus (ksi) 710 1,030 1,200
Notched Izod Impact (ft-lb/in) 0.8 0.5 0.5 Unnotched Izod Impact (ft-lb/in) 2.2 1.2 .8
HOT @ 264 psi (ºC. ) 124.3 150.0 160.2
UL94 Fail V-0 V-0
Limiting Oxygen Index
(LOI) (%) 25.5 30.0 34.9 a PO-64P represents polydibromophenylene oxide (64% Br) available from Great Lakes Chemical Corporation.
Example X
This example describes flame retarded glass reinforced PMP molding compositions containing 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 Lakes 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 flame retardant in the sample of run 101 and 104
reduced properties except for modulus and rated V-0 in the UL94 flammability test. The control sample in run 105 without flame 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 levels enhanced modulus and HDT values. These samples rated V-0 in the UL94 flammability test and possessed LOI values of about 32.
TABLE X
PMP and PPS Blends:
Interaction with Flame Retardant
Tetrabromobisphenol A Carbonate Oligomer
(30 Wt% Glass Reinforced)
Run 101 102 103 104 105
% BC-58a 22.5 22.5 22.5 27.0 Control
% PPS 0 5.0 10.0 0 0
Tensile Strength, Break (ksi) 4.9 6.0 6.4 4.9 6.1
Flexural Strength (ksi) 7.2 8.0 8.0 7.2 8.6
Flexural Modulus (ksi) 1,030 1,020 1,110 : 1,060 710
Notched Izod Inpact (ft-lb/in) 0.4 0.6 0.6 0.5 0.8
Unnotched Izod Inpact (ft-lb/in) 1.4 1.3 1.4 .9 2.2
HOT @ 264 psi (C) 109.9 148.1 158.6 114.1 124.3
UL94 V-0 V-0 V-0 V-0 Fail
Limiting Oxygen Index
(LOI) (%) 31.5 31.5 33.0 31.5 25.5 a BC-58 represents tetrabromobisphenol A carbonate oligomer (58% Br), available from Great Lakes Chemical Corporation.

Claims

C L A I M S
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.
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 ε-bout 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.
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- methyl-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.
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.
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.
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.
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 45 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.
EP92908871A 1991-03-21 1992-03-19 Polymethylpentene compositions. Withdrawn EP0576573A4 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US67360291A 1991-03-21 1991-03-21
US673602 1996-06-25

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EP0576573A4 EP0576573A4 (en) 1995-02-22

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EP (1) EP0576573A4 (en)
JP (1) JPH06507431A (en)
CA (1) CA2105082A1 (en)
WO (1) WO1992016586A1 (en)

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Publication number Priority date Publication date Assignee Title
EP1452567B1 (en) * 2001-11-30 2012-03-07 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

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0360439A2 (en) * 1988-09-02 1990-03-28 Mitsui Petrochemical Industries, Ltd. Heat resistant poly-4-methyl-1-pentene resin compostition and shaped article thereof

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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

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0360439A2 (en) * 1988-09-02 1990-03-28 Mitsui Petrochemical Industries, Ltd. Heat resistant poly-4-methyl-1-pentene resin compostition and shaped article thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO9216586A1 *

Also Published As

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EP0576573A4 (en) 1995-02-22
CA2105082A1 (en) 1992-09-22
JPH06507431A (en) 1994-08-25
WO1992016586A1 (en) 1992-10-01

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