WO1992016586A1 - Composition de polymethylpentene - Google Patents

Composition de polymethylpentene Download PDF

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Publication number
WO1992016586A1
WO1992016586A1 PCT/US1992/002209 US9202209W WO9216586A1 WO 1992016586 A1 WO1992016586 A1 WO 1992016586A1 US 9202209 W US9202209 W US 9202209W WO 9216586 A1 WO9216586 A1 WO 9216586A1
Authority
WO
WIPO (PCT)
Prior art keywords
weight percent
composition
reinforcer
flame retardant
weight
Prior art date
Application number
PCT/US1992/002209
Other languages
English (en)
Inventor
Edwin Boudreaux, Jr.
Original Assignee
Phillips Petroleum Company
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 Company filed Critical Phillips Petroleum Company
Priority to JP4508356A priority Critical patent/JPH06507431A/ja
Priority to CA002105082A priority patent/CA2105082A1/fr
Publication of WO1992016586A1 publication Critical patent/WO1992016586A1/fr

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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

  • 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
  • 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 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
  • 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 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
  • 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
  • thermoplastics are G-filament (about 9 micrometers) and K-filament (about 13 micrometers).
  • thermoplastics 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
  • 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.
  • 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.
  • 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 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
  • metallic hydroxides such as magnesium hydroxide, aluminum hydroxide, calcium hydroxide, barium hydroxide, etc.
  • 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.
  • 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 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.
  • 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
  • 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.
  • This example shows the properties of injection molded samples prepared from 30% glass
  • 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.
  • DE-83R represents decabromodiphenyloxide (DBDPO) (83% Br), available from Great Lakes Chemical Corporation.
  • 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 .
  • Run 81B 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
  • 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.
PCT/US1992/002209 1991-03-21 1992-03-19 Composition de polymethylpentene WO1992016586A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP4508356A JPH06507431A (ja) 1991-03-21 1992-03-19 ポリメチルペンテン組成物
CA002105082A CA2105082A1 (fr) 1991-03-21 1992-03-19 Compositions de polymethylpentene

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US67360291A 1991-03-21 1991-03-21
US673,602 1991-03-21

Publications (1)

Publication Number Publication Date
WO1992016586A1 true WO1992016586A1 (fr) 1992-10-01

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ID=24703332

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1992/002209 WO1992016586A1 (fr) 1991-03-21 1992-03-19 Composition de polymethylpentene

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

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1452567A1 (fr) * 2001-11-30 2004-09-01 Polyplastics Co Ltd Composition de resine ignifuge
CN114196126A (zh) * 2022-01-13 2022-03-18 宁夏清研高分子新材料有限公司 一种聚4-甲基-1-戊烯阻燃材料的制备方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4025582A (en) * 1975-07-03 1977-05-24 Phillips Petroleum Company Ultraviolet-stabilized polyolefin compositions
EP0305539A1 (fr) * 1987-03-03 1989-03-08 Mitsui Petrochemical Industries, Ltd. Composition a base de polyolefine renforcee par des fibres et resistant a la chaleur

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
MY104182A (en) * 1988-09-02 1994-02-28 Mitsui Petrochemical Ind Heat resistant poly-4-methyl-1-pentene resin composition and shaped article thereof.

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4025582A (en) * 1975-07-03 1977-05-24 Phillips Petroleum Company Ultraviolet-stabilized polyolefin compositions
EP0305539A1 (fr) * 1987-03-03 1989-03-08 Mitsui Petrochemical Industries, Ltd. Composition a base de polyolefine renforcee par des fibres et resistant a la chaleur

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP0576573A4 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1452567A1 (fr) * 2001-11-30 2004-09-01 Polyplastics Co Ltd Composition de resine ignifuge
EP1452567A4 (fr) * 2001-11-30 2005-09-07 Polyplastics Co Composition de resine ignifuge
US7115677B2 (en) 2001-11-30 2006-10-03 Polyplastics Co., Ltd. Flame-retardant resin composition
CN114196126A (zh) * 2022-01-13 2022-03-18 宁夏清研高分子新材料有限公司 一种聚4-甲基-1-戊烯阻燃材料的制备方法
CN114196126B (zh) * 2022-01-13 2023-03-10 宁夏清研高分子新材料有限公司 一种聚4-甲基-1-戊烯阻燃材料的制备方法

Also Published As

Publication number Publication date
EP0576573A1 (fr) 1994-01-05
JPH06507431A (ja) 1994-08-25
EP0576573A4 (fr) 1995-02-22
CA2105082A1 (fr) 1992-09-22

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