GB1567849A - Flame-retardant polyphenylene ether resin composition - Google Patents
Flame-retardant polyphenylene ether resin composition Download PDFInfo
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- GB1567849A GB1567849A GB28102/77A GB2810277A GB1567849A GB 1567849 A GB1567849 A GB 1567849A GB 28102/77 A GB28102/77 A GB 28102/77A GB 2810277 A GB2810277 A GB 2810277A GB 1567849 A GB1567849 A GB 1567849A
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- resin composition
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- organic phosphorus
- phosphorus compound
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- 239000011342 resin composition Substances 0.000 title claims description 57
- 229920001955 polyphenylene ether Polymers 0.000 title claims description 33
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims description 7
- 239000003063 flame retardant Substances 0.000 title claims description 7
- 150000002903 organophosphorus compounds Chemical class 0.000 claims description 48
- 150000001875 compounds Chemical class 0.000 claims description 27
- 229920000642 polymer Polymers 0.000 claims description 22
- 229920005989 resin Polymers 0.000 claims description 19
- 239000011347 resin Substances 0.000 claims description 19
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- 229920000578 graft copolymer Polymers 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- -1 polyethylene Polymers 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 2
- 239000004698 Polyethylene Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 125000001309 chloro group Chemical group Cl* 0.000 claims 1
- 229920000573 polyethylene Polymers 0.000 claims 1
- 238000000034 method Methods 0.000 description 37
- 238000012360 testing method Methods 0.000 description 23
- 239000000047 product Substances 0.000 description 18
- 239000000203 mixture Substances 0.000 description 16
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 12
- 229920002857 polybutadiene Polymers 0.000 description 12
- 239000005062 Polybutadiene Substances 0.000 description 10
- 238000002347 injection Methods 0.000 description 10
- 239000007924 injection Substances 0.000 description 10
- 239000004793 Polystyrene Substances 0.000 description 9
- 239000008188 pellet Substances 0.000 description 9
- 229920002223 polystyrene Polymers 0.000 description 9
- 239000011369 resultant mixture Substances 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 7
- 229910052698 phosphorus Inorganic materials 0.000 description 7
- 239000011574 phosphorus Substances 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 238000000862 absorption spectrum Methods 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 2
- FOZNBFJYVWWMSZ-UHFFFAOYSA-N 1-N,4-N-bis(methoxymethyl)benzene-1,4-diamine Chemical compound COCNC1=CC=C(C=C1)NCOC FOZNBFJYVWWMSZ-UHFFFAOYSA-N 0.000 description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- 238000010559 graft polymerization reaction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- CISIJYCKDJSTMX-UHFFFAOYSA-N 2,2-dichloroethenylbenzene Chemical compound ClC(Cl)=CC1=CC=CC=C1 CISIJYCKDJSTMX-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 229920001890 Novodur Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
- C08L71/123—Polyphenylene oxides not modified by chemical after-treatment
-
- 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
- C08K5/49—Phosphorus-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
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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)
Description
(54) FLAME-RETARDANT POLYPHENYLENE ETHER RESIN
COMPOSITION
(71) We, ASAHI-DOW LIMITED, a corporation organized under the laws of Japan, of 1--2, Yurakucho 1-chome, Chiyoda-ku, Tokyo, Japan, and We,
SANKO KAIHATSU KAGAKU KENKYUSHO, a research laboratory in Japan, of 40, Andojibashidori 3-chome, Minami-ku, Osaka-shi, Japan, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- This invention relates to a flame-retardant polyphenylene ether resin composition.More particularly, the present invention relates to a flame-retardant resin composition having a novel organic phosphorus compound incorporated into a resin composition which has a styrenic polymer added to either a polyphenylene ether or a polyphenylene ether having graft copolymerized thereto a styrenic compound.
Polyphenylene ethers are excellent in mechanical properties, electrical properties, resistance to chemicals and thermal resistance and enjoy advantageous attributes such as low hydroscopicity and high dimensional stability. For their outstanding qualities, they have been attracting keen attention. Further, polyphenylene ethers exhibit an excellent flame-retarding property such that they are rated as self-extinguishing and non-dripping by the Testing Method D635 of
ASTM and the Specification No. 94 of the Underwriter' Laboratories (hereinafter referred to UL-94). However, it has been long since deficient fabricability of polyphenylene ethers was pointed out. The poor fabricability has so far remained as the most serious defect for polyphenylene ethers.As measures for overcoming this defect, there have been suggested a number of methods resorting to incorporation of styrenic polymers. For example, Japanese Patent Publication No.
17812/1968, U.S. Patent No. 3,383,435 and others have disclosed blended compositions of polyphenylene ethers with styrenic polymers, Resin compositions which contain graft copolymers having styrenic compounds grafted onto polyphenylene ethers have been disclosed in Japanese Patent Publication Nos.
1210/1972 and 27809/1971, Japanese Patent Laid-open Publication Nos. 98446/1974 and 51150/1975, U.S. Patent Nos. 3,586,736 and 3,929,931 and others.
These resin compositions formulated to impart improved fabricability to polyphenylene ethers, however, have a disadvantage that they do not prove suitable for a wide range of industrial applications in terms of inflammability because styrenic polymers incorporated therein are resins of a type such that they are destitute of self-extinguishing property and non-dripping property and, once ignited, cannot but be left to burn out completely.
The present invention provides a flame-retardant composition which is characterized by substantially comprising 80 to 98 o by weight (based on the total composition) of a resin component obtained by mixing a styrenic polymer with either a polyphenylene ether or a polyphenylene ether having a styrenic compound with or without another ethylenically unsaturated compound copolymerizable therewith graft-copolymerized thereon, in such a proportion that the polyphenylene ether component, having a number average molecular weight from 6,000 to 30,000 and represented by the generic formula::
(wherein, R1 and R2 each denote an alkyl group having 1 to 4 carbon atoms and n denotes the degree of polymerization), will account for 20 to 80% by weight (based on the total weight of resin component) and 2 to 20, ó by weight of at least one organic phosphorus compound represented by the generic formula::
(wherein, Ar denotes a trifunctional aromatic residue, Z and Z' each denote a monofunctional residue selected from a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms and aNH2~yXy group,
X denotes a residue of the formula
wherein R3, R4 and R5 each denote a monofunctional residue selected from a hydrogen atom, a halogen atom, an alkyl having 1 to 8 carbon atoms, an aralkyl group, a cyclohexyl group and a phenyl group, x is 1 or 2 and y is 0, 1 or 2).
Examples of the aforementioned polyphenylene ethers used for the present invention include poly(2,6-dimethylphenylene- 1,4-ether), poly(2,6diethylphenylene-1,4-ether), poly(2-methyl-6-ethylphenylene-1,4-ether), poly(2methyl-6-propylphenylene- 1,4-ether), poly(2,6-dipropylphenylene- 1,4-ether), poly(2-ethyl-6-propylphenylene- 1,4-ether), poly(2-methyl-6-butylphenylene- 1,4ether) and poly(2-ethyl-6-butylphenylene- 1,4-ether). The most advantageous polyphenylene ether for the purpose of the present invention is poly(2,6dimethylphenylene-l,4-ether). This particular polymer excels in compatibility with styrenic polymers, permits resin compositions of varying proportions to be readily prepared and manifests an outstanding effect in imparting flame-retardancy due to its synergism with organic phosphorus compounds.
For the present invention to be effectively worked, the number-average molecular weight of a polyphenylene ether is selected from the range of 6,000 to 30,000, preferably 7,000 to 25,000. Use of a polyphenylene ether having a numberaverage molecular weight of less than 6,000 proves undesirable because the polymer notably degrades the resultant resin composition in physical properties, particularly creep properties. Use of a polyphenylene ether having a higher molecular weight exceeding 30,000 is likewise undesirable because the polymer seriously degrades the resin composition in fabricability, causes degradation of the
styrenic polymer and inhibits maintenance of balanced physical properties.
In the polyphenylene ether having a styrenic compound graft-copolymerized
thereon for use in the present invention, the term "styrenic compound" is meant to
embrace styrene and various derivatives of styrene such as alkylation products and
halogenation products of styrene. Concrete examples are styrene, methyl styrene, 2,4-dlmethyl styrene, monochloro-styrene, dichloro-styrene, p-methyl
styrene and ethyl styrene.
At the time of polymerization, these styrenic compounds may be used in
combination with 30 Ó by weight or less of another copolymerizable, ethylenically
unsaturated compound such as, for example, methyl methacrylate, acrylonitrile, methacrylonitrile and butyl acrylate. Alternatively, the graft copolymerization may
be effected by using two or more kinds of styrenic compounds at the same time.
The graft copolymer to be used in the resin composition of the present
invention is desired to have 20 to 200 parts by weight of a styrenic compound with
or without another ethylenically unsaturated compound copolymerizable therewith
graft polymerized onto 100 parts by weight of a polyphenylene ether. If the amount
of the styrenic compound with or without the vinyl comonomer is less than the
lower limit, 20 parts by weight, then the resultant graft copolymerized
polyphenylene ether is substantially the same in quality as the polyphenylene ether
in the form of a homopolymer.If the amount of the styrenic compound with or
without the vinyl comonomer used in the graft polymerization exceeds the upper
limit, 200 parts by weight, then the styrenic compound with or without the vinyl
comonomer degrades the physical properties, particularly, impact strength, of the
resultant resin composition.
The term "styrenic polymer" as used in the present invention is meant to refer to a polymer formed preponderantly of a styrenic compoud and possessed of a
number-average molecular weight desirably in the range of from 50,000 to 200,000,
preferably from 60,000 to 150,000. If the number-average molecular weight of the
styrenic polymer is beow 50,000, there is a disadvantage that the physical properties
of the resultant resin, particularly impact strength and creep properties, are
deficient. If it exceeds 200,000, however, there ensues an adverse effect upon the
moldability and fabricability, which results in various undesirable phenomena such
as thermal deterioration of the composition at the time of fabrication and inferior
impact resistance of the shaped article due to residual strain.
The term "styrenic compound" as used herein refers to the same compound as
is used for the graft copolymerization described above. The styrenic polymers
usable for this invention further include those commonly known rubber-reinforced
styrenic resins. For example, rubber-reinforced polystyrene resins and
acrylonitrile-butadiene-styrene copolymer resins are embraced in the scope of this
invention. The proportion of the styrenic polymer to the total resin component of
the composition (inclusive of the styrenic polymer which is chemically bonded to
the polyphenylene ether in consequence of the graft copolymerization) is selected
from the range of 20 to 80% by weight, preferably from 25 to 75% by weight. If the
content of the styrenic polymer is less than the lower limit, 20% by weight, the
styrenic polymer fails to impart ample fabricability to the resultant resin
composition. If the content exceeds the upper limit, 80% by weight, it is difficult to
confer desired flame-retardancy upon the resultant resin composition, even after
mixing with the organic phosphorus compound used in the present invention.
Concrete examples of the trifunctional aromatic residue in the generic formula
(B) are as follows:
Concrete examples of the X component contained in the organic phosphorus compound represented by the generic formula (B) will be shown below in structural formulae:
The compounds of the generic formula (B) are used either singly or in the form of a mixture consisting of two or more members.
The organic phosphorus compounds represented by the generic formula (B) (hereinafter called novel organic phosphorus compounds) which are usable for the present invention are novel ones that are obtained by a method in which organic phosphorus compounds represented by the generic formula:
(wherein, R3, R4 and R5 each denote a hydrogen atom, a halogen atom, an alkyl having I to 8 carbon atoms, an aralkyl group, a cyclohexyl group or a phenyl group) (refer to Japanese Patent Publication No. 17979/1975 in the Official Gazette) to dehydrogenation condensation in conjunction with an aromatic amino compound having amino groups directly bonded with aforementioned trifunctional aromatic residue.Alternatively, organic phosphorus compounds represented by the generic formula:
(wherein, R3, R4 and R5 are as defined in the immediately preceding generic formula) (refer to Japanese Patent Publication No. 45397/1974 in the Official
Gazette) may be subjected to dehydrogenation (or de-alcohol) condensation in conjunction with an aromatic compound having methylolated amino groups directly bonded with the above trifunctional aromatic residue or said aromatic compound whose methylol groups are esterified.) Some of these compounds are disclosed under the title "organic phosphorus compounds" by the inventors in the specification of Japanese Published Unexamined Patent Application No.
5181/1978.
The novel organic phosphorus compound content required for manifestation of the effect of this invention is selected in the range of from 2 to 20%, preferably from 3 to 15%, by weight based on the total weight of the composition. If the content of the novel organic phosphorus compound is less than the lower limit 2%, there is an undesirable result that the resin composition will not easily acquire a quality capable of satisfying UL-94 tests for self-extinguishing property and nondripping property. If the novel organic phosphorus compound is added in an amount greater than the upper limit 20%, then the resin composition has a disadvantage that its physical properties, particularly heat deflection temperature and impact strength, cannot be maintained in the ranges warranting practical utility.
The method to be used for the production of the composition of the present invention is not particularly limited, i.e. the components may be mixed by any method effective at all for the purpose. One typical example of the methods advantageously available comprises the steps of thoroughly mixing the resin destined to form the backbone of the final composition with the novel organic phosphorus compound in a dry blender, melting and kneading the mixture in an extruder and molding the molten mixture into pellets.
Needless to mention, it is permissible to incorporate in the composition of the present invention other additives such as, for example, a plasticizer, a pigment, a reinforcing agent, a filler, an extender and a stabilizer as occasion demands.
Now, the present invention will be described more specifically with reference to examples thereof. Whenever there are mentioned parts and percents, they means parts by weight and percents by weight.
EXAMPLE 1.
In a four-necked flask fitted with a stirrer and a thermometer, 77 parts of a phosphorus compound represented by the following formula and 29 parts of benzoguanamine were heated in an oil bath until the temperature within the flask rose to 1700C.
With the contents kept under agitation, the temperature was elevated to 2300C over a period of one hour. Under a reduced pressure (30 mmHg of inner pressure), the water formed by the reaction was removed. When the reaction was continued for two hours at 2300C under the reduced pressure, distillation of water ceased to proceed. At this point, the product of reaction was taken out of the flask, cooled and pulverized. The product was found to have a melting point of 128"C. The infrared absorption spectrum indicated decreases of OH group and NH2 group. It was ascertained by the results of the elementary analysis that the reaction produced a novel organic phosphorus compound of the following formula.
In a blender, 35 parts of oly(2,6-dimethylphenylene-l,4-ether) having a number-average molecular weight of 12,500, 65 parts of a rubber-reinforced styrene-acrylonitrile copolymer having an average acrylonitrile content of 40o and a styrene-butadiene copolymer rubber content of 9.0% and 8 parts of the novel organic phosphorus compound mentioned above were thoroughly mixed.
Thereafter, the resultant mixture was melted and kneaded and molded into pellets by use of an extruder maintained at temperatures in the range of from 220 to 270"C. The mixed resin thus produced could be injection molded under conditions of 250"C and 600 kg/cm2. The molded product was found by tests to have a tensile strength of 440 kg/cm2 (by the method of ASTM D638, which applies hereinafter), an Izod impact strength of 12.0 kg.cm/cm (by the method of ASTM D256, which applies hereinafter) and a heat deflection temperature of 88.2"C (by the method of
ASTM D648, which applies hereinafter). The mixed resin of this example was tested for inflammability by the method of UL-94. The ignition time was found to be 7.5 seconds at the most and 2.8 seconds on the average.In the creep test under tension which was performed at 23"C under a load of 210 kg, the amount of creep after 1,000 hours of test was 0.99%.
EXAMPLE 2.
In a blender, 60 parts of poly(2,6-dimethylphenylene-1,4-ether) having a number-average molecular weight of 21,000, 40 parts of a rubber-reinforced polystyrene containing 8% of polybutadiene rubber and 6 parts of the same novel organic phosphorus compound as used in Example 1 were mixed. The resultant mixture was melted and kneaded in an extruder kept at temperatures in the range of from 230 to 2800 C, to produce pellets. The mixed resin thus produced could be injection molded under conditions of 2600C and 700 kg/cm2. It was found to have a tensile strength of 620 kg/cm2, an Izod impact strength of 10.5 kg.cm/cm and a heat deflection temperature of 109.00C.In the test for inflammability by the method of ULc94, the ignition time was found to be 5.5 seconds at most and 1.8 seconds on the average. Thus, the product was in the V-O grade. In the creep tests under tension which were performed at 60"C under a load of 105 kg and at 230C under a load of 210 kg, the amounts of creep after 1,000 hours were 0.58or and 1.01No, respectively.
EXAMPLE 3.
In an extruder maintained at temperatures in the range of from 220 to 280"C, a resin component consisting of 65 parts of poly(2,6-dimethylphenylene-1,4-ether) having a number-average molecular weight of 9,500, 20 parts of a polystyrenegrafted polybutadiene having a polybutadiene content of 40 Ó and 15 parts of a polystyrene having a number-average molecular weight of 105,000 was melted and kneaded and molded to produce a mixed resin in the form of pellets. In a blender, 100 parts of the pellets and 4.5 parts of the same novel organic phosphorus compound as used in Example 1 were mixed.The resultant mixture was melted and kneaded in an extruder kept at temperatures in the range of from 200 to 260"C. The resin composition thus produced could be injection molded under conditions of 240"C and 450 kg/cm2. It was found to have a tensile strength of 660 kg/cm2, an
Izod impact strength of 18.5 kg.cm/cm and a heat deflection temperature of 120"C.
In the test for inflammability by the method of UL-94, the ignition time was 4.2 second at most and 2.6 seconds on the average. Thus, the product was in the V-O grade. In the creep tests under tension performed at 60 C. under a load of 105 kg and at 23 C under a load of 210 kg, the amounts of creep were 0.51% and 0.83% respectively, after 1,000 hours.
EXAMPLE 4.
The procedure of Example I for the preparation of the organic phosphorus compound was repeated, except 99 parts of a phosphorus compound of the formula
was used in place of
It was confirmed by the infrared absorption spectrum and the results of elementary analysis that the reaction produced a novel organic phosphorus compound of the following formula:
In a blender, 5 parts of this novel organic phosphorus compound and 100 parts of the mixed resin pellets obtained in Example 3 were thoroughly mixed. The resultant mixture was melted and kneaded in an extruder. The resin composition thus produced could be injection molded under conditions of 240"C and 500 kg/cm2.It was found to have a tensile strength of 590 kg/cm2, an Izod impact strength of 16.8 kg.cm/cm and a heat deflection temperature of 116.5"C. In the inflammability test by the method of UL-94, the ignition time was 3.5 seconds at most and 1.6 seconds on the average. Thus, the product was in the V-O grade.
REFERENCE EXAMPLE 1.
This example involved use of an organic phosphorus compound which had not undergone the reaction with an amino group-containing compound to illustrate, through comparison of the results with those of Example 4, how much the omission of said reaction affected the heat deflection temperature.
In a blender, 100 parts of the mixed resin pellets obtained in Example 3 and 5 parts of an organic phosphorus compound represented by the following formula were thoroughly mixed and then melted and kneaded in an extruder. The resin composition thus produced could be injection molded under conditions of 280"C and 550 kg/cm2.
It was found to have a tensile strength of 590 kg/cm2, an Izod impact strength of 11.8 kg.cm/cm and a heat deflection temperature of 109.5"C. In the inflammability test by the method of UL-94, the ignition time was 7.4 seconds at most and 3.1 seconds on the average. Thus, the product was in the V-O grade.
EXAMPLE 5.
Under continued agitation, 50 parts of poly(2,6-dimethylphenylene- 1,4-ether) having a number-average molecular weight of 9,700, 20 parts of styrene and 1.0 part of di-t-butyl peroxide were heated to 1500C over a period of 10 minutes and then to 240"C over the following period of 10 minutes. The reaction product was molded
into pellets by use of an extruder. The graft copolymer thus produced was found to
have a polystyrene content of 26%. In 40 ml of methylene chloride, 2.0 g of the
polymer was dissolved and was left to stand at 30"C. Even after 6 hours of this
standing, absolutely no precipitation was recognized. This proves that no
homopolymer of polyphenylene ether remained in the graft copolymer.
In a blender, a mixture consisting of 50 parts of this graft copolymer, 20 parts
of a polystyrene-grafted polybutadiene having a polybutadiene content of 40% and
30 parts of a polystyrene having a number-average molecular weight of 88,000 was
thoroughly mixed with 5.0 parts of the same novel organic phosphorus compound
as used in Example 1. The resultant mixture was melted and kneaded in an extruder
kept at temperatures in the range of from 200 to 260"C. The resin composition thus
produced could be injection molded under conditions of 2200C and 450 kg/cm2.It
was found to have a tensile strength of 430 kg/cm2, an Izodimactstrength of 22.5
kg.cm/cm and a heat deflection temperature of 106.50 . In the test for
inflammability performed by the method of UL-94, the ignition time was found to
be 8.8 seconds at most and 4.2 seconds on the average. Thus the product was in the VW grade.
EXAMPLE 6.
In a blender, 60 parts of the graft copolymer obtained in Example 5, 30 parts of
a rubber-reinforced polystyrene having a polybutadiene rubber content of 8%, 10
parts of a polystyrene-grafted polybutadiene having a polybutadiene content of
40% and 3.5 parts of the same novel organic phosphorus compound as used in
Example 4 were thoroughly mixed. In an extruder kept at temperatures in the range
of from 200 to 2600 C, the resultant mixture was melted and kneaded. The resin
composition thus produced could be injection molded under conditions of 2300C
and 450 kg/cm2.It was found to have a tensile strength of 460 kg/cm2, an Izod
impact strength of 23.0 kg.cm/cm and a heat deflection temperature of 1120C. In
the test for inflammability performed by the method of UL-94, the ignition time
was found to be 11.8 seconds at most and 6.8 seconds on the average. Thus, the
product was in the V-I grade.
EXAMPLES 7-10.
By following the procedure of Example 1, novel organic phosphorus
compounds were prepared by using not the phosphorus compound
itself but its derivatives. By following the procedure of Example 4, the compounds were converted into resin compositions. These compositions were tested for inflammability by the method of UL-94. The results are shown collectively in
Table 1.
TABLE 1
Test of resin composition for inflammability by the method of UL-94 Example Organic phosphorus Maximum Average No. compound used (seconds) (seconds) Rating 7 < 9.2 4.5 V-O t-Bu 8 CH3% 10.3 4.3 V-i CH3 cH3 CH3 9 X 7.4 4.4 V-0 0 CIOH 10 C6H3 3$C3 11.2 4.9 V-i CH20H EXAMPLES 11-13.
The procedure of Example 5 was repeated with the amount of styrene for graft polymerization varied, to produce resin compositions. The compositions were tested for inflammability. The results are collectively shown in Table 2.
TABLE 2
Test of resin composition for inflammability by the method of UL-94 Amount of polystyrene in Example graft copolymer Maximum Average No. (%) (seconds) (seconds) Rating 11 34 13.5 8.4 V-1 12 45 20.2 12.6 V-1 13 58 24.4 20.8 V-1 EXAMPLES 14-1 8.
The procedure of Example 6 was repeated with the added amount of the novel organic phosphorus compound varied. The resin compositions obtained consequently were tested for inflammability. The results are collectively shown in
Table 3.
TABLE 3
Test of resin composition for inflammability by the method of UL-94 Amount of organic phosphorus Example compound added Maximum Average No. (parts) (seconds) (seconds) Rating 14 2.5 20.5 14.6 V-1 15 4.5 10.1 4.8 V-1 16 9 4.0 2.5 V-0 17 13 3.5 1.4 V-0 18 18 1.9 0.9 V-0 EXAMPLE 19.
A novel organic phosphorus compound was synthesized by repeating the procedure of Example 1, except 9.7 parts of melamine was used in place of the benzoguanaminc. The product showed a melting point of 137 C. The infrared absorption spectum indicated decreasses of OH group and NH2 group. It was confirmed by the results of the elementary analysis that the reaction produced a novel organic phosphorus compound of the following formula.
In a blender, 4.0 parts of this novel organic phosphorus compound was thoroughly mixed with 100 parts of pellets of the mixed resin obtained in Example 3. The resultant mixture was melted and kneaded in an extruder kept at temperatures in the range of from 200 to 2600 C. The resin composition thus produced could be injection molded under conditions of 240"C and 450 kg/cm2. It was found to have a tensile strength of 620 kg/cm2, an Izod impact strength of 19.2 kg.cm/cm and a heat deflection temperature of 121"C. In the test for inflammability conducted by the method of UL-94, the ignition time was 10.6 seconds at most and 4.1 seconds on the average. Thus, the product was in the V-l grade.
EXAMPLE 20.
In a four-necked flask fitted with a stirrer and a thermometer, 85 parts of a phosphorus compound represented by the following formula
and 15 parts of metaphenylene diamine were heated in an oil bath until the temperature within the flask rose to 1800C. Under continued agitation, the temperature was further raised to 230"C over a period of one hour, during which period the formed water was removed under reduced pressure (interior pressure 40 mmHg). When the reaction was continued at 2300C under said reduced pressure for two hours, distillation of water ceased to occur. At this time, the product was taken out of the flask, cooled and pulverized.It showed a melting point of 119 C. It was confirmed by the results of the infrared absorption spectrum and the elementary analysis that the reaction produced a novel organic phosphorus compound of the following formula:
A thorough mixture of 65 parts of poly(2,6-dimethylphenylene- 1,4-ether) having a number-average molecular weight of 18,000, 15 parts of styrene and part of di-t-butyl peroxide was passed through an extruder kept at temperatures in the range of from 190 to 2300C to undergo polymerization and pelletization at the same time. The graft copolymer thus obtained was found to have a polystyrene content of 17.7%. When a 2.0-g portion of the polymer was dissolved in 40 ml of methylene chloride and the solution was left to stand at 300C overnight, absolutely no precipitate was found.This proves that no homopolymer of polyphenylene ether remained in the graft copolymer.
In a blender, a resin component consisting of 50 parts of this graft copolymer, 20 parts of a styrene-grafted polybutadiene having a polybutadiene content of 40% and 30 parts of a polystyrene having a number-average molecular weight of 85,000 was thoroughly mixed with 6 narts of the novel organic phosphorus compound of which the method of pre aratiron has been indicated in this example. The resultant mixture was melted and kneaded in an extruder kept at temperatures in the range of from 200 to 2400 C. The resin composition thus produced could be injection molded under conditions of 220"C and 450 kg/cm2.It was found to have a tensile strength of 440 kg/cm2, an Izod impact strength of 18.5 kg.cmlcm and a heat deflection temperature of 107"C. In the test for inflammability performed by the method of UL-94, the ignition time was found to be 7.5 seconds at most and 3.9 seconds on the average. Thus, the product was in the V--O grade.
EXAMPLE 21.
In a four-necket flask fitted with a stirrer and a thermometer, 72 parts of a phosphorus compound represented by the following formula:
and 28 parts of bis(methoxymethyl)-paraphenylenediamine were heated in an oil bath until the temperature within the flask rose to 160"C. Under continued agitation, the temperature was further raised to 220"C over a period of one hour, during which period the reaction was continued removing the formed methanol under a reduced pressure (interior pressure 30 mmHg).The interior temperature was raised up to 2500 C. After the distillation of methanol ceased to proceed, the product was taken out of the flask, cooled and finely pulverized. this product showed a melting point of 152"C. It was confirmed from the results of the infrared absorption spectrum and the elementary analysis that the reaction produced a novel organic phosphorus compound of the following formula:
In a blender, 3.5 parts of this novel organic phosphorus compound, 70 parts of the styrene-grafted polyphenylene ether obtained in Example 20, 20 parts of a styrene-grafted polybutadiene having a polybutadiene content of 40% and 10 parts of a polystyrene having a number-average molecular weight of 92,000 were thoroughly mixed.The resultant mixture was melted and kneaded in an extruder kept at temperatures in the range of from 210 to 2600C. The resin composition thus produced could be injection molded under conditions of 240"C and 550 kg/cm2. It was found to have a tensile strength of 520 kg/cm2, an Izod impact strength of 23.5 kg.cm/cm and a heat deflection temperature of 224"C. In the test for inflammability performed by the method of UL-94, the ignition time was found to be 6.5 seconds at most and 3.8 seconds on the average. Thus, the product was in the V--O grade.
EXAMPLE 22-24.
The procedure of Example 21 was repeated, except the aromatic amino compound derivatives shown in Table 4 were used in place of bis(methoxymethyl)paraphenylenediamine.
The results of the inflammability test conducted on the resultant resin compositions by the method of UL-94 are shown in the following Table 4.
TABLE 4
r Test of resin composition for inflarurnability by the method of UL-94 Aromatic amino Example compound derivative Maximum Average No. used (seconds) (seconds) Rating 22 (cH3OCH2NH#4c 7.2 4.5 to CH3OCH2NH ANHCH20CH3 23 S) 5.0 2.9 V-0 NHCH20CH3 NHCOH9 24 + 9.2 5.I V-1 NHCHz0C4Hg EXAMPLES 25-27.
The procedure of Example 20 was repeated, except the diamines shown in
Table 5 were used in place of metaphenylene diamine. The results of the test performed on the resultant resin compositions for inflammability by the method of UL-94 are shown in the following table.
TABLE 5
Test of resin composition for inflammability by the method of UL-94 Example Maximum Average No. Do gamine used (seconds) (seconds) Rating NH2 25 CH3 8.6 4.6 V-O NH2 26 2 XN)NH2 5.2 4.1 V-0 27 H2NglNH2 9.1 5.2 V-l EXAMPLES 28-31.
The procedure of Example 21 was repeated, except varying combinaticns of phosphorus compounds and aromatic amino compound derivatives were used. The resultant resin compositions were tested for strengths and for inflammability by UL-94. The results are collectively shown in Table 6.
TABLE 6
; I I I d t H l - h . P N m by UL-94 YX Izod impact =S e N No. compound used derivative used (kg/cmf) (kg/cm (seconds) (seconds) N oo Ct 28 Thy CH3OCH2NH0NHCH2OCH3 Q 20.5 t 2.7 3 t 2 v o E U E m x o m NHCHCH3 N N N Oviv ~ 29 t Bu NHCHCH3 E N" Om X o m o 3 H F M M 7 CH3 30 OHP1CH3 CH2OCH2NH NHCH2OC 530 22.0 9.2 5.3 Ct CH3OCH2 NH N E z z r H T C) 6 t O C o X CS ~
Claims (22)
1. A flame-retardant polyphenylene ether resin composition, substantially comprising 80 to 98% by weight of a mixed resin consisting of 20 to 80% by weight of a polyethylene ether having a number average molecular weight from 6,000 to 30,000 and represented by the gereric formula:
(wherein, R1 and R2 each denote an alkyl group having I to 4 carbon atoms and n denotes the degree of polymerization) and 20 to 80% by weight of a styrenic polymer and 2 to 20% by weight of at least one organic phosphorus compound represented by the generic formula::
(wherein, Ar denotes a trifunctional aromatic residue, Z and Z' each denote a monofunctional residue selected from a hydrogen atom, an alkyl group having I to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms and a -N 2 group, X denotes a residue of the formula
wherein, R3, R4 and R5 each denote a monofunctional residue selected from a hydrogen atom, a halogen atom, an alkyl having 1 to 8 carbon atoms, an aralkyl group a cyclohexyl group and a phenyl group, x is 1 or 2 and y is 0, 1 or 2).
2. A flame-retardant polyphenylene ether resin composition, substantially comprising 80 to 98% by weight of a resin component and 2 to 20% by weight of at least one organic phosphorus compound represented by the generic formula:
(wherein, Ar denotes a trifunctional aromatic residue, Z and Z' each denote a monofunctional residue selected from a hydrogen atom, an alkyl group having I to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms and a NH2yXy group,
X denotes a residue of the formula
(wherein R3, R4 and R6 each denote a monofunctional residue selected from a hydrogen atom, a halogen atom, an alkyl having I to 8 carbon atoms, an aralkyl group, a cyclohexyl group and a phenyl group, x is 1 or 2 and y is 0, 1 or 2), said resin component comprising a graft copolymer and a styrenic polymer, said graft copolymer having polyphenylene ether in an amount of 20 to 80% by weight of the resin component and having 20 to 200 parts by weight of a styrenic compound or a combination of a styrenic compound and another ethylenically unsaturated compound copolymerizable therewith grafted onto 100 parts by weight of a polyphenylene ether having a number average molecular weight from 6,000 to 30,000 and represented by the generic formula:
(wherein, R, and RB each denote an alkyl group having 1 to 4 carbon atoms and n denotes the degree of polymerization).
3. A resin composition according to Claim I or 2, wherein the residue (C) is such that all R3, R4 and R, each are a hydrogen atom.
4. A resin composition according to Claim I or 2, wherein the residue (C) is such that R4 and R5 each are a chlorine atom and R3 is a hydrogen atom.
5. A resin composition according to Claim 1 or 2, wherein the residue (C) is such that R3, R4 and R each are a t-butyl group.
6. A resin composition according to Claim 1 or 2, wherein the residue (C) is such that RB is a phenyl group and RB and R4 each are a hydrogen atom.
7. A resin composition according to Claim 1 or 2, wherein the residue (C) is such that R3 and R6 each are a methyl group and R4 is a t-butyl group.
8. A resin composition according to Claim I or 2, wherein the organic phosphorus compound (B) is such that Ar is a group of the formula
and Z and Z' each are a --NH,~,X, group.
9. A resin composition according to Claim 1 or 2, wherein the organic phosphorus compound (B) is such that Ar is a group of the formula
Z is a phenyl group and Z' is a -NH2-vXv group.
10. A resin composition according to Claim 1 or 2, wherein the organic phosphorus compound (B) is such that Ar is a
group, Z is a hydrogen atom and Z' is a -NH2,,X, group.
11. A resin composition according to Claim 1 or 2, wherein the organic phosphorus compound (B) is such that Ar is a
group, Z is a hydrogen atom and Z' is a -NH2-vXv group.
12. A resin composition according to Claim 1 or 2, wherein the organic phosphorus compound (B) is such that Ar is a
group and Z and Z' each are a -NH2-Xv group.
13. A resin composition according to Claim 1 or 2, wherein the organic phosphorus compound (B) is such that Ar is a
group, Z is a phenyl group and Z' is a NH2yXy group.
14. A resin composition according to Claim I or 2, wherein the organic phosphorus compound (B) is such that Ar is a
group, Z is a hydrogen atom and Z' is a -NH2-vXv group.
15. A resin composition according to Claim 1 or 2, wherein the organic phosphorus compound (B) is such that Ar is a
group, Z is a hydrogen atom and Z' is a -NH2-vXv group.
16. A resin composition according to Claim 1 or 2, wherein the organic phosphorus compound (B) is such that Ar is a
group, Z is a hydrogen atom and Z' is aNH2~yXy group.
17. A resin composition according to Claim 1 or 2, wherein the organic phosphorus compound (B) is such that Ar is a
group, Z is a hydrogen atom and Z' is a -NH2-vXv group.
18. A resin composition according to Claim 1 or 2, wherein the organic phosphorus compound (B) is such that Ar is a
group or
group and Z and Z' each are a phenyl group.
19. A resin composition according to Claim 1 or 2, wherein the organic phosphorus compound (B) is such that Ar is a
group, Z is a hydrogen atom and Z' is a -NH2-vXv group.
20. A resin composition according to Claim 1 or 19, wherein the polyphenylene ether (A) is such that R, and RB each are a methyl group.
21. A resin composition according to Claim 1 or Claim 2 substantially as described in any one of the Examples.
22. An article molded from a resin composition according to any one of Claims 1 to 21.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP51078893A JPS5925822B2 (en) | 1976-07-05 | 1976-07-05 | Flame retardant polyphenylene ether resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB1567849A true GB1567849A (en) | 1980-05-21 |
Family
ID=13674482
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB28102/77A Expired GB1567849A (en) | 1976-07-05 | 1977-07-05 | Flame-retardant polyphenylene ether resin composition |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPS5925822B2 (en) |
| CA (1) | CA1088238A (en) |
| DE (1) | DE2730345C3 (en) |
| FR (1) | FR2357602A1 (en) |
| GB (1) | GB1567849A (en) |
| NL (1) | NL166271C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7973191B2 (en) | 2008-08-14 | 2011-07-05 | Ems-Patent Ag | Method for the production of dibenz[c,e] [1,2]-oxaphosphorin derivatives, amino-dibenz[c,e] [1,2]-oxaphosphorin and also use thereof |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5925822B2 (en) * | 1976-07-05 | 1984-06-21 | 旭化成株式会社 | Flame retardant polyphenylene ether resin composition |
| JPH0269011A (en) * | 1988-09-05 | 1990-03-08 | Takayuki Chikaki | Tone quality adjusting device |
| CH699310B1 (en) | 2008-08-14 | 2012-03-30 | Ems Patent Ag | A process for preparing bridged dibenz [c, e] [1,2] oxaphosphorin-6-oxide. |
| EP3540000A1 (en) | 2018-03-16 | 2019-09-18 | Stutz, Felix Benjamin | Flame retardant polyamide 6 master batch and fibers made thereof |
| JP7432282B2 (en) * | 2022-02-14 | 2024-02-16 | 三光株式会社 | A novel dihydroxaphosphaphenanthrene derivative having a triazine ring and exhibiting a high refractive index and its production method |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1555489A (en) * | 1975-06-16 | 1979-11-14 | Ici Ltd | Process for preparing a granular herbicidal composition |
| JPS5925822B2 (en) * | 1976-07-05 | 1984-06-21 | 旭化成株式会社 | Flame retardant polyphenylene ether resin composition |
-
1976
- 1976-07-05 JP JP51078893A patent/JPS5925822B2/en not_active Expired
-
1977
- 1977-07-05 NL NL7707437.A patent/NL166271C/en not_active IP Right Cessation
- 1977-07-05 FR FR7720623A patent/FR2357602A1/en active Granted
- 1977-07-05 GB GB28102/77A patent/GB1567849A/en not_active Expired
- 1977-07-05 CA CA282,053A patent/CA1088238A/en not_active Expired
- 1977-07-05 DE DE2730345A patent/DE2730345C3/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7973191B2 (en) | 2008-08-14 | 2011-07-05 | Ems-Patent Ag | Method for the production of dibenz[c,e] [1,2]-oxaphosphorin derivatives, amino-dibenz[c,e] [1,2]-oxaphosphorin and also use thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| NL166271B (en) | 1981-02-16 |
| DE2730345B2 (en) | 1979-05-17 |
| JPS5925822B2 (en) | 1984-06-21 |
| NL7707437A (en) | 1978-01-09 |
| DE2730345A1 (en) | 1978-01-12 |
| FR2357602A1 (en) | 1978-02-03 |
| CA1088238A (en) | 1980-10-21 |
| DE2730345C3 (en) | 1980-01-10 |
| JPS535253A (en) | 1978-01-18 |
| NL166271C (en) | 1981-07-15 |
| FR2357602B1 (en) | 1980-01-18 |
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