CA1088238A - Flame-retardant polyphenylene ether resin composition - Google Patents
Flame-retardant polyphenylene ether resin compositionInfo
- Publication number
- CA1088238A CA1088238A CA282,053A CA282053A CA1088238A CA 1088238 A CA1088238 A CA 1088238A CA 282053 A CA282053 A CA 282053A CA 1088238 A CA1088238 A CA 1088238A
- Authority
- CA
- Canada
- Prior art keywords
- group
- resin composition
- composition according
- organic phosphorus
- yxy
- 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.)
- Expired
Links
- 229920001955 polyphenylene ether Polymers 0.000 title claims abstract description 29
- 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 abstract description 7
- 239000003063 flame retardant Substances 0.000 title claims abstract description 7
- 239000011342 resin composition Substances 0.000 title claims description 71
- 150000002903 organophosphorus compounds Chemical class 0.000 claims abstract description 59
- 150000001875 compounds Chemical class 0.000 claims abstract description 25
- 239000000203 mixture Substances 0.000 claims abstract description 25
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 24
- 229920005989 resin Polymers 0.000 claims abstract description 22
- 239000011347 resin Substances 0.000 claims abstract description 22
- -1 aromatic amino compound Chemical class 0.000 claims abstract description 19
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 14
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 14
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 11
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 5
- 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 abstract description 5
- 125000005843 halogen group Chemical group 0.000 claims abstract description 5
- 229920000642 polymer Polymers 0.000 claims description 22
- 229920000578 graft copolymer Polymers 0.000 claims description 12
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 11
- 125000003118 aryl group Chemical group 0.000 claims description 9
- 229920002554 vinyl polymer Polymers 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 6
- 229910052801 chlorine Inorganic materials 0.000 claims 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims 2
- 239000004793 Polystyrene Substances 0.000 abstract description 10
- 229920002223 polystyrene Polymers 0.000 abstract description 10
- 125000003277 amino group Chemical group 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract 1
- 238000007493 shaping process Methods 0.000 abstract 1
- 125000001424 substituent group Chemical group 0.000 abstract 1
- 238000000034 method Methods 0.000 description 36
- 238000012360 testing method Methods 0.000 description 23
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 19
- 239000000047 product Substances 0.000 description 18
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 229920002857 polybutadiene Polymers 0.000 description 11
- 239000005062 Polybutadiene Substances 0.000 description 9
- 239000008188 pellet Substances 0.000 description 9
- 229910052698 phosphorus Inorganic materials 0.000 description 9
- 235000014786 phosphorus Nutrition 0.000 description 9
- 239000011574 phosphorus Substances 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 239000011369 resultant mixture Substances 0.000 description 6
- 238000000862 absorption spectrum Methods 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 150000004985 diamines Chemical class 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
- 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
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 2
- 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 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-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
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 230000007423 decrease 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
- 150000002170 ethers Chemical class 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
- 150000003018 phosphorus compounds Chemical class 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- OEVVKKAVYQFQNV-UHFFFAOYSA-N 1-ethenyl-2,4-dimethylbenzene Chemical compound CC1=CC=C(C=C)C(C)=C1 OEVVKKAVYQFQNV-UHFFFAOYSA-N 0.000 description 1
- 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
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-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
- 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
- 229920001577 copolymer Polymers 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- CBOIHMRHGLHBPB-UHFFFAOYSA-N hydroxymethyl Chemical compound O[CH2] CBOIHMRHGLHBPB-UHFFFAOYSA-N 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 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
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 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
- IOVGROKTTNBUGK-SJCJKPOMSA-N ritodrine Chemical compound N([C@@H](C)[C@H](O)C=1C=CC(O)=CC=1)CCC1=CC=C(O)C=C1 IOVGROKTTNBUGK-SJCJKPOMSA-N 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Flame-retardant composition comprising (1) a novel organic phosphorous compound having a substituent of where R3, R4 and R5 each is a monofunctional residue selected from a hydrogen atom, a halogen atom, an alkyl or aralkyl group having 1 to 8 carbon atoms, a cyclohexyl group and a phenyl group, on an amino group of an aromatic amino compound and (2) a mixture resin of polystyrene and polyphenylene ether grafted or not with a styrenic compound, said (1) being 2-20% by weight and (2) 80-98%
by weight, on the basis of the composition. The resins of the present invention are useful as raw materials for shaping articles which require flame retardancy.
Flame-retardant composition comprising (1) a novel organic phosphorous compound having a substituent of where R3, R4 and R5 each is a monofunctional residue selected from a hydrogen atom, a halogen atom, an alkyl or aralkyl group having 1 to 8 carbon atoms, a cyclohexyl group and a phenyl group, on an amino group of an aromatic amino compound and (2) a mixture resin of polystyrene and polyphenylene ether grafted or not with a styrenic compound, said (1) being 2-20% by weight and (2) 80-98%
by weight, on the basis of the composition. The resins of the present invention are useful as raw materials for shaping articles which require flame retardancy.
Description
1088;~38 Thi~ invcntion rela~es to a flame-retardant poly-phenylene ether r~sin composition. More particularLy, the present invention relates to a flame-retardant resin composition having a novel organic phosphorus compound incorpoxated into a resin composition which has a styrenic polymer added to either a poly-phenylene ether or a polyphenylene ether having ~raft copolymerized thereto a styrenic compound.
Polyphenylene ethers are excellent in mechanical properties, electrical properties, res~stance to chemicals and thermal resistance and en~oy advantageous attributes such as low hydroscopicity and high dimensional stability. For the out-standing quality, they have been arresting keen attention.
Further, olyphenylene ethers exhibit an excellent flame-retarding property such that they are rated as self-extinguishing a~d non-dripping by the Testing Method D-635 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 polyphenvlene 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/lg68 (July 29/68, A. Fujiwara et al.), U.S. Patent No.
3,383,435 (May 1~/68, E.P. Cijek) 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 PublicatiGn Nos. 1210/1972 (Jan. 13/72, S. Nakashio et al.) and 27809/1971 (Aug. 12/71, A. Nakanishi et al.), Japanese 30 Patent Laid-open Publication Nos. 98446/1974 (Sept. 18/74, H.
Suzaki et al.) and 51150/1975 (~ay 7/75, S. Izawa et al.), U.S.
.~
1088Z3~
Pat~nt No~. 3,S86,73~ (June 22/71, T. Takemura et al.) and 3,929,931 (Dec. 30/75, S. Izawa et al.) 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 n~n-dripping property and, once ignited, cannot but be left to burn out completely.
An object of the present invention is to provide polyphenylene ether resin compositions improved both in fabric- -ability and flame-retardancy.
To be more specific, the present invention aims to -provide a flame-retardant composition which is characterized by -substantially comprising 80 to 98~ 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 a vinyl compound co-polymerizable therewith graft-copolymerized thereon, in such a proportion that the polyphenylene ether component represented by the generic formula: ~
~ R
- t `R2 1 (A ;
(wherein, Rl and R2 each denote an alkyl group having 1 to 4 carbon atoms and n denotes the degree of polymerization) will B
.
1088Z3~
account for 20 to 80% by weight (based on the total weight of resin component~ and 2 to 20% by weight of at least one member selected from the group consisting of novel organic phosphorus compounds represe~ted by the generic formulas:
[ 2-x ~
(wherein, Ar denotes a trifunctional aromatic residue, Z
and Z' each denote a monofunctional residue selected from the class consisting of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms and a -NH2 yXy group, X denotes a residue of the formula ~3 ~ (C) 0= P o 5 wherein R3, R4 and R5 each denote a monofunctional residue selected from the class consisting of 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 denotes an integer having the value of 1 or 2 and y denotes an integer having the value of 0, 1 or 2).
Examples of the aforementioned polyphenylene ethers used for the present invention include poly(2,6-dimethyl-phenylene-1,4-ether), poly(2,6-diethylphenylene-1,4-ether), 1~88238 pol~y(2-methyl-6-ethylphenylene-1,4-ether), polyt2-methyl-6-propylphen~lene-1,4-ether), poly(2,6-dipropylphenylene-1,4-ether), poly(2-ethyl-6-propylphenylene-1,4-ether), poly(2-methyl-6-butylphenylene-1,4-ether) and poly(2--ethyl-6-butylphenylene-1,4-ether). The most advantageous poly-phenylene ether for the purpose of the present lnvention is poly(2,6-dimethylphenylene-1,4-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 poIyphenylene ether -is selected from the range of 6,000 to 30,000, preferably 7gO00 to 25,000. Use of a polyphenylene ether having a mlmber-average molecular weight of less than 6,ooo 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 ~abricability, causes degradation of the styrenic polymer andinhibits maintenance of balanced physical properties.
In the polyphenylene ether having a ~tyrenic com-pound 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 ;
eYamples are styrene, ~-methyl styrene, 2,4-dimethyl styrene, monochloro-styrene, dichloro-styrene, p-methyl styrene, ethyl styrene and the like.
At the time of polymerization, these styrenic compounds may be used in combination with 30% by weight or less of copolymerizable vinyl compounds 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 com-position of the present invention is desired to have 20 to -200 parts by weight of a styrenic compound with or without a vinyl 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 compound and possessed of a num~er-average molecular weight desirably in the range of from 50,000 t~
2009000, preferably from 60,000 to 150,000. If the number-: . ,. ~ , .
- ` ' - :
`
average molecular weight of the styrenic polymer is below 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 and 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 poly-phenylene ether in consequence of the graft copalymerization)is selected from the range of 20 to 80% by weight, preferably from 25 to 75% by weight. If the content of the styrenlc 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 by mixing with the organic phosphorus compound of the present invention.
.
.
Concrete examples of the trifunctional aromatic residue in the generlc formula (B) are as follows:
N N ~ ~ ~ CH2 ~ , , ~o~ ~ lrS~
Concrete examples of the X component contalned in the organic phosphorus compound represented by the generic formula (B) will be shown below in structural formula.
t-Bu . :
O=P O O=P- O CH3 CH2- CH2~
, ~C~
CH2- ~ =P CQ
~ / 3 O = P--O O = P--O
CH2- CH2 ::
.:
.-.. -- 8 --, - 10882~
.: ' , t-Bu 8 17 .
O= P- O t-Bu = P_ t-Bu CH
~\~) C6H13 O ~ O= P- CH~
CH2 \=:/ ' CH2 t-Bu ~: t-Bu ~
O= P- O :t-Bu i O ~ p_ O
: : CH2- CH2- ~ ~:-The compounds of the generic formula (B~ are used ~.
either singly or 1n the form of a mixture consi~king of two - or more members.
he organic phosphorus compounds represented by : :
: 5 the generic formula (B) (hereinafter called novel organic ~ phosphorus compounds) which are usable for the present ::: invention are novel ones that are obkained by a method in , ~ : : .
which organic phosphorus compounds represented by the generic formula:
.
_ g _ . .
-` ~088238 ~ 4 3 ~ ~
0= P- 0 R
~l2OH
(wherein, R3, R4 and R5 each clenote a hydrogen atom, a halogen atom, an alkyl having 1 to ~ carbon atoms, an aralkyl group, a cyclohexyl group or a phenyl group) (refer to Japanese Patent Publication No. 17979/1975 (June 5/75, T. Saito) in the Offici.al 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:
3 ~ /
0= ~- 0 R5 (wherein, R3, R4 and R5 are as defined in the immediately pre-ceding generic formula) (refer to Japanese Patent Publication No. 45397/1974 (Dec. 4/74, T. Saito) in the Official Gazette) may be subjected to dehydrogenation (or de-alcohol) condensation in conjunction with an aromatic compound having methylolated s amino groups directly bonded with the above trifunctional aromatic residue or said aromatic compound whose methylol groups ~ :
are esterified.) ~ - 10 - .
! ~
108823~
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 qualitv capable of satisfying UL-94 tests for self-extinguishing property and non-dripping property. If the novel organic phosphorus compound is added in an amount greater than the upper limit 20%, then the resin com-position 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 advantage-ously 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 incor- ~;
~orate in the composition of the present invention other additives such as, for example, a plasticizer, a pigment, .`' , . . .
1~8238 a reinforcing agent a riller, an extender and a stabilizer as occasion demands.
Now, the present inventlon will be described more specifically with reference to examples thereof. Whenever there are mentioned parts and percents, they invariably mean parts by weight and percents by weight.
Example l:
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 170C.
~ ,.~, O = P--O
With the contents kept under agitation, the temperature was elevated to 230C 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 230C 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 128C. The infrared absorption spectrum indicated decreases of OH group and NH2 groupO It was ascertained by the results of the elementary analysis that the reaction produced a novel organic phosphorus compound of the following , , ' "' formula. , , G ~1~ J 2 (e~)2 In a blender, 35 parts of poly(2,6-dimethyl-phenylene-1,4~ether) having a number-average molecular weight of 12,500, 65 parts of a rubber-reinforced styrene-acrylo- . -nitrile copolymer having an average acrylonitrile content of ' ' 4% and a styrene-butadiene copolymer rubber content of 9.0%
and 8 parts of thè novel organic phosphorus compound mentioned above were thoroughly mixed. ~hereafter, the result- ~ -ant mixture was melted and kneaded and molded into pellets by use of an extruder maintained at temperatures in the range of from 220 to 270C. The mixed resin thus produced could be injection molded under conditions of 250C and 600 kg/cm . The molded product was found by tests to have a tensile strength of 440 kg/cm2 (by the method of ASTM D638, : which applie,s hereinafter), an Izod impact strength of 12.0 kg.cm/cm (by the method of ASTM D256, which applies hereln-after) and a heat deflection temperature of 88,2C (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 23C under a load of 210 kg, the amount of creep after 1,000 hours of test was 0.99%. "
1~88238 i`xample 2:
In a blender, 60 parts of poly(2,6-dlmethylphenylene-].,4-ether) having a number-average molecular weight of 21,000, 40 parts of a rubber-reinforced polystyrene containing 8% Or polybutadiene rubber and 6 parts of the same r.ovel 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 280C, to produce pellets. Tne mixed resin thus produced could be in~ection molded under conditions of 260C 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 109.0C. In the test for inflammability by the method of UL-94, the i~nition time was found to be 5.5 seconds at most and 1.8 seconds on the average. Thus, the product was in the V-0 grade. In the creep tests under tension which were performed at 60C under a load of 105 kg and at 23C under a load of 210 kg, the amounts of creep ~ .
after 1,000 hours were o . 58% and 1.01%, respectively.
Example 3:
In an extruder maintained at temperatures in the range of from 220 to 280C, a resin component consisting of 65 parts of poly(2,6-dimethylphenylene-1,4-ether) having a number-average molecular weight of 99500, 20 parts of a polystyrene-grafted polybutadiene having a polybutadiene content of 40% 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 -108823~
as used in Example 1 were mixed. The resultant mlxture was melted and kneaded in an extruder kept at temperatures in the range of from 200 to 260C. The resln composition thus produced could be in~ection molded under conditions of 240C ;~
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 120C. In the test for inflammability by the method of ~JL-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 60C. under a load of 105 kg and at 23C
under a load of 210 kg, the amounts of creep were 0.51% and o.83% respectively, after 1,000 hours.
Example 4: `
The procedure of Example 1 for the prepar~tion of the organic phosphorus compound was repeated, except 99 parts of a phosphorus compound of the formula : ~ ~ ' ' , ~;~ 1- CR
was used in place o~
.
: O=P--O
~: CH2-OH
' -` 1088238 :[t was confirmed by the infrared absorption spectrum and the re~ults of elementary analysis that the reaction produced c~n novel organic phosphorus compound of the following formula:
Polyphenylene ethers are excellent in mechanical properties, electrical properties, res~stance to chemicals and thermal resistance and en~oy advantageous attributes such as low hydroscopicity and high dimensional stability. For the out-standing quality, they have been arresting keen attention.
Further, olyphenylene ethers exhibit an excellent flame-retarding property such that they are rated as self-extinguishing a~d non-dripping by the Testing Method D-635 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 polyphenvlene 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/lg68 (July 29/68, A. Fujiwara et al.), U.S. Patent No.
3,383,435 (May 1~/68, E.P. Cijek) 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 PublicatiGn Nos. 1210/1972 (Jan. 13/72, S. Nakashio et al.) and 27809/1971 (Aug. 12/71, A. Nakanishi et al.), Japanese 30 Patent Laid-open Publication Nos. 98446/1974 (Sept. 18/74, H.
Suzaki et al.) and 51150/1975 (~ay 7/75, S. Izawa et al.), U.S.
.~
1088Z3~
Pat~nt No~. 3,S86,73~ (June 22/71, T. Takemura et al.) and 3,929,931 (Dec. 30/75, S. Izawa et al.) 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 n~n-dripping property and, once ignited, cannot but be left to burn out completely.
An object of the present invention is to provide polyphenylene ether resin compositions improved both in fabric- -ability and flame-retardancy.
To be more specific, the present invention aims to -provide a flame-retardant composition which is characterized by -substantially comprising 80 to 98~ 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 a vinyl compound co-polymerizable therewith graft-copolymerized thereon, in such a proportion that the polyphenylene ether component represented by the generic formula: ~
~ R
- t `R2 1 (A ;
(wherein, Rl and R2 each denote an alkyl group having 1 to 4 carbon atoms and n denotes the degree of polymerization) will B
.
1088Z3~
account for 20 to 80% by weight (based on the total weight of resin component~ and 2 to 20% by weight of at least one member selected from the group consisting of novel organic phosphorus compounds represe~ted by the generic formulas:
[ 2-x ~
(wherein, Ar denotes a trifunctional aromatic residue, Z
and Z' each denote a monofunctional residue selected from the class consisting of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms and a -NH2 yXy group, X denotes a residue of the formula ~3 ~ (C) 0= P o 5 wherein R3, R4 and R5 each denote a monofunctional residue selected from the class consisting of 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 denotes an integer having the value of 1 or 2 and y denotes an integer having the value of 0, 1 or 2).
Examples of the aforementioned polyphenylene ethers used for the present invention include poly(2,6-dimethyl-phenylene-1,4-ether), poly(2,6-diethylphenylene-1,4-ether), 1~88238 pol~y(2-methyl-6-ethylphenylene-1,4-ether), polyt2-methyl-6-propylphen~lene-1,4-ether), poly(2,6-dipropylphenylene-1,4-ether), poly(2-ethyl-6-propylphenylene-1,4-ether), poly(2-methyl-6-butylphenylene-1,4-ether) and poly(2--ethyl-6-butylphenylene-1,4-ether). The most advantageous poly-phenylene ether for the purpose of the present lnvention is poly(2,6-dimethylphenylene-1,4-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 poIyphenylene ether -is selected from the range of 6,000 to 30,000, preferably 7gO00 to 25,000. Use of a polyphenylene ether having a mlmber-average molecular weight of less than 6,ooo 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 ~abricability, causes degradation of the styrenic polymer andinhibits maintenance of balanced physical properties.
In the polyphenylene ether having a ~tyrenic com-pound 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 ;
eYamples are styrene, ~-methyl styrene, 2,4-dimethyl styrene, monochloro-styrene, dichloro-styrene, p-methyl styrene, ethyl styrene and the like.
At the time of polymerization, these styrenic compounds may be used in combination with 30% by weight or less of copolymerizable vinyl compounds 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 com-position of the present invention is desired to have 20 to -200 parts by weight of a styrenic compound with or without a vinyl 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 compound and possessed of a num~er-average molecular weight desirably in the range of from 50,000 t~
2009000, preferably from 60,000 to 150,000. If the number-: . ,. ~ , .
- ` ' - :
`
average molecular weight of the styrenic polymer is below 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 and 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 poly-phenylene ether in consequence of the graft copalymerization)is selected from the range of 20 to 80% by weight, preferably from 25 to 75% by weight. If the content of the styrenlc 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 by mixing with the organic phosphorus compound of the present invention.
.
.
Concrete examples of the trifunctional aromatic residue in the generlc formula (B) are as follows:
N N ~ ~ ~ CH2 ~ , , ~o~ ~ lrS~
Concrete examples of the X component contalned in the organic phosphorus compound represented by the generic formula (B) will be shown below in structural formula.
t-Bu . :
O=P O O=P- O CH3 CH2- CH2~
, ~C~
CH2- ~ =P CQ
~ / 3 O = P--O O = P--O
CH2- CH2 ::
.:
.-.. -- 8 --, - 10882~
.: ' , t-Bu 8 17 .
O= P- O t-Bu = P_ t-Bu CH
~\~) C6H13 O ~ O= P- CH~
CH2 \=:/ ' CH2 t-Bu ~: t-Bu ~
O= P- O :t-Bu i O ~ p_ O
: : CH2- CH2- ~ ~:-The compounds of the generic formula (B~ are used ~.
either singly or 1n the form of a mixture consi~king of two - or more members.
he organic phosphorus compounds represented by : :
: 5 the generic formula (B) (hereinafter called novel organic ~ phosphorus compounds) which are usable for the present ::: invention are novel ones that are obkained by a method in , ~ : : .
which organic phosphorus compounds represented by the generic formula:
.
_ g _ . .
-` ~088238 ~ 4 3 ~ ~
0= P- 0 R
~l2OH
(wherein, R3, R4 and R5 each clenote a hydrogen atom, a halogen atom, an alkyl having 1 to ~ carbon atoms, an aralkyl group, a cyclohexyl group or a phenyl group) (refer to Japanese Patent Publication No. 17979/1975 (June 5/75, T. Saito) in the Offici.al 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:
3 ~ /
0= ~- 0 R5 (wherein, R3, R4 and R5 are as defined in the immediately pre-ceding generic formula) (refer to Japanese Patent Publication No. 45397/1974 (Dec. 4/74, T. Saito) in the Official Gazette) may be subjected to dehydrogenation (or de-alcohol) condensation in conjunction with an aromatic compound having methylolated s amino groups directly bonded with the above trifunctional aromatic residue or said aromatic compound whose methylol groups ~ :
are esterified.) ~ - 10 - .
! ~
108823~
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 qualitv capable of satisfying UL-94 tests for self-extinguishing property and non-dripping property. If the novel organic phosphorus compound is added in an amount greater than the upper limit 20%, then the resin com-position 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 advantage-ously 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 incor- ~;
~orate in the composition of the present invention other additives such as, for example, a plasticizer, a pigment, .`' , . . .
1~8238 a reinforcing agent a riller, an extender and a stabilizer as occasion demands.
Now, the present inventlon will be described more specifically with reference to examples thereof. Whenever there are mentioned parts and percents, they invariably mean parts by weight and percents by weight.
Example l:
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 170C.
~ ,.~, O = P--O
With the contents kept under agitation, the temperature was elevated to 230C 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 230C 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 128C. The infrared absorption spectrum indicated decreases of OH group and NH2 groupO It was ascertained by the results of the elementary analysis that the reaction produced a novel organic phosphorus compound of the following , , ' "' formula. , , G ~1~ J 2 (e~)2 In a blender, 35 parts of poly(2,6-dimethyl-phenylene-1,4~ether) having a number-average molecular weight of 12,500, 65 parts of a rubber-reinforced styrene-acrylo- . -nitrile copolymer having an average acrylonitrile content of ' ' 4% and a styrene-butadiene copolymer rubber content of 9.0%
and 8 parts of thè novel organic phosphorus compound mentioned above were thoroughly mixed. ~hereafter, the result- ~ -ant mixture was melted and kneaded and molded into pellets by use of an extruder maintained at temperatures in the range of from 220 to 270C. The mixed resin thus produced could be injection molded under conditions of 250C and 600 kg/cm . The molded product was found by tests to have a tensile strength of 440 kg/cm2 (by the method of ASTM D638, : which applie,s hereinafter), an Izod impact strength of 12.0 kg.cm/cm (by the method of ASTM D256, which applies hereln-after) and a heat deflection temperature of 88,2C (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 23C under a load of 210 kg, the amount of creep after 1,000 hours of test was 0.99%. "
1~88238 i`xample 2:
In a blender, 60 parts of poly(2,6-dlmethylphenylene-].,4-ether) having a number-average molecular weight of 21,000, 40 parts of a rubber-reinforced polystyrene containing 8% Or polybutadiene rubber and 6 parts of the same r.ovel 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 280C, to produce pellets. Tne mixed resin thus produced could be in~ection molded under conditions of 260C 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 109.0C. In the test for inflammability by the method of UL-94, the i~nition time was found to be 5.5 seconds at most and 1.8 seconds on the average. Thus, the product was in the V-0 grade. In the creep tests under tension which were performed at 60C under a load of 105 kg and at 23C under a load of 210 kg, the amounts of creep ~ .
after 1,000 hours were o . 58% and 1.01%, respectively.
Example 3:
In an extruder maintained at temperatures in the range of from 220 to 280C, a resin component consisting of 65 parts of poly(2,6-dimethylphenylene-1,4-ether) having a number-average molecular weight of 99500, 20 parts of a polystyrene-grafted polybutadiene having a polybutadiene content of 40% 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 -108823~
as used in Example 1 were mixed. The resultant mlxture was melted and kneaded in an extruder kept at temperatures in the range of from 200 to 260C. The resln composition thus produced could be in~ection molded under conditions of 240C ;~
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 120C. In the test for inflammability by the method of ~JL-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 60C. under a load of 105 kg and at 23C
under a load of 210 kg, the amounts of creep were 0.51% and o.83% respectively, after 1,000 hours.
Example 4: `
The procedure of Example 1 for the prepar~tion of the organic phosphorus compound was repeated, except 99 parts of a phosphorus compound of the formula : ~ ~ ' ' , ~;~ 1- CR
was used in place o~
.
: O=P--O
~: CH2-OH
' -` 1088238 :[t was confirmed by the infrared absorption spectrum and the re~ults of elementary analysis that the reaction produced c~n novel organic phosphorus compound of the following formula:
2 ,~= p- 0 c~)2 ~N~ ~ CH2-In a blender, 5 parts of this novel organlc phos-phorus 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 in~ection molded under conditions of 240C 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 116.5C. `
In the inflammability test by the method of U~-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 . . .
. . ~ ...~:.
`:
` 108823~
compos~tion thus produced could be in~ection molded under cond1tions Or 280C and 550 kg/cm2.
~\~ ' .
O = P--O
It was found to have a tenslle strength of 590 kg/cm2, an Izod impact strength of 11.8 kg.cm/cm and a heat deflection temperature of 109.5C. 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-0 grade.
Example 5:
10Under 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 150C over a period of 10 minutes and then to 240C 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 mQ of methylene chloride, 2.0 g of the polymer was dissolved and was left to stand at 30C. 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 blenderg a mixture consisting of 50 parts of this graft copolymer~ 20 parts of a polystyrene-grafted 11~88Z38 polybutadiene having a polybutadiene content Or 40% and 30 parts of a polystyrene havin~ a number-average molecular weight of 88,ooo was thorou~lly mixed with 5.0 parts of the same novel organic phosphorus compound as used in ~xample 1.
The resultant mixture was melted and kneaded in an extruder kept at temperatures in the range of from 200 to 260C.
The resin composition thus produced could be in~ection molded under conditions of 220C and 450 kg/cm2. It was found to have a tensile strength of 430 kg/cm2, an Izod impact strength of 22.5 kg.cm/cm and a heat deflection temperature of 106.5C. 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 V-0 grade.
Example 6:
In a blender, 60 parts of the graft copolymer obtained in Example 5, 30 parts of a rubbRr-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 260C, the resultant mixture was melted and kneaded. The resin composition thus produced could be in~ection molded under conditions of 230C 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 112'`C. In the test for inflam-mability performed by the method of UL-94, the ignition time was found to be 11.8 seconds at most and 6.8 seconds on ., .
-.. ~ ' t;he average. Thus, the product was in the V-l ~rade.
Examples 7 ~10:
By followin~ the procedure of Example 1, novel organic phosphorus compounds were prepared by using not the phosphorus compound ~9 o = P o itself but its derivatives. By following the procedure of Example 4, the compounds were converted into resin compo-sitions. 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 composltion Example Organic for inflammability by the ~o. phosphorus method of UL-94 compound used Maximum Averaee Ratin (seconds) (seconds) g 7 ~, 9 . 2 Ll ~ 5 V_O
t-Bu CH3--.
8 =I~ CH3 10.3 4.3 V-l ".,: .
CH3 ~
9 o=P~o ?.4 4.4 V-0 ` ~:
6 13 ~CLI3 11.2 4,9 ~ V_1 :~ ~
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 inflam- ~ .
mability. The results are collectively shown ln Table 2. -:
"
' 20 - ~ :
., ,, . - ~ , .~ .. . . .
~C~88Z3B ., Table 2 Test of resin composition for Example Amount of inflammability by the method ~!o. polystyrene in of UL-94 graft copolymer (%) Maximum Average Rating (seconds) (seconds) 11 34 13.5 8.4 V-l 12 45 20.2 12.6 V-1 13 58 24.4 20.8 V-l Examples 14 -18: `~
The procedure of Example 6 was repeated with the added amount of the nove' organic phosphorus compound varied.
The resin compositions obtained consequently were tested for inf'lammability. The results are collectively shown in Table 3.
Table 3 Test of resin composition Example Amount of organic for inflammability by the No.phosphorus method of UL-94 compound added (parts) (seconds) (seconds) Rating 142.5 20.5 14.6 V-l 154.5 10.1 4.8 V-l 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 synthe-sized by repeating the procedure of Example 1, except 9.7 parts of melamine was used in place of the benzoguanamine.
The product showed a melting point of 137C. The infrared absorption spectrum indicated decreases of OH group and NH2 group. It was confirmed b~y the results of the elernentary ~nalysis that the reactlon produced a novel organic phos-~horus compound of the followin~ formula.
N~ N ~ ( ~ )4 N- C~ ~C- N 2 CH2 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 260C.
The resin composition thus produced could be injection molded under conditions of 240C and 450 kg/cm . 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 121C. In the test for inflammability conducted by the method of UL-94 a the ignition time was 10.6 seconds at most and 4.1 seconds on the av~ra~e.
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 - , . , . :
o= P-o CH2OH ~
and 15 parts of methaphenylene diamine were heated in an oil bath until the temperature within the flask rose to 180C. Under continued agi~ation, the temperature was further raised to 230C 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 230C 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 119C. 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:
N ~ N ~] H2 ~ )2 ~ thorough mixture of 65 parts of polyt2,6-dimethylphenylene-1,4-ether) having a number-average molecular weight of 18,000, 15 parts of styrene and l.0 part of di-t-butyl peroxide was passed through an extruder kept at temperatures in the range of from l90 to 230C 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 - --` 108823~
the polymer was dissolved in 40 mQ of methylene chloride and the solution was left to stand at 30C overnight, absolutely no precipitate was found. This proves that no homopolymer of polyphenylene ether remained in the graft copolymer.
In a blender, a resln component consisting of 50 parts of this graft copolymer, 20 parts of a styrene-grafted polybutadiene having a polybutadie~;? content of 40% and 30 parts of a polystyrene having a number-average molecular weight of 85,ooo was thoroughly mixed with 6 parts of the novel organic phosphorus compound of which the method of preparation 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 240C.
The resin composition thus produced could be inJection molded under conditions of 220C and 450 kg/cm2. It was found to have a tensile strength of 440 kg/cm2, an Izod impact strength of 18.5 kg.cm/cm and a heat deflection temperature of 107C. In the test for inflammability performed by the method of UL-94 3 the ignition tiMe was -`
found to be 7.5 second at most and 3.9 seconds on the average. Thus~ the product was in the V-O grade.
Example 21:
In a four-necked flask fitted with a stirrer and a thermometer, 72 parts of a phosphorus compound represented by the following formula:
. .
O = I - O
' ' ' .
1~8238 and 28 ~arts of bis(methoxymethyl)-paraphenylenediamine :~ere heated in an oil bath until the temperature within the flask rose to 160C. Under continued agitation, the temperature was further raised to 220C over a period of one hour, during which period the reaction was continued removlng the formed methanol under a reduced pressure (interior pressure 30 mmHg). The interior temperature was raised up to 250C. 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 152C. 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:
L N~ N 1~ ( O = ~=O ))2 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 260C.
The resin composition thus produced could be injection molded under conditions of 240C and 550 kg/cm2. It was found to have a tensile strength of 520 kg/cm2, an Izod ~.
~mpact strength of 23.5 kg.cm/cm and a heat deflection temperature of 224C. In the test for lnflamma~illty 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 aromatlc 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.
Table Test of resin composition Ex- Aromatic amino for inflammability by the ample compound derivatlve method of UL-94 No. used Maximum Average Ratin (seconds) (seconds) g '"
22 (CH3OCH2NH - ~CH2 7.2 4.5 V-O ~
23 CH3OCH2NHl~NHCH2OcH3 5.0 2.9 V-0 ;
NHC~120C4H9 .
24 ~ 9.2 5.1 V-l ~; NHcH2oc4H9 ~ .
Examples 25 - 27:
The procedure of Example 20 was repeated~ except the diamines shown in Table 5 were used in place of .
:; : . .. .
' ' . ' . ~
; ~
rnethaphenylene dlamine. The re~ults of the test performed on the resultant resin compositions for inflammability by l;he method of UL-94 are shown in the ollowing table.
Table 5 Test of resin composition for inflammabllity by the method Example Diamine used of UL-94 No. Maximum Average Ratlng (seconds) (seconds) CH3 ~ 8.6 4.6 V-O
:
26 H2N - ~ NH2 5.2 4.1 V-O
27 ~2N ~ N~2 9.1 2 V-l Example 28-31:
The procedure of Example 21 was repeated~ except varying combinations of phosphorus compounds and aromatic amino compound derivatives were used. The resultant resin compositions were tested for strengths and l'or inflammability by UL-94. The results are collectively shown in Table 6.
~, - 27 --:~
W ~ ~ ~ tq - o ~ co o 1- 3 x ~ W
~o~ o~ ~ ~o~ ' ~' o~ o~ o,~, o~ C~ ~. ' C~
~ ~ ~ ~ ~ D
W W ~ W ~D ~
g g g o ~ ~ :.
~ ~ X ~ ~ P~ :' ~
~ C~ . :~
~ ~CD~-~ I X ~o ~ ~Z :C o O ~ O r3 ¢ ~ roO w ,,- .- .
w ' - ~
. ~ u~ ~3 . ~ ~D
Ul Ul ~ \~109 ~ 3 ~.
IJ W ~ 1--~ tD ~q .:
.o o ~n o~ 3 ~
I`~ ~ .-. ~ ~
Ul 1'~ H
C~ ~ N
l-- ~ ~ ~ ~ O O
o ~n o o~ ~n ~o ~_ ~ .' 1-- ~ 3 cs H ~ :.
. . . . o 1' ~ ~ ~
co ~ ~ ~ C~n ~q ~ ~ P~
_~ I ~ ~
~n ~ ~ p~ O
~D C ~ 3 (D
. . . . O
~o w 1\) ~ 3 P' IJ- o ~q ~
~ ¢ ¢ ¢ ' ~ ' ~
~ I I I ~ P~
o 1- 1- o ~ ~ .' ;
.
: . :- . .
.:~ ,. .
obtained in Example 3 were thoroughly mixed. The resultant mixture was melted and kneaded in an extruder. The resin composition thus produced could be in~ection molded under conditions of 240C 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 116.5C. `
In the inflammability test by the method of U~-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 . . .
. . ~ ...~:.
`:
` 108823~
compos~tion thus produced could be in~ection molded under cond1tions Or 280C and 550 kg/cm2.
~\~ ' .
O = P--O
It was found to have a tenslle strength of 590 kg/cm2, an Izod impact strength of 11.8 kg.cm/cm and a heat deflection temperature of 109.5C. 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-0 grade.
Example 5:
10Under 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 150C over a period of 10 minutes and then to 240C 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 mQ of methylene chloride, 2.0 g of the polymer was dissolved and was left to stand at 30C. 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 blenderg a mixture consisting of 50 parts of this graft copolymer~ 20 parts of a polystyrene-grafted 11~88Z38 polybutadiene having a polybutadiene content Or 40% and 30 parts of a polystyrene havin~ a number-average molecular weight of 88,ooo was thorou~lly mixed with 5.0 parts of the same novel organic phosphorus compound as used in ~xample 1.
The resultant mixture was melted and kneaded in an extruder kept at temperatures in the range of from 200 to 260C.
The resin composition thus produced could be in~ection molded under conditions of 220C and 450 kg/cm2. It was found to have a tensile strength of 430 kg/cm2, an Izod impact strength of 22.5 kg.cm/cm and a heat deflection temperature of 106.5C. 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 V-0 grade.
Example 6:
In a blender, 60 parts of the graft copolymer obtained in Example 5, 30 parts of a rubbRr-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 260C, the resultant mixture was melted and kneaded. The resin composition thus produced could be in~ection molded under conditions of 230C 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 112'`C. In the test for inflam-mability performed by the method of UL-94, the ignition time was found to be 11.8 seconds at most and 6.8 seconds on ., .
-.. ~ ' t;he average. Thus, the product was in the V-l ~rade.
Examples 7 ~10:
By followin~ the procedure of Example 1, novel organic phosphorus compounds were prepared by using not the phosphorus compound ~9 o = P o itself but its derivatives. By following the procedure of Example 4, the compounds were converted into resin compo-sitions. 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 composltion Example Organic for inflammability by the ~o. phosphorus method of UL-94 compound used Maximum Averaee Ratin (seconds) (seconds) g 7 ~, 9 . 2 Ll ~ 5 V_O
t-Bu CH3--.
8 =I~ CH3 10.3 4.3 V-l ".,: .
CH3 ~
9 o=P~o ?.4 4.4 V-0 ` ~:
6 13 ~CLI3 11.2 4,9 ~ V_1 :~ ~
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 inflam- ~ .
mability. The results are collectively shown ln Table 2. -:
"
' 20 - ~ :
., ,, . - ~ , .~ .. . . .
~C~88Z3B ., Table 2 Test of resin composition for Example Amount of inflammability by the method ~!o. polystyrene in of UL-94 graft copolymer (%) Maximum Average Rating (seconds) (seconds) 11 34 13.5 8.4 V-l 12 45 20.2 12.6 V-1 13 58 24.4 20.8 V-l Examples 14 -18: `~
The procedure of Example 6 was repeated with the added amount of the nove' organic phosphorus compound varied.
The resin compositions obtained consequently were tested for inf'lammability. The results are collectively shown in Table 3.
Table 3 Test of resin composition Example Amount of organic for inflammability by the No.phosphorus method of UL-94 compound added (parts) (seconds) (seconds) Rating 142.5 20.5 14.6 V-l 154.5 10.1 4.8 V-l 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 synthe-sized by repeating the procedure of Example 1, except 9.7 parts of melamine was used in place of the benzoguanamine.
The product showed a melting point of 137C. The infrared absorption spectrum indicated decreases of OH group and NH2 group. It was confirmed b~y the results of the elernentary ~nalysis that the reactlon produced a novel organic phos-~horus compound of the followin~ formula.
N~ N ~ ( ~ )4 N- C~ ~C- N 2 CH2 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 260C.
The resin composition thus produced could be injection molded under conditions of 240C and 450 kg/cm . 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 121C. In the test for inflammability conducted by the method of UL-94 a the ignition time was 10.6 seconds at most and 4.1 seconds on the av~ra~e.
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 - , . , . :
o= P-o CH2OH ~
and 15 parts of methaphenylene diamine were heated in an oil bath until the temperature within the flask rose to 180C. Under continued agi~ation, the temperature was further raised to 230C 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 230C 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 119C. 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:
N ~ N ~] H2 ~ )2 ~ thorough mixture of 65 parts of polyt2,6-dimethylphenylene-1,4-ether) having a number-average molecular weight of 18,000, 15 parts of styrene and l.0 part of di-t-butyl peroxide was passed through an extruder kept at temperatures in the range of from l90 to 230C 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 - --` 108823~
the polymer was dissolved in 40 mQ of methylene chloride and the solution was left to stand at 30C overnight, absolutely no precipitate was found. This proves that no homopolymer of polyphenylene ether remained in the graft copolymer.
In a blender, a resln component consisting of 50 parts of this graft copolymer, 20 parts of a styrene-grafted polybutadiene having a polybutadie~;? content of 40% and 30 parts of a polystyrene having a number-average molecular weight of 85,ooo was thoroughly mixed with 6 parts of the novel organic phosphorus compound of which the method of preparation 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 240C.
The resin composition thus produced could be inJection molded under conditions of 220C and 450 kg/cm2. It was found to have a tensile strength of 440 kg/cm2, an Izod impact strength of 18.5 kg.cm/cm and a heat deflection temperature of 107C. In the test for inflammability performed by the method of UL-94 3 the ignition tiMe was -`
found to be 7.5 second at most and 3.9 seconds on the average. Thus~ the product was in the V-O grade.
Example 21:
In a four-necked flask fitted with a stirrer and a thermometer, 72 parts of a phosphorus compound represented by the following formula:
. .
O = I - O
' ' ' .
1~8238 and 28 ~arts of bis(methoxymethyl)-paraphenylenediamine :~ere heated in an oil bath until the temperature within the flask rose to 160C. Under continued agitation, the temperature was further raised to 220C over a period of one hour, during which period the reaction was continued removlng the formed methanol under a reduced pressure (interior pressure 30 mmHg). The interior temperature was raised up to 250C. 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 152C. 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:
L N~ N 1~ ( O = ~=O ))2 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 260C.
The resin composition thus produced could be injection molded under conditions of 240C and 550 kg/cm2. It was found to have a tensile strength of 520 kg/cm2, an Izod ~.
~mpact strength of 23.5 kg.cm/cm and a heat deflection temperature of 224C. In the test for lnflamma~illty 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 aromatlc 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.
Table Test of resin composition Ex- Aromatic amino for inflammability by the ample compound derivatlve method of UL-94 No. used Maximum Average Ratin (seconds) (seconds) g '"
22 (CH3OCH2NH - ~CH2 7.2 4.5 V-O ~
23 CH3OCH2NHl~NHCH2OcH3 5.0 2.9 V-0 ;
NHC~120C4H9 .
24 ~ 9.2 5.1 V-l ~; NHcH2oc4H9 ~ .
Examples 25 - 27:
The procedure of Example 20 was repeated~ except the diamines shown in Table 5 were used in place of .
:; : . .. .
' ' . ' . ~
; ~
rnethaphenylene dlamine. The re~ults of the test performed on the resultant resin compositions for inflammability by l;he method of UL-94 are shown in the ollowing table.
Table 5 Test of resin composition for inflammabllity by the method Example Diamine used of UL-94 No. Maximum Average Ratlng (seconds) (seconds) CH3 ~ 8.6 4.6 V-O
:
26 H2N - ~ NH2 5.2 4.1 V-O
27 ~2N ~ N~2 9.1 2 V-l Example 28-31:
The procedure of Example 21 was repeated~ except varying combinations of phosphorus compounds and aromatic amino compound derivatives were used. The resultant resin compositions were tested for strengths and l'or inflammability by UL-94. The results are collectively shown in Table 6.
~, - 27 --:~
W ~ ~ ~ tq - o ~ co o 1- 3 x ~ W
~o~ o~ ~ ~o~ ' ~' o~ o~ o,~, o~ C~ ~. ' C~
~ ~ ~ ~ ~ D
W W ~ W ~D ~
g g g o ~ ~ :.
~ ~ X ~ ~ P~ :' ~
~ C~ . :~
~ ~CD~-~ I X ~o ~ ~Z :C o O ~ O r3 ¢ ~ roO w ,,- .- .
w ' - ~
. ~ u~ ~3 . ~ ~D
Ul Ul ~ \~109 ~ 3 ~.
IJ W ~ 1--~ tD ~q .:
.o o ~n o~ 3 ~
I`~ ~ .-. ~ ~
Ul 1'~ H
C~ ~ N
l-- ~ ~ ~ ~ O O
o ~n o o~ ~n ~o ~_ ~ .' 1-- ~ 3 cs H ~ :.
. . . . o 1' ~ ~ ~
co ~ ~ ~ C~n ~q ~ ~ P~
_~ I ~ ~
~n ~ ~ p~ O
~D C ~ 3 (D
. . . . O
~o w 1\) ~ 3 P' IJ- o ~q ~
~ ¢ ¢ ¢ ' ~ ' ~
~ I I I ~ P~
o 1- 1- o ~ ~ .' ;
.
: . :- . .
.:~ ,. .
Claims (40)
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 polyphenylene ether represented by the generic formula:
(A) (wherein, R1 and R2 each denote an alkyl group having 1 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 member selected from the group consisting of organic phosphorus compounds represented by the generic formula:
(B) (wherein, Ar denotes a trifunctional aromatic residue, Z
and Z' each denote a monofunctional residue selected from the class consisting of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms and a -NH2-yXy group, X denotes a residue of the formula (C) wherein, R3, R4 and R5 each denote a monofunctional residue selected from the class consisting of 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 denotes an integer having the value of 1 or 2 and y denotes an integer having the value of 0, 1 or 2).
(A) (wherein, R1 and R2 each denote an alkyl group having 1 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 member selected from the group consisting of organic phosphorus compounds represented by the generic formula:
(B) (wherein, Ar denotes a trifunctional aromatic residue, Z
and Z' each denote a monofunctional residue selected from the class consisting of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms and a -NH2-yXy group, X denotes a residue of the formula (C) wherein, R3, R4 and R5 each denote a monofunctional residue selected from the class consisting of 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 denotes an integer having the value of 1 or 2 and y denotes an integer having the value of 0, 1 or 2).
2. The resin composition according to Claim 1, wherein the residue (C) is such that all R3, R4 and R5 each are a hydrogen atom.
3. The resin composition according to Claim 1, wherein the residue (C) is such that R4 and R5 each are a chlorine atom and R3 is a hydrogen atom.
4. The resin composition according to Claim 1, wherein the residue (C) is such that all R3, R4 and R5 each are a t-butyl group.
5. The resin composition according to Claim 1, wherein the residue (C) is such that R5 is a phenyl group and R3 and R4 each are a hydrogen atom.
6. The resin composition according to Claim 1, wherein the residue (C) is such that R3 and R5 each are a methyl group and R4 is a t-butyl group.
7. The resin composition according to Claim 1, wherein the organic phosphorus compound (B) is such that Ar is a group of the formula and Z and Z' each are a -NH2-yXy group.
8. The resin composition according to Claim 1, wherein the organic phosphorus compound (B) is such that Ar is a group of the formula , Z is a phenyl group and Z' is -NH2-yXy group.
9. The resin composition according to Claim 1, wherein the organic phosphorus compound (B) is such that Ar is a group, Z is a hydrogen atom and Z' is a -NH2-yXy group.
10. The resin composition according to Claim 1, wherein the organic phosphorus compound (B) is such that Ar is a group, Z is a hydrogen atom and Z' is a-NH2-yXy group.
11. The resin composition according to Claim 1, wherein the organic phosphorus compound (B) is such that Ar is a group and Z and Z' each are a-NH2-yXy group.
12. The resin composition according to Claim 1, wherein the organic phosphorus compound (B) is such that Ar is a group, Z is a phenyl group and Z' is a -NH2-yXy group.
13. The resin composition according to Claim 1, wherein the organic phosphorus compound (B) is such that Ar is a group, Z is a methyl group and Z' is a -NH2-yXy group.
14. The resin composition according to Claim 1, wherein the organic phosphorus compound (B) is such that Ar is a group, Z a hydrogen atom and Z' is a -NH2-yXy group.
15. The resin composition according to Claim 1, wherein the organic phosphorus compound (B) is such that Ar is a group, Z is a hydrogen atom and Z' is a -NH2-yXy group.
16. The resin composition according to claim 1, wherein the organic phosphorus compound (B) is such that Ar is a group, Z is a hydrogen atom and Z' is a -NH2-yXy group.
17. The resin composition according to claim 1, wherein the organic phosphorus compound (B) is such that Ar is a group or group and Z and Z' each are a phenyl group.
18. The resin composition according to claim 1, wherein the organic phosphorus compound (B) is such that Ar is a group and Z' is a -NH2-yXy group.
19. The resin composition according to claim 1, wherein the organic phosphorus compound to be used is a mixture consisting of organic phosphorus compounds of the formula (B) wherein x is 1 or 2 and y is 0, 1 or 2.
20. The resin composition according to claim 1, wherein the polyphenylene ether (A) is such that R1 and R2 each are a methyl group.
21. A flame-retardant polyphenylene ether resin com-position, substantially comprising 80 to 98% by weight of a resin component and 2 to 20% by weight of at least one member selected from the group of organic phosphorus compounds represented by the generic formula:
(B) (wherein, Ar denotes a trifunctional aromatic residue, Z and Z' each denote a monofunctional residue selected from the class con-sisting of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms and a -NH2-yXy group, X denotes a residue of the formula (C) wherein R3, R4 and R5 each denote a monofunctional residue selected from the class consisting of 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 denotes an integer having the value of 1 or 2 and y denotes an integer having the value of 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 a vinyl compound copolymerizable therewith grafted onto 100 parts by weight of a polyphenylene ether represented by the generic formula:
(A) (wherein, R1 and R2 each denote an alkyl group having 1 to 4 carbon atoms and n denotes the degree of polymerization).
(B) (wherein, Ar denotes a trifunctional aromatic residue, Z and Z' each denote a monofunctional residue selected from the class con-sisting of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms and a -NH2-yXy group, X denotes a residue of the formula (C) wherein R3, R4 and R5 each denote a monofunctional residue selected from the class consisting of 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 denotes an integer having the value of 1 or 2 and y denotes an integer having the value of 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 a vinyl compound copolymerizable therewith grafted onto 100 parts by weight of a polyphenylene ether represented by the generic formula:
(A) (wherein, R1 and R2 each denote an alkyl group having 1 to 4 carbon atoms and n denotes the degree of polymerization).
22. The resin composition according to Claim 21, wherein the residue (C) is such that all R3, R4 and R5 each are a hydrogen atom.
23. The resin composition according to Claim 21, wherein the residue (C) is such that R4 and R5 each are a chlorine atom and R3 is a hydrogen atom.
24. The resin composition according to Claim 21, wherein the residue (C) is such that R3, R4 and R5 each are a t-butyl group.
25. The resin composition according to Claim 21, wherein the residue (C) is such that R5 is a phenyl group and R3 and R4 each are a hydrogen atom.
26. The resin composition according to Claim 21, wherein the residue (C) is such that R3 and R5 each are a methyl group and R4 is a t-butyl group.
27. The resin composition according to Claim 21, wherein the organic phosphorus compound (B) is such that Ar is a group of the formula and Z and Z' each are a -NH2-yXy group.
28. The resin composition according to Claim 21, wherein the organic phophorus compound (B) is such that Ar is a group of the formula , Z is a phenyl group and Z' is a -NH2-yXy group.
29. The resin composition according to Claim 21, wherein the organic phosphorus compound (B) is such that Ar is a group, Z is a hydrogen atom and Z' is a -NH2-yXy group.
30. The resin composition according to Claim 21, wherein the organic phosphorus compound (B) is such that Ar is a group, Z is a hydrogen atom and Z' is a -NH2-yXy group.
31. The resin composition according to Claim 21, wherein the organic phosphorus compound (B) is such that Ar is a group and Z and Z' each are a -NH2-yXy group.
32. The resin composition according to Claim 21, wherein the organic phosphorus compound (B) is such that Ar is a group, Z is a phenyl group and Z' is a -NH2-yXy group.
33. The resin composition according to Claim 21, wherein the organic phosphorus compound (B) is such that Ar is a group, Z is a methyl group and Z' is a -NH2-yXy group.
34. The resin composition according to Claim 21, wherein the organic phosphorus compound (B) is such that Ar is a group, Z is a hydrogen atom and Z' is a -NH2-yXy group.
35. The resin composition according to Claim 21, wherein the organic phosphorus compound (B) is such that Ar is a group, Z is a hydrogen atom and Z' is a -NH2-yXy group.
36. The resin composition according to Claim 21, wherein the organic phosphorus compound (B) is such that Ar is a group, Z is a hydrogen atom and Z' is a -NH2-yXy group.
37. The resin composition according to claim 21, wherein the organic phosphorus compound (B) is such that Ar is a group or group and Z and Z' each are a phenyl group.
38. The resin composition according to claim 21, wherein the organic phosphorus compound (B) is such that Ar is a group, Z is a phenyl group and Z' is a -NH2-yXy group.
39. The resin composition according to claim 21, wherein the organic phosphorus compound to be used is a mixture consisting of organic phosphorus compounds of the formula (B) wherein x is 1 or 2 and y is 0, 1 or 2.
40. The resin composition according to claim wherein the polyphenylene ether (A) is such that R1 and R2 each are a methyl group.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP78893/76 | 1976-07-05 | ||
| JP51078893A JPS5925822B2 (en) | 1976-07-05 | 1976-07-05 | Flame retardant polyphenylene ether resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1088238A true CA1088238A (en) | 1980-10-21 |
Family
ID=13674482
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA282,053A Expired CA1088238A (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) |
Families Citing this family (6)
| 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 |
| CH699311B1 (en) | 2008-08-14 | 2012-03-30 | Ems Patent Ag | A process for preparing dibenz [c, e] [1,2] oxaphosphorin-derivatives, amino-dibenz [c, e] [1,2] oxaphosphorin and the use thereof. |
| 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 FR FR7720623A patent/FR2357602A1/en active Granted
- 1977-07-05 CA CA282,053A patent/CA1088238A/en not_active Expired
- 1977-07-05 DE DE2730345A patent/DE2730345C3/en not_active Expired
- 1977-07-05 GB GB28102/77A patent/GB1567849A/en not_active Expired
- 1977-07-05 NL NL7707437.A patent/NL166271C/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| NL166271B (en) | 1981-02-16 |
| FR2357602B1 (en) | 1980-01-18 |
| NL7707437A (en) | 1978-01-09 |
| DE2730345B2 (en) | 1979-05-17 |
| JPS5925822B2 (en) | 1984-06-21 |
| FR2357602A1 (en) | 1978-02-03 |
| DE2730345A1 (en) | 1978-01-12 |
| DE2730345C3 (en) | 1980-01-10 |
| GB1567849A (en) | 1980-05-21 |
| NL166271C (en) | 1981-07-15 |
| JPS535253A (en) | 1978-01-18 |
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