CN100352852C - Flame retardant polymeric electrical parts - Google Patents

Flame retardant polymeric electrical parts Download PDF

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CN100352852C
CN100352852C CNB2003801016346A CN200380101634A CN100352852C CN 100352852 C CN100352852 C CN 100352852C CN B2003801016346 A CNB2003801016346 A CN B2003801016346A CN 200380101634 A CN200380101634 A CN 200380101634A CN 100352852 C CN100352852 C CN 100352852C
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butyl
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CN1705709A (en
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N·卡普里尼迪斯
N·莱利
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BASF Schweiz AG
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Ciba Spezialitaetenchemie Holding AG
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/30—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule
    • C08C19/34—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with oxygen or oxygen-containing groups
    • 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
    • C08K5/02—Halogenated hydrocarbons
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring

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Abstract

Disclosed is a flame retardant lighting assembly comprising thermoplastic insulation, plugs and sockets. The thermoplastic resin is for example polypropylene homopolymer and comprises a synergistic combination of an N-alkoxyoxy hindered amine and a conventional organohalogen flame retardant. The addition of low levels of acid scavengers such as hydrotalcites is advantageous.

Description

Flame retardant polymeric electrical parts
The present invention relates to flame retardant polymeric electrical/electronic unit, relate to the wire insulation, the plug and socket that are used to throw light on and use especially based on fire retardant polyolefin.
Background technology
USP5,096,950 discloses in polypropylene shared some NOR (N-alkoxyl group) bulky amine and has contained bromination Sb 2O 3Fire retardant.
USP5,393,812 disclose polyolefin compositions, and it is manufactured with flame retardant resistance by means of the mixture of halo alkyl phosphate or phosphonate fire retardant and the functional bulky amine of alkoxylamine.
USP5,844,026 disclose polyolefin compositions, and it comprises some NOR bulky amine and some conventional flame retardants.
USP6,117,995 disclose some N-alkoxyl group bulky amine can be as the fire retardant of organic polymer.
USP6,271,377 disclose polyolefin compositions, and it comprises N-hydroxy alkoxy base bulky amine and halogenated fire-retardants.
USP6,309,987 and suitable WO99/54530 instructed the polyolefine woven, flame resistant fabrics that comprises the N-alkoxylamine.
Be used for polyolefinic revolutionary UV stable fire retardant systems-R.Srinivasan, A.Gupta and D.Horsey, Int.Conf.Addit. polyolefine, 1998,69-83 has instructed the polyolefine of the conventional flame retardants that comprises some NOR bulky amine and halogen-containing and phosphorus.
Progress-the R.Srinivasan that is used for polyolefinic revolutionary fire retardant systems, B.Rotzinger, polyolefine 2000,2000 polyolefine international conferences, 571-581 has instructed to comprise some NOR bulky amine and bromination and the polyolefine phosphorated fire retardant.
N.Kaprinidis and R.King, the digest that on Society of Plastics Engineers network address, puts up, put up September calendar year 2001, the NOR bulky amine has been discussed as the purposes of fire retardant in polyolefine.This digest is a digest of submitting to the paper of polymer modifiers and additive branch, and this paper will be gone up in polyolefine 2002 meetings (Houston, TX, on February 24th, 2002) and propose.Network address is www.PMAD.org.
EP 0792911 A2 discloses polyolefin compositions, and it comprises the alkoxylamine official can bulky amine and three (three halogen amyl groups) phosphate flame retardant.
WO99/00450, the U.S. application number of common pending trial proposed and proposition on November 16th, 09/714,717,2000 on November 3rd, 09/502,239,1999, disclosed the purposes of some N-alkoxyl group bulky amine as fire retardant.
USP6,225,387 disclose the Organohalogen compounds flame retardant compositions.
Have been found that some combination of sterically hindered alkoxylamine stablizer and organic halogen fire retardant, it is effective especially providing flame retardant resistance for the plastics electric component of using for being used to throw light on.
Summary of the invention
Especially, the present invention relates to the flame retardant polymeric electrical parts composition, it comprises
(a) thermoplastic resin and
(b) synergistic mixt of the effective flame retardance volume of following component:
(i) at least a sterically hindered alkoxylamine stablizer and
(ii) at least a conventional organic halogen fire retardant.
The sterically hindered alkoxylamine stablizer of component (i)
Bulky amine of the present invention is for example monomeric compound or oligomeric or polymerizable compound.
The sterically hindered stablizer of component of the present invention (i) is well known in the art, and for example has following general formula:
Figure C20038010163400071
G wherein 1And G 2Being the alkyl of 1 to 8 carbon atom independently, perhaps is pentamethylene together,
Z 1And Z 2Each is methyl, perhaps Z naturally 1And Z 2Form the connection portion together, its can be in addition replaced by ester, ether, acid amides, amino, carboxyl or carbamate groups and
E is the alkoxyl group of 1-18 carbon atom, the cycloalkyloxy of a 5-12 carbon atom or the aralkoxy of 7-15 carbon atom, and perhaps E is-O-T-(OH) b,
T is the alkylidene group of 1 to 4 carbon atom of the ring alkenylene of the cycloalkylidene of the alkylidene group of 1 to 18 carbon atom of straight chain or side chain, 5 to 18 carbon atoms, 5 to 18 carbon atoms, the straight chain that replaces by phenyl or by the phenyl that is replaced by the alkyl group of one or two 1 to 4 carbon atom or side chain;
B is 1,2 or 3, and condition is that b can not surpass the carbonatoms among the T, and when b was 2 or 3, each oh group was connected to the different carbon atom of T.
E is for example alkoxyl group, cycloalkyloxy or aralkoxy.For example, E is methoxyl group, propoxy-, cyclohexyl oxygen base or octyloxy.
The sterically hindered stablizer of component of the present invention (i) is for example following general formula A-R:
Figure C20038010163400081
Figure C20038010163400091
Figure C20038010163400101
Figure C20038010163400111
Figure C20038010163400121
Wherein
E is the cycloalkyloxy of the alkoxyl group of 1 to 18 carbon atom, 5 to 12 carbon atoms or the aralkoxy of 7 to 15 carbon atoms, and perhaps E is-O-T-(OH) b,
T is the alkylidene group of 1 to 4 carbon atom of the ring alkenylene of the cycloalkylidene of the alkylidene group of 1 to 18 carbon atom of straight chain or side chain, 5 to 18 carbon atoms, 5 to 18 carbon atoms, the straight chain that replaces by phenyl or by the phenyl that is replaced by the alkyl group of one or two 1 to 4 carbon atom or side chain;
B is 1,2 or 3, and condition is that b can not surpass the carbonatoms among the T, and when b was 2 or 3, each oh group was connected to the different carbon atom of T;
R is hydrogen or methyl,
M is 1 to 4,
When m is 1,
R 2Be hydrogen, C 1-C 18Alkyl or the described alkyl, the C that are randomly inserted by one or more Sauerstoffatoms 2-C 12Alkenyl, C 6-C 10Aryl, C 7-C 18Aralkyl; glycidyl, aliphatic, alicyclic or aromatic carboxylic acid or carbamic unit price acyl group, for example acyl group of the aliphatic carboxylic acid of 2-18 C atom; have 5-12 C atom alicyclic carboxylic acid acyl group or have the aromatic carboxylic acid's of 7-15 C atom acyl group, perhaps
Figure C20038010163400131
Wherein x is 0 or 1,
Figure C20038010163400132
Wherein y is 2-4;
When m is 2,
R 2Be C 1-C 12Alkylidene group, C 4-C 12Alkenylene, xylylene, the divalence acyl group of aliphatic, alicyclic, araliphatic or aromatic dicarboxylic acid, the perhaps divalence acyl group of diamino acid, the acyl group that for example has the aliphatic dicarboxylic acid of 2-18 carbon atom, acyl group with alicyclic or aromatic dicarboxylic acid of 8-14 carbon atom perhaps has the aliphatic series of 8-14 carbon atom, the acyl group of alicyclic or aromatics diamino acid;
Figure C20038010163400141
Or
Figure C20038010163400142
Figure C20038010163400143
Wherein, D 1And D 2Be hydrogen independently, comprise the alkyl of maximum 8 carbon atoms, comprise 3, the aryl or the aralkyl of 5-di-tert-butyl-4-hydroxyl benzyl group, D 3Be hydrogen, perhaps comprise the alkyl or the kiki alkenyl group of maximum 18 carbon atoms, and d be 0-20;
When m is 3, R 2It is aliphatic series, unsaturated aliphatic, alicyclic or aromatic tricarboxylic acid's trivalent acyl group;
When m is 4, R 2Be saturated or unsaturated aliphatic or aromatic acid's tetravalence acyl group, comprise 1,2,3,4-BTCA, 1,2,3,4-but-2-ene tetracarboxylic acid and 1,2,3,5-and 1,2,4, the tetravalence acyl group of 5-pentane tetracarboxylic acid;
P is 1,2 or 3,
R 3Be hydrogen, C 1-C 12Alkyl, C 5-C 7Cycloalkyl, C 7-C 9Aralkyl, C 2-C 18Alkyloyl, C 3-C 5Enoyl-, perhaps benzoyl;
When p is 1,
R 4Be hydrogen, C 1-C 18Alkyl, C 5-C 7Cycloalkyl, C 2-C 8Alkenyl, they are unsubstituted or are replaced by cyano group, carbonyl or urea groups, aryl, aralkyl, perhaps it is a glycidyl, general formula-CH 2The group of-CH (OH)-Z, perhaps general formula-CO-Z or-group of CONH-Z, wherein Z is hydrogen, methyl or phenyl; The perhaps group of following general formula
Figure C20038010163400151
Or
Wherein h is 0 or 1,
R 3And R 4Together, when p is 1, can be the alkylidene group or the 2-oxo polyalkylene of 4 to 6 carbon atoms, aliphatic series or aromatics 1,2-or 1, the ring-type acyl group of 3-dicarboxylic acid,
When p is 2,
R 4Be Direct Bonding or C 1-C 12Alkylidene group, C 6-C 12Arylidene, xylylene ,-CH 2CH (OH)-CH 2Group or group-CH 2-CH (OH)-CH 2-O-X-O-CH 2-CH (OH)-CH 2-, wherein X is C 2-C 10Alkylidene group, C 6-C 15Arylidene or C 6-C 12Cycloalkylidene; Perhaps, if R 3Not alkanol, enoyl-or benzoyl, R 4Can also be the divalence acyl group of aliphatic, alicyclic or aromatic dicarboxylic acid or diamino acid, perhaps can be group-CO-; Perhaps
R 4Be
Figure C20038010163400161
Wherein, T 8And T 9Be hydrogen independently, the alkyl of 1 to 18 carbon atom, perhaps T 8And T 9Be alkylidene group or 3-oxa-pentamethylene, for example T of 4 to 6 carbon atoms together 8And T 9Be 3-oxa-pentamethylene together;
When p is 3,
R 4Be 2,4, the 6-triazinyl,
N is 1 or 2,
When n is 1,
R 5And R ' 5Be C independently 1-C 12Alkyl, C 2-C 12Alkenyl, C 7-C 12Aralkyl, perhaps R 5Or hydrogen, perhaps R 5And R ' 5Be C together 2-C 8Alkylidene group or hydroxy alkylidene or C 4-C 22The acyloxy alkylidene group;
When n is 2,
R 5And R ' 5Be (CH together 2) 2C (CH 2-) 2
R 6Be hydrogen, C 1-C 12Alkyl, allyl group, benzyl, glycidyl or C 2-C 6Alkoxyalkyl;
When n is 1,
R 7Be hydrogen, C 1-C 12Alkyl, C 3-C 5Alkenyl, C 7-C 9Aralkyl, C 5-C 7Cycloalkyl, C 2-C 4Hydroxyalkyl, C 2-C 6Alkoxyalkyl, C 6-C 10Aryl, glycidyl, general formula-(CH 2) tThe group of-COO-Q or general formula-(CH 2) tThe group of-O-CO-Q, wherein t be 1 or 2 and Q be C 1-C 4Alkyl or phenyl; Perhaps
When n is 2,
R 7Be C 2-C 12Alkylidene group, C 6-C 12Arylidene, group-CH 2CH (OH)-CH 2-O-X-O-CH 2-CH (OH)-CH 2-, wherein X is C 2-C 10Alkylidene group, C 6-C 15Arylidene or C 6-C 12Cycloalkylidene, perhaps group CH 2CH (OZ ') CH 2-(OCH 2-CH (OZ ') CH 2) 2-, wherein Z ' is a hydrogen, C 1-C 18Alkyl, allyl group, benzyl, C 2-C 12Alkyloyl or benzoyl;
Q 1Be-N (R 8)-or-O-; E 7Be C 1-C 3Alkylidene group, group-CH 2-CH (R 9)-O-, wherein R 9Be hydrogen, methyl or phenyl, group-(CH 2) 3-NH-or Direct Bonding;
R 10Be hydrogen or C 1-C 18Alkyl, R 8Be hydrogen, C 1-C 18Alkyl, C 5-C 7Cycloalkyl, C 7-C 12Aralkyl, cyanoethyl, C 6-C 10Aryl, group-CH 2-CH (R 9)-OH, wherein R 9Has the meaning that limits above; The group of following general formula
The perhaps group of following general formula
Figure C20038010163400172
G wherein 4Be C 2-C 6Alkylidene group or C 6-C 12Arylidene; Perhaps R 8Be group-E 7-CO-NH-CH 2-OR 10
General formula F represents the repeated structural unit of polymkeric substance, wherein T 3Being ethylidene or propylene, is the repeated structural unit derived from alpha-olefin copolymer and alkyl acrylate or alkyl methacrylate; The multipolymer of ethene and ethyl propenoate for example, and wherein k is 2 to 100;
When p is 1 or 2, T 4Have and R 4Identical meaning,
T 5Be methyl,
T 6Be methyl or ethyl, perhaps T 5And T 6Be tetramethylene or pentamethylene, for example T together 5And T 6Each is methyl naturally,
M and Y are methylene radical or carbonyl independently, and T 4Be ethylidene, wherein n is 2;
T 7With R 7Identical, and T 7Be octamethylene for example, wherein n is 2,
T 10And T 11Be the alkylidene group of 2 to 12 carbon atoms, perhaps T independently 11Be
Figure C20038010163400181
T 12Be piperazinyl,
-NR 11-(CH 2) o-NR 11-or
Figure C20038010163400182
Wherein, R 11With R 3Identical, perhaps still
Figure C20038010163400183
A, b and c be independently 2 or 3 and f be 0 or 1, for example a and c each naturally 3, b be 2 and f be 1; And
E is 2,3 or 4, for example 4;
T 13With R 2Identical, condition is, when n is 1, and T 13Can not be hydrogen;
E 1And E 2Be different, each naturally-CO-or-N (E 5)-, be E wherein 5Be hydrogen, C 1-C 12Alkyl or C 4-C 22Alkoxy carbonyl alkyl, for example E 1Be-CO-, and E 2Be-N (E 5)-,
E 3Be hydrogen, the alkyl of 1 to 30 carbon atom, phenyl, naphthyl is by chlorine or by the described phenyl or the described naphthyl of the replacement of the alkyl of 1 to 4 carbon atom, the perhaps phenylalkyl of 7 to 12 carbon atoms, perhaps by the described phenylalkyl of the alkyl of 1 to 4 carbon atom replacement
E 4Be hydrogen, the alkyl of 1 to 30 carbon atom, phenyl, the phenylalkyl of naphthyl or 7 to 12 carbon atoms, perhaps
E 3And E 4Be the polymethylene of 4 to 17 carbon atoms together, perhaps by for example methyl substituted described polymethylene of the alkyl group of maximum four 1 to 4 carbon atoms,
E 6Be aliphatic series or aromatics quaternary groups,
When m is 1, the R of general formula (N) 2Be to limit previously;
G 1Be Direct Bonding, C 1-C 12Alkylidene group, phenylene or-NH-G '-NH, wherein G ' is C 1-C 12Alkylidene group; Perhaps
Wherein the bulky amine compound is the compound of general formula I, II, III, IV, V, VI, VII, VIII, IX, X or XI
Figure C20038010163400191
Figure C20038010163400201
Figure C20038010163400221
E wherein 1, E 2, E 3And E 4Be the alkyl of 1 to 4 carbon atom, perhaps E independently 1And E 2Be the alkyl and the E of 1 to 4 carbon atom independently 3And E 4Be pentamethylene, perhaps E altogether 1And E 2And E 3And E 4Be pentamethylene separately altogether,
R 1It is the alkyl of 1 to 18 carbon atom, the cycloalkyl of 5 to 12 carbon atoms, two ring or tricyclic hydrocarbon groups of 7 to 12 carbon atoms, the phenylalkyl of 7 to 15 carbon atoms, the aryl of 6 to 10 carbon atoms or the described aryl that is replaced by one to three alkyl with 1 to 8 carbon atom
R 2Be the straight or branched alkyl of hydrogen or 1 to 12 carbon atom,
R 3Be the alkylidene group of 1 to 8 carbon atom, perhaps R 3Be-CO--CO-R 4-,-CONR 2-, perhaps-CO-NR 2-R 4-
R 4Be the alkylidene group of 1 to 8 carbon atom,
R 5Be hydrogen, the straight or branched alkyl of 1 to 12 carbon atom, perhaps
Perhaps work as R 4When being ethylidene, two R 5Methyl substituents can connect by Direct Bonding, makes triazine bridge linkage group-N (R 5)-R 4-N (R 5)-be piperazine-1,4-two base section,
R 6Be the alkylidene group of 2 to 8 carbon atoms, perhaps R 6Be
Condition is to work as R 6When being above-described structure, Y is not-OH,
A is-O-or-NR 7-, R wherein 7Be hydrogen, the straight chain or the branched-chain alkyl of 1 to 12 carbon atom, perhaps R 7Be
Figure C20038010163400233
T is a phenoxy group, by the phenoxy group that one or two alkyl group with 1 to 4 carbon atom replaces, the alkoxyl group of 1 to 8 carbon atom or-N (R 2) 2, condition is R 2Be not hydrogen, perhaps T is
X is-NH 2,-NCO ,-OH ,-the O-glycidyl, perhaps-NHNH 2And
Y is-OH ,-NH 2,-NHR 2, R wherein 2Not hydrogen; Perhaps Y be-NCO ,-COOH, Oxyranyle ,-the O-glycidyl or-Si (OR 2) 3Perhaps make up R 3-Y-is-CH 2CH (OH) R 2, R wherein 2Be alkyl or the described alkyl that inserted by one to four Sauerstoffatom, perhaps R 3-Y-is-CH 2OR 2Perhaps
Wherein the bulky amine compound is following mixture: N, N ', N " three { 2, two [(1--oxyl-2,2,6,6-tetramethyl piperidine-4-yl) the alkylamino]-s-triazine-6-yls of 4-}-3,3 '-ethylene imino-dipropylamine; N, N ', N " three { 2, two [(1--oxyl-2,2,6,6-tetramethyl piperidine-4-yl) the alkylamino]-s-triazine-6-yls of 4-}-3,3 '-ethylene imino-dipropylamine, and the derivative of the bridge joint of describing by general formula I, II, IIA and III
R 1NH-CH 2CH 2CH 2NR 2CH 2CH 2NR 3CH 2CH 2CH 2NHR 4 (I)
T-E 1-T 1 (II)
T-E 1 (IIA)
G-E 1-G 1-E 1-G 2 (III)
Wherein, in the tetramine of formula I,
R 1And R 2Be s-triazine part E; And R 3And R 4One of be s-triazine part E, R 3Perhaps R 4Another be hydrogen,
E is
Figure C20038010163400251
R is methyl, propyl group, cyclohexyl or octyl group, cyclohexyl for example,
R 5Be the alkyl of 1 to 12 carbon atom, normal-butyl for example,
Wherein in the compound of general formula I I or IIA, when R is propyl group, cyclohexyl or octyl group,
T and T 1Each is naturally by R 1-R 4The tetramine that replaces, R 1-R 4As limiting, wherein about general formula I
(1) in every kind of tetramine, one of s-triazine part E is by group E 1Substitute, it is at two tetramine T and T 1Between form bridge joint,
E 1Be
Figure C20038010163400252
Perhaps
(2) E 1Can have two not ends in same tetramine T, as in general formula I IA, wherein two of tetramine E parts are by an E 1Group substitutes, perhaps
(3) three s-triazine substituting groups of all of tetramine T can be E 1, make an E connect T and T 1, and second E 1In tetramine T, have two not ends,
L is propane two bases, hexanaphthene two bases or octane two bases;
Wherein, in the compound of general formula III
G, G 1And G 2Each is naturally by R 1-R 4The tetramine that replaces, R 1-R 4As limiting, except G and G about general formula I 2Has one separately by E 1Alternate s-triazine part E, and G 1Have two by E 1Alternate triazine part E makes at G and G 1Between have bridge joint and at G 1And G 2Between have second bridge joint;
This mixture is normal 2 by two to four, the N of two [(1--oxyl-2,2,6,6-tetramethyl piperidine-4-yl) butyl amino]-6-chloro-s-triazines of 4-and monovalent, and N '-two (3-aminopropyl) reacting ethylenediamine prepares;
Perhaps this bulky amine is the compound of general formula III b
Figure C20038010163400261
Wherein subscript n is 1 to 15;
R 12Be C 2-C 12Alkylidene group, C 4-C 12Alkenylene, C 5-C 7Cycloalkylidene, C 5-C 7Cycloalkylidene-two (C 1-C 4Alkylidene group), C 1-C 4Alkylidene group two (C 5-C 7Cycloalkylidene), phenylene two (C 1-C 4Alkylidene group) or by 1,4-piperazine two bases ,-O-or＞N-X 1The C that inserts 4-C 12Alkylidene group, wherein X 1Be C 1-C 12Acyl group or (C 1-C 12Alkoxyl group) carbonyl perhaps has the following R that provides 14Definition a kind of, except hydrogen; Perhaps R 12It is the group of general formula (Ib ') or (Ic ');
X wherein 2Be C 1-C 18Alkyl, C 5-C 12Cycloalkyl, it is unsubstituted or by 1,2 or 3 C 1-C 4Alkyl replaces; Phenyl, it is unsubstituted or by 1,2 or 3 C 1-C 4Alkyl or C 1-C 4Alkoxyl group replaces; C 7-C 9Phenylalkyl, its be unsubstituted or on phenyl by 1,2 or 3 C 1-C 4Alkyl replaces; With
Radicals X 3Be C independently of each other 2-C 12Alkylidene group;
R 13, R 14And R 15, it is identical or different, is hydrogen, C 1-C 18Alkyl, C 5-C 12Cycloalkyl, it is unsubstituted or by 1,2 or 3 C 1-C 4Alkyl replaces; C 3-C 18Alkenyl, phenyl, it is unsubstituted or by 1,2 or 3 C 1-C 4Alkyl or C 1-C 4Alkoxyl group replaces; C 7-C 9Phenylalkyl, its be unsubstituted or on phenyl by 1,2 or 3 C 1-C 4Alkyl replaces; Tetrahydrofurfuryl or C 2-C 4Alkyl, it replaces at 2,3 or 4 following groups of quilt :-OH, C 1-C 8Alkoxyl group, two (C 1-C 4Alkyl) group of amino or general formula (Ie ');
Figure C20038010163400272
Wherein Y is-O-,-CH 2-,-CH 2CH 2-or＞N-CH3,
Perhaps-N (R 14) (R 15) be the group of other general formula (Ie ');
Group A is-OR independently of each other 13,-N (R 14) (R 15) or the group of general formula (IIId);
Figure C20038010163400273
X is-O-or＞N-R 16
R 16Be hydrogen, C 1-C 18Alkyl, C 3-C 18Alkenyl, C 5-C 12Cycloalkyl, it is unsubstituted or by 1,2 or 3 C 1-C 4Alkyl replaces; C 7-C 9Phenylalkyl, its be unsubstituted or on phenyl by 1,2 or 3 C 1-C 4Alkyl replaces; Tetrahydrofurfuryl, the group of general formula (IIIf),
Figure C20038010163400281
Perhaps C 2-C 4Alkyl, it replaces at 2,3 or 4 following groups of quilt :-OH, C 1-C 8Alkoxyl group, two (C 1-C 4Alkyl) group of amino or general formula (Ie ');
R 11Have for R 16The definition that provides a kind of; With
Group B has a kind of of the definition that provides for A independently of each other.
Alkyl is straight chain or side chain, and is for example methyl, ethyl, n-propyl, normal-butyl, sec-butyl, the tertiary butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, positive decyl, positive undecyl, dodecyl, n-tridecane base, n-tetradecane base, n-hexadecyl or Octadecane base.
Group of naphthene base comprises cyclopentyl and cyclohexyl; Typical cycloalkenyl group comprises cyclohexenyl; Simultaneously typical aralkyl comprises benzyl, Alpha-Methyl-benzyl, α, α-Er Jiajibianji or styroyl.
Alkoxyl group and cycloalkyloxy comprise corresponding alkyl and group of naphthene base.
If R 2Be the unit price acyl group of carboxylic acid, it is the acyl group of acetate, stearic acid, Whitfield's ointment, phenylformic acid or β-(3,5-di-t-butyl-4-hydroxyphenyl) propionic acid for example.
If R 2It is the divalence acyl group of dicarboxylic acid; it is for example following sour acyl group: oxalic acid, hexanodioic acid, succsinic acid, suberic acid, sebacic acid, phthalic acid, dibutyl propanedioic acid, dibenzyl propanedioic acid or butyl-(3; 5-two-tertiary butyl-4-hydroxy benzyl)-propanedioic acid; perhaps double-heptene dicarboxylic acid, wherein succsinic acid, sebacic acid, phthalic acid and m-phthalic acid are special examples.
If R 2Be the divalence acyl group of diamino acid, it for example is hexa-methylene diamino formic acid or 2, the acyl group of 4-tolylene diamino acid.
The steric hindrance alkoxylamine stablizer of component (i) is well-known in the art, also claims N-alkoxyl group bulky amine and NOR bulky amine or NOR hindered amine as light stabilizer or NORHALS.
They are disclosed in for example USP5, and 004,770,5,204,473,5,096,950,5,300,544,5,112,890,5,124,378,5,145,893,5,216,156,5,844,026,6,117,995,6,271,377, with U. S. application series number 09/505,529 (submission on February 17th, 2000), 09/794,710 (submissions on February 27 calendar year 2001), 09/714,717 (submission on November 16th, 2000), 09/502,239 (submission on November 3rd, 1999) and 60/312,517 (submission on August 15 calendar year 2001).The relevant of these patents and application is disclosed in this adding as a reference.
Above-cited USP6,271,377 and U. S. application series number 09/505,529 (proposition on February 17th, 2000) and 09/794,710 (proposition on February 27 calendar year 2001) steric hindrance hydroxy alkoxy base amine stabiliser is disclosed.For purpose of the present invention, steric hindrance hydroxy alkoxy base amine stabiliser is considered to the subclass of steric hindrance alkoxylamine stablizer and is the part of component of the present invention (i).Steric hindrance hydroxy alkoxy base amine stabiliser also claims N-hydroxy alkoxy base bulky amine, or NORol HALS.
The bulky amine that is fit to of component (i) for example comprises:
NOR1 1-cyclohexyl oxygen base-2,2,6,6-tetramethyl--4-octadecyl amino piperidine;
Two (1-octyloxy-2,2,6, the 6-tetramethyl piperidine-4-yl) sebates of NOR2;
NOR3 2, two [(1-cyclohexyl oxygen base-2,2,6,6-tetramethyl piperidine-4-yl) the butyl amino]-6-(2-hydroxyl-ethylamino-s-s-triazine of 4-;
NOR4 2, two [(1-cyclohexyl oxygen base-2,2,6,6-tetramethyl piperidine-4-yl) butyl the amino]-6-chloro-s-triazines of 4-;
NOR5 1-(2-hydroxy-2-methyl propoxy-)-4-hydroxyl-2,2,6, the 6-tetramethyl piperidine;
NOR6 1-(2-hydroxy-2-methyl propoxy-)-4-oxo-2,2,6, the 6-tetramethyl piperidine;
NOR7 1-(2-hydroxy-2-methyl propoxy-)-4-octadecane acyl-oxygen base-2,2,6, the 6-tetramethyl piperidine;
Two (1-(2-hydroxy-2-methyl propoxy-)-2,2,6, the 6-tetramethyl piperidine-4-yl) sebates of NOR8;
Two (1-(2-hydroxy-2-methyl propoxy-)-2,2,6, the 6-tetramethyl piperidine-4-yl) adipic acid esters of NOR9;
NOR10 2,4-pair N-[1-(2-hydroxy-2-methyl propoxy-)-2,2,6,6-tetramethyl piperidine-4-yl]-N-butyl amino]-6-(2-hydroxyethyl amino)-s-triazine;
NOR11 2, two [(1-cyclohexyl oxygen base-2,2,6,6-tetramethyl piperidine-4-yl) butyl amino]-6-chloro-s-triazine and the N of 4-, N '-two (3-aminopropyl) quadrol) reaction product [CAS number of registration 191680-81-6]; With
The compound of the following general formula of NOR12
Wherein, n is 1 to 15.Compound N OR12 is disclosed in U.S. Patent number 6,117, among 995 the embodiment 2.
Two (1-cyclohexyl oxygen base-2,2,6, the 6-tetramethyl piperidine-4-yl) adipic acid esters of NOR13;
For example, steric hindrance alkoxylamine of the present invention is a steric hindrance cyclohexyl oxygen base amine.
N-cyclohexyl oxygen base bulky amine for example is selected from
(a) mixture of the compound of general formula I, II, IIA and III, wherein R is a cyclohexyl;
(b) 1-cyclohexyl oxygen base-2,2,6,6-tetramethyl--4-octadecyl amino piperidine;
(c) 2, two [(1-cyclohexyl oxygen base-2,2,6,6-tetramethyl piperidine-4-yl) the butyl amino]-6-(2-hydroxyl-ethylamino-s-s-triazine of 4-;
(d) two (1-cyclohexyl oxygen base-2,2,6,6-tetramethyl piperidine-4-yl) adipic acid ester;
(e) oligomeric compound, it is 4,4 '-hexa-methylene-two (amino-2,2,6, the 6-tetramethyl piperidine) and 2,4-two chloro-6-[(1-cyclohexyl oxygen bases-2,2,6,6-tetramethyl piperidine-4-yl) butyl amino]-condensation product of s-triazine, with 2-chloro-4, two (the dibutylamino)-s-triazine end-blockings of 6-; With
(f) 2, two [(1-cyclohexyl oxygen base-2,2,6,6-tetramethyl piperidine-4-yl) butyl the amino]-6-chloro-s-triazines of 4-.
The organic halogen fire retardant
The organic halogen fire retardant for example is:
Chlorine alkyl phosphate (ANTIBLAZE  AB-100, Albright ﹠amp; Wilson; FYROL  FR-2, Akzo Nobel),
Three (2-chloroethyl) phosphoric acid ester,
Many bromos phenyl ether (DE-60F, Great Lakes Corp.),
Decabromodiphynly oxide (DBDPO; SAYTEX  102E),
Three [3-bromo-2, two (brooethyl) propyl group of 2-] phosphoric acid ester (PB370 , FMC Corp.),
Three (2, the 3-dibromopropyl) phosphoric acid ester,
Three (2,3-two chloropropyls) phosphoric acid ester,
Chlorendic acid,
Tetrachlorophthalic acid,
Tetrabromophthalate,
It is two-(N, N '-hydroxyethyl) tetrachlorobenzene diamines,
It is poly--β-chloroethyl tri methylene phosphonic acid ester mixture,
Two (2,3-dibromopropyl ether) of tetrabromo-bisphenol (PE68),
Brominated epoxy resin,
Ethylidene-two (tetrabromo phthalimide) (SAYTEX  BT-93),
Two (hexachlorocyclopentadiene base) cyclooctane (DECLORANE PLUS ),
Clorafin,
Octabromodiphenyl ether,
The hexachlorocyclopentadiene derivative,
1, two (tribromophenoxy) ethane (FF680) of 2-
Tetrabromo-bisphenol (SAYTEX  RB100),
Ethylenebis-(two bromo-norcamphane dicarboximides) (SAYTEX  RN-451),
It is two-(hexachlorocyclopentadiene base) cyclooctane,
PTFE
Three-(2, the 3-dibromopropyl)-isocyanuric acid ester and
Ethylidene-two-tetrabromo phthalimide.
For example, the organic halogen fire retardant is the organic bromine fire retardant, is preferably selected from
Polybromodiphenyl ether,
Decabromodiphynly oxide,
Three [3-bromo-2, two (brooethyl) propyl group of 2-] phosphoric acid ester,
Three (2, the 3-dibromopropyl) phosphoric acid ester,
Tetrabromophthalate,
Two (2,3-dibromopropyl ether) of tetrabromo-bisphenol,
Brominated epoxy resin,
Ethylidene-two (tetrabromo phthalimide),
Octabromodiphenyl ether,
1, two (tribromophenoxy) ethane of 2-,
Tetrabromo-bisphenol,
Ethylenebis-(two bromo-norcamphane dicarboximides),
Three-(2, the 3-dibromopropyl)-isocyanuric acid ester and
Ethylidene-two-tetrabromo phthalimide.
Composition equally preferably, wherein the organic halogen fire retardant is bromination alkyl phosphate or phosphonic acid ester, for example three [3-bromo-2, two (monobromethane) propyl group of 2-] phosphoric acid ester (PB370 ).
Can be used for halogenated flame of the present invention and can be selected from organic halogenated aromatic compounds, for example halogeno-benzene, biphenyl, phenol, ether or its ester, bis-phenol, phenyl ether, aromatic carboxylic acid or polyprotonic acid, its acid anhydrides, acid amides or imide; Organic alicyclic or how alicyclic halogenated compound; With organic aliphatic halogenated compound, for example halogenated alkane, oligomeric or polymkeric substance, alkyl phosphate or alkyl isocyanide urea acid esters.These components are as known in the art to a great extent, reference example such as U.S. Patent number 4,579,906 (for example the 3rd hurdle 30-41 is capable), 5,393,812; Also with reference to the plastics additive handbook, H.Zweifel edits, and the 5th edition, Hanser Publ., Munich, 2001, the 681-698 pages or leaves.
Thermoplastic resin
The thermoplastic resin of component (a) is any polymkeric substance in the various polymer types, comprises polyolefine, polystyrene type and PVC.For example, thermoplastic resin can be selected from following resin: polyolefine, thermoplastic olefin, styrenic polymer and multipolymer, ABS and comprise the polymkeric substance of heteroatoms, two key or aromatic ring.Specific embodiment is that wherein component (a) is the embodiment of polypropylene, polyethylene, thermoplastic olefin (TPO), ABS or polystyrene.
For example, thermoplastic resin is selected from following resin: polyolefine, thermoplastic olefin, styrenic polymer and multipolymer and ABS.
Another embodiment of the invention is that wherein thermoplastic resin is selected from polypropylene, polyethylene, thermoplastic olefin (TPO), ABS and polystyrene.
For example, thermoplastic resin is polypropylene, polyethylene or thermoplastic olefin (TPO).The organic polymer of component (a) is a thermoplastic polymer for example, and polyolefine for example is as polyethylene, polypropylene or its multipolymer.Thermoplastic polymer is a polypropylene for example.
For example, the thermoplastic resin of component (a) is:
1, the polymkeric substance of monoolefine and diolefine, polypropylene for example, polyisobutene, poly-but-1-ene, poly--4-methylpent-1-alkene, polyvinyl eyclohexane, polyisoprene or polyhutadiene, and the cycloolefin polymkeric substance of cyclopentenes or norbornylene for example, (randomly can be crosslinked) polyethylene is high density polyethylene(HDPE) (HDPE) for example, high-density and High molecular weight polyethylene (HDPE-HMW), high-density and ultrahigh molecular weight polyethylene(UHMWPE) (HDPE-UHMW), medium-density polyethylene (MDPE), new LDPE (film grade) (LDPE), LLDPE (LLDPE), (VLDPE) and (ULDPE).
Polyolefine, i.e. for example polyethylene and polypropylene of the polymkeric substance of the monoolefine enumerated of the preceding paragraph, can be with the especially following method preparation of different methods:
A) radical polymerization (usually under high pressure and high temperature)
B) catalyzed polymerization of use catalyzer, this catalyzer contains a kind of or more than a kind of metal of periodic table of chemical element IVb family, Vb family, VIb family or VIII family usually.These metals have one or a more than part usually, typically are oxide compound, halogenide, alkoxide, ester, ether, amine, alkyl, alkenyl and/or aryl, and these can be π-coordination or σ-coordinate.These metal complexs can be free form, also can be fixed on the base material, typically are fixed on active magnesium chloride, titanium chloride (III), aluminum oxide or the silicon oxide.These catalyzer can dissolve in or be insoluble in the polymerisation medium.These catalyzer can be used for polymerization with itself, also can use further activator, metal alkyl, metal hydride, metal alkyl halides, metal alkyl oxide compound or metal alkyl oxygen alkane typically, described metal is the element of periodic table of chemical element Ia family, IIa family and/or IIIa family.These activators can carry out modification with further ester, ether, amine or silyl ether easily.These catalyst systems are commonly referred to Phillips, Standard Oil Indiana, Ziegler (Natta), TNZ (DuPont), metallocenes or single site catalysts (SSC).
2, the 1st mixture of polymers of mentioning, for example mixture of the mixture of polypropylene and polyisobutene, polypropylene and polyethylene (for example PP/HDPE, PP/LDPE) and dissimilar polyethylene (for example LDPE/HDPE).
3, monoolefine and diolefine each other multipolymer or with the multipolymer of other vinyl monomer, ethylene/propene copolymer for example, LLDPE (LLDPE) and with the mixture of new LDPE (film grade) (LDPE), propylene/but-1-ene multipolymer, propylene/isobutylene copolymers, ethene/but-1-ene multipolymer, the ethylene/hexene multipolymer, ethene/methylpentene multipolymer, ethene/heptene multipolymer, ethylene/octene, ethylene/vinyl basic ring hexane multipolymer, ethene/cyclic olefine copolymer (for example ethene/norbornylene such as COC), ethene/1-olefin copolymer, wherein 1-alkene is that original position takes place; Propylene/butadienecopolymer, iso-butylene/isoprene copolymer, ethylene/vinyl basic ring hexene copolymer, ethylene/acrylic acid alkyl ester copolymer, ethylene/methacrylic acid alkyl ester copolymer, ethylene or ethylene/acrylic acid copolymer and salt (iolon) thereof and ethene and propylene and a kind of diene be the terpolymer of hexadiene, dicyclopentadiene or inclined to one side ethylidene norbornene for example; Such multipolymer each other mixture and with above first mixture of polymers of mentioning, for example polypropylene/ethylene-propylene copolymer, LDPE/ vinyl-vinyl acetate copolymer (EVA), LDPE/ ethylene-acrylic acid copolymer (EAA), LLDPE/EVA, LLDPE/EAA and alternately or atactic polyolefin/carbon monoxide multipolymer and with other polymkeric substance mixture of polymeric amide for example.
4, hydrocarbon resin (for example C5-C9) comprises the mixture of its hydrogenation modification thing (for example tackifier) and polyolefine and starch.
The 1st to the 4th homopolymer and multipolymer can have any three-dimensional arrangement, comprise syndiotaxy, isotaxy, half isotaxy or random, for example unregulated polymer.Also comprise stereoblock polymer.
5, polystyrene, poly-(p-methylstyrene), poly-(alpha-methyl styrene).
6, from comprising vinylbenzene, alpha-methyl styrene, all isomer of Vinyl toluene are especially to Vinyl toluene, all isomer of ethyl styrene, propylstyrene, vinyl biphenyl, vinyl naphthalene and vinyl anthracene are at interior vinyl aromatic monomers deutero-aromatic series homopolymer and multipolymer, and composition thereof.Homopolymer and multipolymer can have any three-dimensional arrangement, comprise syndiotaxy, isotaxy, half isotaxy or random; Unregulated polymer for example.Also comprise stereoblock polymer.
A) comprise above-mentioned vinyl aromatic monomers and the multipolymer that is selected from the comonomer of ethene, propylene, diene, nitrile, acid, maleic anhydride, maleimide, vinyl-acetic ester and vinylchlorid or acrylic acid derivative and composition thereof, for example phenylethylene/butadiene, styrene/acrylonitrile, styrene/ethylene (terpolymer), styrene/methacrylic acid alkane ester, phenylethylene/butadiene/alkyl acrylate, phenylethylene/butadiene/alkyl methacrylate, phenylethylene/maleic anhydride, styrene/acrylonitrile/methyl acrylate; High impact strength of styrene multipolymer and another kind of polymkeric substance be the mixture of polyacrylic ester, diene polymer or ethylene/propene/diene terpolymer for example; With cinnamic segmented copolymer for example styrene/butadiene/styrene, styrene/isoprene/styrene, styrene/ethylene/butylene/styrene or styrene/ethylene/propylene/styrene.
B) from above-mentioned hydrogenation of polymer deutero-hydrogenation aromatic polymer, especially comprise by make the random polystyrene hydrogenation preparing, abbreviate the poly-cyclohexyl ethene (PCHE) of polyvinyl eyclohexane (PVCH) as usually.
C) from above 6a) a hydrogenation of polymer deutero-hydrogenation aromatic polymer of mentioning.
Homopolymer and multipolymer can have any three-dimensional arrangement, comprise syndiotaxy, isotaxy, half isotaxy or random, for example unregulated polymer.Also comprise stereoblock polymer.
7, the vinyl aromatic monomers graft copolymer of vinylbenzene or alpha-methyl styrene for example, for example styrene-grafted in polyhutadiene, styrene-grafted in Polybutadiene-styrene or polybutadiene-acrylonitrile copolymer; Vinylbenzene and vinyl cyanide (or methacrylonitrile) graft on polyhutadiene; Vinylbenzene, vinyl cyanide and methyl methacrylate-grafted are in polyhutadiene; Vinylbenzene and maleic anhydride graft are in polyhutadiene; Vinylbenzene, vinyl cyanide and maleic anhydride or maleimide graft on polyhutadiene; Vinylbenzene and maleimide graft on polyhutadiene; Vinylbenzene and alkyl acrylate or alkyl methacrylate graft on polyhutadiene; Vinylbenzene and acrylonitrile grafting are in ethylene/propene/diene terpolymer; Vinylbenzene and acrylonitrile grafting are in polyacrylic acid alkane ester or polymethyl acrylic acid alkane ester; Vinylbenzene and acrylonitrile grafting are in acrylate/butadiene copolymers; With and with the mixture of the 6th multipolymer of enumerating, for example be called the copolymer mixture of ABS, MBS, ASA or AES polymkeric substance.
8, polymer containing halogen, for example multipolymer, Epicholorohydrin homopolymer and the multipolymer of the chlorination of sovprene, chlorinated rubber, isobutylene-isoprene and brominated copolymer (halobutyl rubber), chlorination or sulphur chlorinatedpolyethylene, ethene and ethylene chloride, the polymkeric substance of especially halogen-containing vinyl compound, for example polyvinyl chloride, poly-inclined to one side dioxy ethene, fluorinated ethylene propylene, poly(vinylidene fluoride), with and multipolymer for example vinylchlorid/vinylidene chloride, vinylchlorid/vinyl-acetic ester or vinylidene chloride/vinyl acetate copolymer.
9, from α, beta-unsaturated acid and derivative derived polymers thereof, for example polyacrylic ester and polymethacrylate; Polymethylmethacrylate, polyacrylamide and polyacrylonitrile carry out impact-resistance modified person with butyl acrylate.
10, the 9th monomer of mentioning each other multipolymer or with the multipolymer of other unsaturated monomer, for example acrylonitrile/butadiene multipolymer, vinyl cyanide/alkyl acrylate ester copolymer, vinyl cyanide/alkyl acrylate oxyalkyl ester or vinyl cyanide/halogen ethylene copolymer or vinyl cyanide/alkyl methacrylate/butadiene terpolymer.
11, from unsaturated alcohol and amine or acyl derivative or its acetal derived polymers, for example polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polymaleic acid vinyl acetate, polyvinyl butyral acetal, poly-O-phthalic allyl propionate or polyene propyl group melamine; With and with the multipolymer of above the 1st alkene of mentioning.
12, the homopolymer of cyclic ether and multipolymer, for example multipolymer of polyalkylene glycol, polyethylene oxide, poly(propylene oxide) or itself and Diglycidyl.
13, for example polyoxymethylene and those contain the polyoxymethylene of oxyethane as comonomer to polyacetal; Polyacetal with thermoplastic polyurethane, acrylate or MBS modification.
14, the mixture of polyphenylene oxide and polyphenylene sulfide and polyphenylene oxide and styrene polymer or polymeric amide.
15, from the one hand for polyethers, polyester or the polyhutadiene of C-terminal being arranged and is aliphatics or aromatic polyisocyanate deutero-urethane on the other hand, with and precursor.
16, from diamines and dicarboxylic acid and/or from the polymeric amide and the copolyamide of aminocarboxylic acid or corresponding lactam derivative, for example polymeric amide 4, polyamide 6, polyamide 6/6,6/10,6/9,6/12,4/6,12/12, polymeric amide 11, polymeric amide 12 are from the aromatic polyamide of m-xylene diamine and hexanodioic acid; From hexamethylene-diamine and m-phthalic acid and/or terephthalic acid and have or nonelastic body as the polymeric amide of properties-correcting agent preparation, for example poly-paraphenylene terephthalamide-2,4,4-trimethylhexamethylenediamine or poly; Also have above-mentioned polymeric amide and polyolefine, olefin copolymer, iolon or chemical bonding or grafted elastomerics or with polyethers for example with the segmented copolymer of polyoxyethylene glycol, polypropylene glycol or polytetramethylene glycol; And with the polymeric amide or the copolyamide of EPDM or ABS modification; Polymeric amide (RIM polymeric amide system) with condensation during the processing.
17, polyureas, polyimide, polyamide-imide, polyetherimide, poly-beta-lactam and polybenzimidazole.
18, from dicarboxylic acid and glycol and/or from hydroxycarboxylic acid or corresponding lactone deutero-polyester, for example polyethylene terephthalate, polybutylene terephthalate, poly terephthalic acid-1,4-two (methylol) hexanaphthene ester, poly-naphthalic acid alkylidene diol ester (PAN) and poly-hydroxybenzoate, and from the polyethers deutero-block copolyether ester of C-terminal is arranged; The polyester of also useful polycarbonate or MBS modification.
19, polycarbonate and polyestercarbonate.
20, polyketone.
21, polysulfones, polyethersulfone and polyetherketone.
22, the blend of above-mentioned polymkeric substance (alloyed polymer), for example PP/EPDM, polymeric amide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/ acrylate, POM/ thermoplasticity PUR, PC/ thermoplasticity PUR, POM/ acrylate, POM/MBS, PPO/HIPS, PPO/PA6.6 and multipolymer, PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS or PBT/PET/PC.
The thermoplastic resin of component (a) is a homopolymer polypropylene for example.Especially, the resin of wire insulation of the present invention, plug and socket is made up of homopolymer polypropylene basically.Term " plug " refers to the plastic lousing part of plug-assembly certainly.Plastics electric component of the present invention for example can be used for hotel (holiday) illumination.
For composition of the present invention, the level of the additive agent mixture of component (b) is about 5% to about 20% weight based on the weight of component (a).For example, component (b) is that the amount of about 8% to about 17% or about 11% to about 14% weight exists with the weight based on component (a).For example, component (b) is that about 5% to about 17%, about 5% to about 14%, about 5% to about 11% or about 5% amount to about 8% weight exists with the weight based on component (a).For example, component (b) is that the amount of about 8% to about 20%, about 11% to about 20%, about 14% to about 20% or about 17% to about 20% weight exists with the weight based on component (a).
For polypropylene-based resin of the present invention, the level of the additive agent mixture of component (b) best for the weight based on component (a) be about 10% to about 20% weight.For example, component (b) is that about 12% to about 18% or about 14% amount to about 16% weight exists with the weight based on component (a).For example, component (b) is that about 12% to about 20%, about 14% to about 20%, about 16% to about 20% or about 18% amount to about 20% weight exists with the weight based on component (a).For example, component (b) is that about 10% to about 18%, about 10% to about 16%, about 10% to about 14% or about 10% amount to about 12% weight exists with the weight based on component (a).
For polyvinyl resin of the present invention, the level of the additive agent mixture of component (b) is best for the weight based on component (a) is about 5% to about 15% weight, is about 7% to about 13% or about 8% to arrive about 11 weight % based on the weight of component (a) for example.For example, component (b) is that about 5% to about 12%, about 5% to about 9% or about 5% amount to about 8% weight exists with the weight based on component (a).For example, component (b) is that about 8% to about 15%, about 11% to about 15% or about 13% amount to about 15% weight exists with the weight based on component (a).
Component (i) and component ratio (weight part) (ii) be for example between about 1: 5 to about 1: 200, for example about 1: 15 to about 1: 100, for example about 1: 25 to about 1: 70 or about 1: 30 to about 1: 50.For example, component (i) is about 1: 40 weight with component ratio (ii).For example, component (i) is about 1: 15 to about 1: 200, about 1: 25 to about 1: 200, about 1: 30 to about 1: 200 or about 1: 40 to about 1: 200 with component ratio (ii).For example, component (i) is about 1: 5 to about 1: 100, about 1: 5 to about 1: 70, about 1: 5 to about 1: 50 or about 1: 5 to about 1: 40 with component weight ratio (ii).
The present composition satisfies the fire retardant standard, only comprises antimony compounds in a small amount simultaneously, for example Sb 2O 3, for example less than component (a) weight about 1%, for example less than about 0.1%; For example the present composition is substantially free of antimony.Yet in some preparation, antimony compounds may be favourable for satisfying flame-retardant standard.
In order to improve flame retardant properties and to reach high grade, for example UL 1694, the grade in UL 94 and the NFPA701 test, and fire-retardant filler is not requirement.Therefore, composition of the present invention can only comprise fire-retardant filler in a small amount, for example less than component (a) about 3%, for example less than about 1%, for example less than about 0.1 weight %; For example the present composition is substantially free of fire-retardant filler.
Fire-retardant filler is well known in the art and is selected from magnesium hydroxide, hibbsite and zinc borate.Fire-retardant filler is the mineral compound that uses for flame retardant properties, and uses with sufficiently high level, therefore is considered to " filler ".
If conventional fillers, for example talcum, lime carbonate or the like are normally used, for example in order to change flow characteristics, so that reduce spread (not being fire-retardant) of burning drop itself, under the situation of using the present composition, this class conventional fillers also can be reduced.For example, composition of the present invention can only comprise conventional fillers in a small amount, for example less than component (a) about 3%, for example less than about 1%, for example less than about 0.1 weight %; For example the present composition is substantially free of conventional fillers.
In addition, the present invention allows to replace more expensive fire-retardant filler with conventional fillers.
The stabilized composition of the present invention that obtains can also randomly comprise various conventional additives, for example its amount is about 0.01 to about 10%, for example about 0.025 to about 4%, for example about 0.1 to arrive about 2% weight based on the weight of component (a), for example list in following material, perhaps its mixture.
1. oxidation inhibitor
1.1. alkylation monophenol, for example 2, the 6-di-tert-butyl-4-methy phenol, the 2-tertiary butyl-4, the 6-xylenol, 2,6-di-t-butyl-4-ethylphenol, 2,6-di-t-butyl-4-normal-butyl phenol, 2,6-di-t-butyl-4-isobutyl-phenol, 2,6-two cyclopentyl-4-methylphenol, 2-(Alpha-Methyl cyclohexyl)-4, the 6-xylenol, 2,6-two (octadecyl)-4-methylphenol, 2,4,6-thricyclohexyl phenol, 2,6-di-t-butyl-4-methoxyl methyl phenol, on the side chain nonylphenol for example 2 of line style or branching, 6-dinonyl-4-methylphenol, 2,4-dimethyl-6-(1 '-methyl undecane-1 '-yl) phenol, 2,4-dimethyl-6-(1 '-methyl heptadecane-1 '-yl) phenol, 2,4-dimethyl-6-(1 '-methyl tridecane-1 '-yl) phenol and composition thereof.
1.2. alkane thiomethyl phenol, for example 2,4-two hot thiomethyl-6-tert.-butyl phenols, 2,4-two hot thiomethyl-6-methylphenols, 2,4-two hot thiomethyl-6-ethylphenols, 2,6-two (dodecane thiomethyl)-4-nonylphenol.
1.3. quinhydrones and alkylation quinhydrones, for example 2,6-di-t-butyl-4-methoxyphenol, 2,5 di tert butylhydroquinone, 2,5 di tert amlyl hydroquinone, 2,6-phenylbenzene-4-(octadecane oxygen base) phenol, 2,6-di-tert-butyl hydroquinone, 2,5-di-t-butyl-4-BHA, 3,5-di-t-butyl-4-BHA, stearic acid 3,5-di-t-butyl-4-hydroxylphenyl ester, hexanodioic acid two (3,5-di-t-butyl-4-hydroxylphenyl ester).
1.4. tocopherol, for example alpha-tocopherol, 5,8-dimethyl tocol, Gamma-Tocopherol, Delta-Tocopherol and composition thereof (vitamin-E).
1.5. hydroxylation phenyl disulfide ether, for example 2,2 '-sulphur two (the 6-tertiary butyl-4-methylphenol), 2,2 '-sulphur two (4-octyl phenol), 4,4 '-sulphur two (the 6-tertiary butyl-3-methylphenol), 4,4 '-sulphur two (the 6-tertiary butyl-2-methylphenol), 4,4 '-sulphur two (3,6-di-sec-amyl phenol), 4,4 '-two (2,6-dimethyl-4-hydroxy phenyl) disulphide.
1.6. inclined to one side alkylidene group biphenol, for example 2,2 '-methylene radical two (the 6-tertiary butyl-4-methylphenol), 2,2 '-methylene radical two (the 6-tertiary butyl-4-ethylphenol), 2,2 '-methylene radical two [4-methyl-6-(Alpha-Methyl cyclohexyl) phenol], 2,2 '-methylene radical two (4-methyl-6-cyclohexylphenol), 2,2 '-methylene radical two (6-nonyl-4-methylphenol), 2,2 '-methylene radical two (4, the 6-DI-tert-butylphenol compounds), 2,2 '-inclined to one side ethylene (4, the 6-DI-tert-butylphenol compounds), 2,2 '-inclined to one side ethylene (the 6-tertiary butyl-4-isobutyl-phenol), 2,2 '-methylene radical two [6-(α-Jia Jibianji)-4-nonylphenol 1,2,2 '-methylene radical two [6-(α, α-Er Jiajibianji)-the 4-nonylphenol], 4,4 '-methylene radical two (2, the 6-DI-tert-butylphenol compounds), 4,4 '-methylene radical two (the 6-tertiary butyl-2-methylphenol), 1,1-two (5-tertiary butyl-4-hydroxy-2-aminomethyl phenyl) butane, 2,6-two (the 3-tertiary butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol, 1,1,3-three (5-tertiary butyl-4-hydroxy-2-aminomethyl phenyl) butane, 1,1-two (5-tertiary butyl-4-hydroxy-2-aminomethyl phenyl)-3-n-dodecane sulfenyl butane, two [3,3-two (3 '-tertiary butyl-4 '-hydroxy phenyl) butyric acid] glycol ester, two (3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) dicyclopentadiene, terephthalic acid two [2-(3 '-tertiary butyl-2 '-hydroxyl-5 '-methyl-benzyl)-the 6-tertiary butyl-4-methyl phenyl ester], 1,1-two (3,5-dimethyl-2-hydroxy phenyl) butane, 2,2-two (3, the 5-di-tert-butyl-hydroxy phenyl) propane, 2,2-two (5-tertiary butyl-4-hydroxy-2-aminomethyl phenyl)-4-n-dodecane sulfenyl butane, 1,1,5,5-four (5-tertiary butyl-4-hydroxy-2-aminomethyl phenyl) pentane.
1.7.O-, N-and S-benzyl compounds, for example 3,5,3 ', 5 '-tetra-tert-4,4 '-dihydroxyl dibenzyl ether, 4-hydroxyl-3,5-dimethylbenzyl ethyl thioglycollic acid octadecane ester, 4-hydroxyl-3,5-di-t-butyl benzylthio-acetate tridecane ester, three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) amine, dithio terephthalic acid two (the 4-tertiary butyl-3-hydroxyl-2,6-dimethylbenzyl ester), two (3, the 5-di-tert-butyl-4-hydroxyl benzyl) thioether, 3,5-di-t-butyl-4-hydroxyl benzylthio-2-ethyl hexyl ethanoate.
1.8. acrinyl malonic ester, for example, 2,2-two (3,5-di-t-butyl-2-hydroxybenzyl) propanedioic acid two (octadecane ester), 2-(3-tertiary butyl-4-hydroxy-5-methyl-benzyl) propanedioic acid two (octadecane ester), 2,2-two (3, the 5-di-tert-butyl-4-hydroxyl benzyl) propanedioic acid two (dodecane sulfenyl ethyl ester), 2,2-two (3, the 5-di-tert-butyl-4-hydroxyl benzyl) [4-(1 for propanedioic acid two, 1,3, the 3-tetramethyl butyl) phenyl ester].
1.9. aromatic series acrinyl compound, for example, 1,3,5-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl)-2,4,6-Three methyl Benzene, 1,4-two (3, the 5-di-tert-butyl-4-hydroxyl benzyl)-2,3,5,6-tetramethyl-benzene, 2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) phenol.
1.10. triaizine compounds, for example, 2,4-two (hot sulfydryl)-6-(3,5-di-t-butyl-4-hydroxybenzene amido)-1,3,5-triazines, the hot sulfydryl-4 of 2-, 6-two (3,5-di-t-butyl-4-hydroxybenzene amido)-1,3,5-triazines, the hot sulfydryl-4 of 2-, 6-two (3,5-di-t-butyl-4-hydroxyphenoxy)-1,3,5-triazines, 2,4,6-three (3,5-di-t-butyl-4-hydroxyphenoxy)-1,3, the 5-triazine, isocyanuric acid-1,3,5-three (3,5-di-t-butyl-4-hydroxyl benzyl ester), isocyanuric acid-1,3,5-three (the 4-tertiary butyl-3-hydroxyl-2,6-dimethylbenzyl ester), 2,4,6-three (3,5-di-tert-butyl-hydroxy phenyl ethyl)-1,3, the 5-triazine, 1,3,5-three (3,5-di-tert-butyl-hydroxy phenyl propionyl) six hydrogen-1,3,5-triazines, isocyanuric acid-1,3,5-three (3,5-dicyclohexyl-4-hydroxyl benzyl ester).
1.11. benzylphosphonic acid ester, for example, 2,5-di-tert-butyl-4-hydroxyl benzyl dimethyl phosphonate, 3,5-di-tert-butyl-4-hydroxyl benzyl diethyl phosphonate, 3,5-di-tert-butyl-4-hydroxyl benzyl phosphonic acids two (octadecane ester), 5-tertiary butyl-4-hydroxy-3-methyl-benzyl phosphonic acids two (octadecane ester), 3,5-di-tert-butyl-4-hydroxyl benzyl phosphonic acids mono ethyl ester calcium salt.
1.12. amide group phenol, for example, 4-hydroxy-n-lauroyl aniline, 4-hydroxy-n-stearanilide, N-(3, the 5-di-tert-butyl-hydroxy phenyl) carboxylamine monooctyl ester.
1.13. β-(3, the 5-di-tert-butyl-hydroxy phenyl) ester of propionic acid and following monobasic or polyvalent alcohol: methyl alcohol for example, ethanol, n-Octanol, isooctyl alcohol, Stearyl alcohol, 1, the 6-hexylene glycol, 1, the 9-nonanediol, ethylene glycol, 1, the 2-propylene glycol, neopentyl glycol, the sulfo-glycol ether, glycol ether, triglycol, tetramethylolmethane, isocyanuric acid three (hydroxy methacrylate), N, N '-two (hydroxyethyl) oxamide, 3-thia hendecanol, 3-thia pentadecylic alcohol, the trimethylammonium hexylene glycol, three (methylol) propane, 4-methylol-1-phospha-2,6,7-trioxa-l-phosphabicyclo [2.2.2] octane.
1.14. the ester of β-(5-tertiary butyl-4-hydroxy-3-aminomethyl phenyl) propionic acid and following monobasic or polyvalent alcohol: methyl alcohol for example, ethanol, n-Octanol, isooctyl alcohol, Stearyl alcohol, 1, the 6-hexylene glycol, 1, the 9-nonanediol, ethylene glycol, 1, the 2-propylene glycol, neopentyl glycol, the sulfo-glycol ether, glycol ether, triglycol, tetramethylolmethane, isocyanuric acid three (hydroxy methacrylate), N, N '-two (hydroxyethyl) oxamide, 3-thia hendecanol, 3-thia pentadecylic alcohol, the trimethylammonium hexylene glycol, three (methylol) propane, 4-methylol-1-phospha-2,6,7-trioxa-l-phosphabicyclo [2.2.2] octane.
1.15. β-(3,5-dicyclohexyl-4-hydroxy phenyl) ester of propionic acid and following monobasic or polyvalent alcohol: for example methyl alcohol, ethanol, octanol, Stearyl alcohol, 1,6-hexylene glycol, 1,9-nonanediol, ethylene glycol, 1,2-propylene glycol, neopentyl glycol, sulfo-glycol ether, glycol ether, triglycol, tetramethylolmethane, isocyanuric acid three (hydroxy methacrylate), N, N '-two (hydroxyethyl) oxamide, 3-thia hendecanol, 3-thia pentadecylic alcohol, trimethylammonium hexylene glycol, three (methylol) propane, 4-methylol-1-phospha-2,6,7-trioxa-l-phosphabicyclo [2.2.2] octane.
1.16.3, the ester of 5-di-tert-butyl-hydroxy phenyl acetate and following monobasic or polyvalent alcohol: for example methyl alcohol, ethanol, octanol, Stearyl alcohol, 1,6-hexylene glycol, 1,9-nonanediol, ethylene glycol, 1,2-propylene glycol, neopentyl glycol, sulfo-glycol ether, glycol ether, triglycol, tetramethylolmethane, isocyanuric acid three (hydroxy methacrylate), N, N '-two (hydroxyethyl) oxamide, 3-thia hendecanol, 3-thia pentadecylic alcohol, trimethylammonium hexylene glycol, three (methylol) propane, 4-methylol-1-phospha-2,6,7-trioxa-l-phosphabicyclo [2.2.2] octane.
1.17. the acid amides of β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid, for example, N, N '-two (3,5-di-tert-butyl-hydroxy phenyl propionyl) hexamethylene-diamine, N, N '-two (3,5-di-tert-butyl-hydroxy phenyl propionyl) trimethylene diamines, N, N '-two (3,5-di-tert-butyl-hydroxy phenyl propionyl) hydrazine, N, N '-two [2-(3-[3, the 5-di-tert-butyl-hydroxy phenyl] propionyloxy) ethyl] oxamide (Naugard  XL-1, the supply of Uniroyal company).
1.18. xitix (vitamins C)
1.19. amine is oxidation inhibitor, for example, N, N '-di-isopropyl Ursol D, N, N '-di-sec-butyl-p-phenyl enediamine, N, N '-two (1,4-dimethyl amyl group) Ursol D, N, N '-two (1-ethyl-3-methyl amyl) Ursol D, N, N '-two (1-methylheptyl) Ursol D, N, N '-dicyclohexyl Ursol D, N, N '-diphenyl-para-phenylene diamine, N, N '-two (2-naphthyl) Ursol D, N-sec.-propyl-N '-diphenyl-para-phenylene diamine, N-(1, the 3-dimethylbutyl)-N '-diphenyl-para-phenylene diamine, N-(1-methylheptyl)-N '-diphenyl-para-phenylene diamine, CPPD N cyclohexyl N, 4-(to the toluino sulphonyl) pentanoic, N, N '-dimethyl-N, N '-di-sec-butyl-p-phenyl enediamine, pentanoic, N-allyl group pentanoic, 4-isopropoxy pentanoic, the N-phenyl-1-naphthylamine, N-(uncle's 4-octyl phenyl)-naphthalidine, N-phenyl-2-naphthylamines, octylated diphenylamine is p for example, p '-two uncle octyl diphenylamine, 4-n-butylamine-based phenol, 4-amide-based small phenol, 4-nonanoyl amino-phenol, 4-dodecanoyl amino-phenol, 4-stearyl amido phenol, two (4-p-methoxy-phenyl) amine, 2,6-di-t-butyl-4-dimethylamino methyl phenol, 2,4 '-diaminodiphenylmethane, 4,4 '-diaminodiphenylmethane, N, N, N ', N '-tetramethyl--4,4 '-diaminodiphenylmethane, 1,2-two [(2-aminomethyl phenyl) amino] ethane, 1,2-two (anilino) propane, (o-tolyl) biguanides, two [4-(1 ', 3 '-dimethylbutyl) phenyl] amine, uncle's octyl group N-phenyl-1-naphthylamine, the mixture of one alkylation and the dialkyl group tertiary butyl/uncle's octyl diphenylamine, the mixture of one alkylation and dialkyl group nonyl diphenylamine, the mixture of one alkylation and dialkyl group dodecyl diphenylamine, the mixture of one alkylation and dialkyl group sec.-propyl/isohexyl pentanoic, the mixture of one alkylation and dialkyl group tertiary butyl pentanoic, 2,3-dihydro-3,3-dimethyl-4H-1, the 4-benzothiazine, thiodiphenylamine, the mixture of one alkylation and the dialkyl group tertiary butyl/uncle's octyl group thiodiphenylamine, the mixture of one alkylation and dialkyl group uncle octyl group thiodiphenylamine, N-allyl group thiodiphenylamine, N, N, N ', N '-tetraphenyl-1,4-diamino but-2-ene, N, N-two (2,2,6,6-tetramethyl piperidine-4-yl) hexamethylene-diamine, sebacic acid two (2,2,6,6-tetramethyl piperidine-4-ester), 2,2,6,6-tetramethyl piperidine-4-ketone, 2,2,6,6-tetramethyl piperidine-4-alcohol.
2. UV light absorber and photostabilizer
(2.1.2-2-hydroxyphenyl)-2H-benzotriazole, for example known commodity hydroxyphenyl-2H-benzotriazole and be disclosed in benzotriazole in the following document: United States Patent (USP) 3,004,896; 3,055,896; 3,072,585; 3,074,910; 3,189,615; 3,218,332; 3,230,194; 4,127,586; 4,226,763; 4,275,004; 4,278,589; 4,315,848; 4,347,180; 4,383,863; 4,675,352; 4,681,905; 4,853,471; 5,268,450; 5,278,314; 5,280,124; 5,319,091; 5,410,071; 5,436,349; 5,516,914; 5,554,760; 5,563,242; 5,574,166; 5,607,987; 5,977,219 and 6,166,218; 2-(2-hydroxy-5-methyl base phenyl)-2H-benzotriazole for example; 2-(3; 5-two-tertiary butyl-2-hydroxyphenyl)-the 2H-benzotriazole; 2-(2-hydroxyl-5-tert-butyl-phenyl)-2H-benzotriazole; 2-(2-hydroxyl-uncle's 5-octyl phenyl)-2H-benzotriazole; 5-chloro-2-(3; 5-two-tertiary butyl-2-hydroxyphenyl)-the 2H-benzotriazole; 5-chloro-2-(the 3-tertiary butyl-2-hydroxy-5-methyl base phenyl)-2H-benzotriazole; 2-(the 3-sec-butyl-5-tertiary butyl-2-hydroxyphenyl)-2H-benzotriazole; 2-(2-hydroxyl-4-octyloxyphenyl)-2H-benzotriazole; 2-(3; 5-two-tert-pentyl-2-hydroxyphenyl)-the 2H-benzotriazole; 2-(3; 5-pair-α-cumyl-2-hydroxyphenyl)-the 2H-benzotriazole; 2-(the 3-tertiary butyl-2-hydroxyl-5-(2-(ω-hydroxyl-eight (ethyleneoxy group) carbonyl-ethyl)-; phenyl)-the 2H-benzotriazole; 2-(3-dodecyl-2-hydroxy-5-methyl base phenyl)-2H-benzotriazole; 2-(the 3-tertiary butyl-2-hydroxyl-5-(2-carbonyl octyloxy) ethylphenyl)-2H-benzotriazole; the 2-of dodecylization (2-hydroxy-5-methyl base phenyl)-2H-benzotriazole; 2-(the 3-tertiary butyl-2-hydroxyl-5-(2-carbonyl octyloxy ethyl) phenyl)-5-chloro-2H-benzotriazole; 2-(the 3-tertiary butyl-5-(2-(2-ethyl hexyl oxy)-carbonyl ethyl)-2-hydroxyphenyl)-5-chloro-2H-benzotriazole; 2-(the 3-tertiary butyl-2-hydroxyl-5-(2-methoxycarbonyl ethyl) phenyl)-5-chloro-2H-benzotriazole; 2-(the 3-tertiary butyl-2-hydroxyl-5-(2-methoxycarbonyl ethyl) phenyl)-2H-benzotriazole; 2-(the 3-tertiary butyl-5-(2-(2-ethyl hexyl oxy) carbonyl ethyl)-2-hydroxyphenyl)-2H-benzotriazole; 2-(the 3-tertiary butyl-2-hydroxyl-5-(2-iso-octyl oxygen base carbonyl ethyl) phenyl-2H-benzotriazole; 2; 2 '-methylene-bis (uncle's 4-octyl group-(6-2H-benzotriazole-2-yl) phenol); 2-(2-hydroxy-3-alpha-cumyl--uncle's 5-octyl phenyl)-2H-benzotriazole; 2-(2-hydroxyl-uncle's 3-octyl group-5-α-cumyl phenyl)-2H-benzotriazole; 5-fluoro 2-(2-hydroxyl-3; 5-two-α-cumyl-phenyl)-the 2H-benzotriazole; 5-chloro-2-(2-hydroxyl-3; 5-two-α-cumyl phenyl)-the 2H-benzotriazole; 5-chloro-2-(2-hydroxy-3-alpha-cumyl--uncle's 5-octyl phenyl)-2H-benzotriazole; 2-(the 3-tertiary butyl-2-hydroxyl-5-(2-iso-octyl oxygen base carbonyl ethyl) phenyl)-5-chloro-2H-benzotriazole; 5-trifluoromethyl-2-(2-hydroxy-3-alpha-cumyl--uncle's 5-octyl phenyl)-2H-benzotriazole; 5-trifluoromethyl-2-(2-hydroxyl-uncle's 5-octyl phenyl)-2H-benzotriazole; 5-trifluoromethyl-2-(2-hydroxyl-3; 5-two-uncle octyl phenyl)-the 2H-benzotriazole; methyl 3-(5-trifluoromethyl-2H-benzotriazole-2-yl)-5-tertiary butyl-4-hydroxy hydrogen laurate; 5-butyl alkylsulfonyl-2-(2-hydroxy-3-alpha-cumyl--uncle's 5-octyl phenyl)-2H-benzotriazole; 5-trifluoromethyl-2-(2-hydroxy-3-alpha-cumyl--5-tert-butyl-phenyl)-2H-benzotriazole; 5-trifluoromethyl-2-(2-hydroxyl-3; 5-two-tert-butyl-phenyl)-the 2H-benzotriazole; 5-trifluoromethyl-2-(2-hydroxyl-3; 5-two-α-cumyl phenyl)-the 2H-benzotriazole; 5-butyl alkylsulfonyl-2-(2-hydroxyl-3; 5-two-tert-butyl-phenyl)-2H-benzotriazole and 5-phenyl sulfonyl-2-(2-hydroxyl-3,5-two-tert-butyl-phenyl)-2H-benzotriazole.
2.2.2-dihydroxy benaophenonel, for example, 4-hydroxyl, 4-methoxyl group, 4-octyloxy, 4-oxygen in last of the ten Heavenly stems base, dodecyloxy, 4-benzyloxy, 4,2 ', 4 '-trihydroxy-and 2 '-hydroxyl-4,4 '-the dimethoxy derivative.
2.3. replacement and benzoic ester that do not have to replace are arranged; for example; Whitfield's ointment 4-tertiary butyl phenyl ester, salol, Whitfield's ointment octyl octylphenyl, dibenzoyl resorcinols, two (4-tert.-butylbenzene formyl radical) Resorcinol, benzoyl Resorcinol, 3; 5-di-tert-butyl-4-hydroxybenzoic acid 2; 4-di-t-butyl phenyl ester, 3; 5-di-tert-butyl-4-hydroxybenzoic acid n-Hexadecane ester, 3; 5-di-tert-butyl-4-hydroxybenzoic acid octadecane ester, 3; 5-di-tert-butyl-4-hydroxybenzoic acid 2-methyl-4,6-di-t-butyl phenyl ester.
2.4. acrylate, for example, alpha-cyano-β, β-diphenyl-ethyl acrylate, alpha-cyano-β, β-diphenyl 2-Propenoic acid-2-ethylhexyl ester, α-methoxycarbonyl methyl cinnamate, alpha-cyano-Beta-methyl-p-methoxycinnamic acid methyl esters, alpha-cyano-Beta-methyl p-methoxycinnamic acid butyl ester, α-methoxycarbonyl p-methoxycinnamic acid methyl esters and N-(beta-methoxy-carbonyl-beta-cyano vinyl)-2-methyl indoline.
2.5. nickel compound, for example, 2,2 '-nickel complex of sulphur two [4-(1,1,3, the 3-tetramethyl butyl) phenol], for example 1: 1 or 1: 2 complex compound, and have or do not have other part for example n-Butyl Amine 99, trolamine or N-cyclohexyl diethanolamine; Dibutyl two thiocarbamate nickel; 4-hydroxyl-3,5-di-t-butyl benzylphosphonic acid list alkane ester be the nickel salt of methyl esters or ethyl ester for example; Ketoxime is the nickel complex of 2-hydroxy-4-methyl phenyl undecyl ketoxime for example; The nickel complex of 1-phenyl-4-lauroyl-5-hydroxypyrazoles has or does not have other part.
2.6. sterically hindered amines, for example, sebacic acid two (2,2,6,6-tetramethyl--4-piperidines ester), succsinic acid two (2,2,6,6-tetramethyl--4-piperidines ester), sebacic acid two (1,2,2,6,6-pentamethyl--4-piperidines ester), sebacic acid two (1-octyloxy-2,2,6,6-tetramethyl--4-piperidines ester), normal-butyl-3,5-di-tert-butyl-4-hydroxyl benzyl propanedioic acid two (1,2,2,6,6-pentamethyl--4-piperidines ester), 1-(2-hydroxyethyl)-2,2,6, the condenses of 6-tetramethyl--4-hydroxy piperidine and succsinic acid, N, N '-two (2,2,6,6-tetramethyl--4-piperidyl) hexamethylene-diamine and 4-tert-Octylamine base-2,6-two chloro-1,3, the line style of 5-triazine or ring-shaped condensate, nitrilotriacetic acid(NTA) three (2,2,6,6-tetramethyl--4-piperidines ester), 1,2,3,4-BTCA four (2,2,6,6-tetramethyl--4-piperidines ester), 1,1 '-(1,2-second two bases) two (3,3,5, the 5-tetramethylpiperidone), 4-benzoyl-2,2,6,6-tetramethyl piperidine, 4-stearoyl-oxy-2,2,6, the 6-tetramethyl piperidine, 2-normal-butyl-2-(2-hydroxyl-3,5-di-t-butyl benzyl) propanedioic acid two (1,2,2,6,6-pentamethyl-piperidines ester), 3-n-octyl-7,7,9,9-tetramethyl--1,3,8-thriazaspiro [4.5] decane-2,4-diketone, sebacic acid two (1-octyloxy-2,2,6,6-tetramethyl piperidine ester), succsinic acid two (1-octyloxy-2,2,6,6-tetramethyl piperidine ester), N, N '-two (2,2,6,6-tetramethyl--4-piperidyl) hexamethylene-diamine and 4-morpholino-2, the line style or the ring-shaped condensate of 6-two chloro-1,3,5-triazines, 2-chloro-4,6-two (4-n-butylamine-based-2,2,6, the 6-tetramethyl-piperidyl)-1,3,5-triazine and 1, the condenses of 2-two (the amino Propylamino of 3-) ethane, 2-chloro-4,6-two (4-n-butylamine-based-1,2,2,6,6-pentamethyl-piperidyl)-1,3,5-triazines and 1, the condenses of 2-two (the amino Propylamino of 3-) ethane, 8-ethanoyl-3-dodecyl-7,7,9,9-tetramethyl--1,3,8-thriazaspiro [4.5] decane-2,4-diketone, 3-dodecyl-1-(2,2,6,6-tetramethyl--4-piperidyl) tetramethyleneimine-2, the 5-diketone, 3-dodecyl-1-(1,2,2,6,6-pentamethyl--4-piperidyl) tetramethyleneimine-2, the 5-diketone, 4-n-Hexadecane oxygen base-and the stearic oxygen base-2 of 4-, 2,6, the mixture of 6-tetramethyl piperidine, N, N '-two (2,2,6,6-tetramethyl--4-piperidyl) hexamethylene-diamine and 4-cyclohexylamino-2,6-two chloro-1,3, the condenses of 5-triazine, 1,2-two (the amino Propylamino of 3-) ethane and 2,4,6-three chloro-1,3,5-triazine and 4-butylamine base-2,2,6, the condenses of 6-tetramethyl piperidine (CAS accession number [136504-96-6]); N-(2,2,6,6-tetramethyl--4-piperidines) dodecyl succinimide; N-(1,2,2,6,6-pentamethyl--4-piperidyl) dodecyl succinimide; 2-undecyl-7,7,9,9-tetramethyl--1-oxa--3,8-diaza-4-oxo spiral shell [4.5] decane; 7,7,9; 9-tetramethyl--2-encircles undecyl-1-oxa--3, the reaction product of 8-diaza-4-oxo spiral shell [4.5] decane and Epicholorohydrin, 1; 1-two (1,2,2; 6,6-pentamethyl--4-piperidines oxygen carbonyl)-2-(4-p-methoxy-phenyl) ethene, N; N '-diformyl-N, N '-two (2,2; 6,6-tetramethyl--4-piperidyl) hexamethylene-diamine, 4-methoxy methylene radical propanedioic acid and 1; 2,2,6; the diester of 6-pentamethyl--4-hydroxy piperidine, poly-[methyl-propyl-3-oxygen-4-(2,2; 6,6-tetramethyl--4-piperidyl)] siloxanes, maleic anhydride/alpha-olefin copolymer and 2; 2,6,6-tetramethyl--4-amino piperidine or 1; 2; 2,6, the reaction product of 6-pentamethyl--4-amino piperidine.
2.7. oxamide, for example, 4,4 '-two octyloxies-N, N '-phenylbenzene oxalamide, 2,2 '-diethoxy-oxalic dianilide, 2,2 '-two octyloxy-5,5 '-two tert.-butoxies-oxalic dianilide, 2,2 '-two (dodecyloxy)-5,5 '-two tert.-butoxies-oxalic dianilide, 2-oxyethyl group-2 '-ethyl-N, N '-phenylbenzene oxalamide, N, N '-two (3-dimethylamino-propyl) oxamide, 2-oxyethyl group-5-the tertiary butyl-2 '-oxyethyl group-N, N '-phenylbenzene oxalamide and with 2-oxyethyl group-2 '-mixture of ethyl-5,4 '-two tert.-butoxies-oxalic dianilide, ortho position and the dibasic N of contraposition methoxyl group are arranged, the mixture of N '-phenylbenzene oxalamide, and the mixture that ortho position and the dibasic oxalic dianilide of contraposition oxyethyl group are arranged.
2.8. three-aryl-salicyl-s-triazine, for example known commodity three-aryl-salicyl-s-triazine, and be disclosed in triazine in the following document: WO96/28431 and U.S. Patent number 3,843,371; 4,619,956; 4,740,542; 5,096,489; 5,106,891; 5,298,067; 5,300,414; 5,354,794; 5,461,151; 5,476,937; 5,489,503; 5,543,518; 5,556,973; 5,597,854; 5,681,955; 5,726,309; 5,736,597; 5,942,626; 5,959,008; 5,998,116; 6,013,704; 6,060,543; 6,187,919; 6,242,598 and 6,255,483, for example 4,6-two-(2, the 4-3,5-dimethylphenyl)-2-(2-hydroxyl-4-octyloxyphenyl)-s-triazine, Cyasorb  1164, Cytec Corp, 4,6-two-(2, the 4-3,5-dimethylphenyl)-2-(2, the 4-dihydroxyphenyl)-the s-triazine, 2,4-two (2, the 4-dihydroxyphenyl)-6-(4-chloro-phenyl-)-s-triazine, 2, two [2-hydroxyl-4-(2-hydroxyl-oxethyl) phenyl]-6-(4-the chloro-phenyl-)-s-triazines of 4-, 2, the two 12-hydroxyl-4-of 4-(2-hydroxyl-4-(2-hydroxyl-oxethyl) phenyl]-6-(2, the 4-3,5-dimethylphenyl)-the s-triazine, 2, two [2-hydroxyl-4-(2-hydroxyl-oxethyl) phenyl]-6-(4-the bromophenyl)-s-triazines of 4-, 2, two [2-hydroxyl-4-(2-acetoxyethoxy) phenyl]-6-(4-the chloro-phenyl-)-s-triazines of 4-, 2,4-two (2, the 4-dihydroxyphenyl)-6-(2, the 4-3,5-dimethylphenyl)-the s-triazine, 2, two (4-the xenyl)-6-(2-hydroxyl-4-carbonyl octyloxy ethyleneoxy group phenyl) of 4--s-triazine, 2-phenyl-4-[2-hydroxyl-4-(3-sec-butoxy-2-hydroxyl propoxy-) phenyl]-6-[2-hydroxyl-4-(the secondary pentyloxy of 3--2-hydroxyl propoxy-)-phenyl]-the s-triazine, 2,4-two (2, the 4-3,5-dimethylphenyl)-6-[2-hydroxyl-4-(3-benzyloxy 2-hydroxyl-propoxy-) phenyl]-the s-triazine, 2, two (the last n-butoxy phenyl of 2-hydroxyl-4-)-6-(2 of 4-, 4-two-n-butoxy-phenyl)-the s-triazine, 2,4-two (2, the 4-3,5-dimethylphenyl)-6-[2-hydroxyl-4-(3-oxygen in ninth of the ten Heavenly Stems base *-2-hydroxyl-propoxy-)-5-α-cumyl phenyl]-(* represents following mixture to the s-triazine: octyloxy, the ninth of the ten Heavenly Stems oxygen base and the last of the ten Heavenly stems oxygen base group), methylene-bis-{ 2,4-two (2, the 4-3,5-dimethylphenyl)-6-[2-hydroxyl-4-(3-butoxy-2-hydroxyl propoxy-) phenyl]-the s-triazine }, 5: 4: 1 at 3: 5 ', the methylene bridge joint dimer mixture of 5: 5 ' and 3: 3 ' position bridge joints, 2,4,6-three (the different carbonyl octyloxy isopropylidene-hydroxyphenyl of 2-hydroxyl-4-)-s-triazine, 2,4-two (2, the 4-3,5-dimethylphenyl)-6-(2-hydroxyl-4-hexyloxy-5-α-cumyl-phenyl)-s-triazine, 2-(2,4, the 6-trimethylphenyl)-4, two [2-hydroxyl-4-(3-butoxy-2-hydroxyl-propoxy-) phenyl]-s-triazines of 6-, 2,4,6-three [2-hydroxyl-4-(the 3-second month in a season-butoxy-2-hydroxyl propoxy-)-phenyl]-s-triazine, 4,6-two-(2, the 4-3,5-dimethylphenyl)-2-(2-hydroxyl-4-(3-dodecyl oxygen base-2-hydroxyl propoxy-)-phenyl)-s-triazine and 4,6-two-(2, the 4-3,5-dimethylphenyl)-mixture of 2-(2-hydroxyl-4-(3-tridecane oxygen base-2-hydroxyl propoxy-)-phenyl)-s-triazine, Tinuvin  400, Ciba Specialty Chemicals Corp., 4,6-two-(2, the 4-3,5-dimethylphenyl)-and 2-(2-hydroxyl-4-(3-(2-ethyl hexyl oxy)-2-hydroxyl propoxy-)-phenyl)-s-triazine and 4,6-phenylbenzene-2-(4-hexyloxy-2-hydroxyphenyl)-s-triazine.
3. metal inactivator, for example, N, N '-phenylbenzene oxamide, N-salicylic aldehyde-N '-salicylyl hydrazine, N, N '-two (salicylyl) hydrazine, N, N '-two (3,5-two-tert-butyl-hydroxy phenyl propionyl) hydrazine, 3-salicylyl amino-1,2, the 4-triazole, two (benzylidene partially) oxalyl two hydrazines, oxalic dianilide, m-p-hthaloyl dihydrazide, sebacoyl phenylbenzene hydrazine, N, N '-diacetyl adipyl dihydrazide, N, N '-two (salicylyl) oxalyl two hydrazines, N, N '-two (salicylyl) sulfo-propionyl two hydrazines.
4. phosphorous acid ester and phosphinate, for example, triphenyl phosphite, phosphorous acid diphenyl ester alkane ester, the phenyl-phosphite dialkyl, tricresyl phosphite (nonyl phenyl ester), trilauryl phosphite, tricresyl phosphite (octadecane ester), diphosphorous acid distearyl ester pentaerythritol ester, tricresyl phosphite (2,4-di-t-butyl phenyl ester), diphosphorous acid two isodecyl ester pentaerythritol esters, diphosphorous acid two (2,4-di-t-butyl phenyl ester) pentaerythritol ester, diphosphorous acid two (2,6-di-t-butyl-4-methyl phenyl ester) pentaerythritol ester, diphosphorous acid two isodecyl oxygen base pentaerythritol esters, diphosphorous acid two (2,4-di-t-butyl-6-methyl phenyl ester) pentaerythritol ester, diphosphorous acid two (2,4,6-tri-tert phenyl ester) pentaerythritol ester, three tricresyl phosphite stearyl ester sorbitol esters, 4,4 '-biphenyl two phosphonous acid four (2,4-di-t-butyl phenyl ester), 6-different octyloxy-2,4,8,10-tetra-tert-12H-dibenzo [d, g]-1,3,2-two oxa-phosphocin, phosphorous acid two (2,4-di-t-butyl-6-methyl phenyl ester) methyl esters, phosphorous acid two (2,4-di-t-butyl-6-methyl phenyl ester) ethyl ester, 6-fluoro-2,4,8,10-tetra-tert-12-methyldiphenyl is [d, g]-1,3 also, 2-two oxa-phosphocin, 2,2 ', 2 " nitrilo [triethyl three (3; 3 '; 5,5 '-tetra-tert-1,1 '-biphenyl-2; 2 '-two bases) phosphorous acid ester]; phosphorous acid 2-ethylhexyl (3,3 ', 5; 5 '-tetra-tert-1,1 '-biphenyl-2,2 '-two) ester, 5-butyl-5-ethyl-2-(2,4, the 6-tri-butyl-phenoxy)-1,3,2-two oxa-phosphirane.
Specifically following phosphorous acid ester:
Tricresyl phosphite (2,4-di-t-butyl phenyl ester) (Irgafos  168, Ciba-Geigy), tricresyl phosphite (nonyl phenyl ester),
Figure C20038010163400471
Figure C20038010163400481
5. azanol, for example, N, N-dibenzyl hydroxylamine, N, N-diethyl hydroxylamine, N, N-dioctyl azanol, N, N-dilauryl azanol, N, N-two (tetradecyl) azanol, N, N-two (hexadecyl) azanol, N, N-two (octadecyl) azanol, N-hexadecyl-N-octadecyl azanol, N-heptadecyl-N-octadecyl azanol is from hydrogenation tallow amine deutero-N, N-dialkyl group azanol.
6. nitrone, for example, N-benzyl-alpha-phenyl nitrone, N-ethyl-Alpha-Methyl nitrone, N-octyl group-α-heptyl nitrone, N-lauryl-α-undecyl nitrone, N-tetradecyl-α-tridecyl nitrone, N-hexadecyl-α-pentadecyl nitrone, N-octadecyl-α-heptadecyl nitrone, N-hexadecyl-α-heptadecyl nitrone, N-octadecyl-α-pentadecyl nitrone, N-heptadecyl-α-heptadecyl nitrone, N-octadecyl-α-hexadecyl nitrone, from hydrogenation tallow amine deutero-N, N-dialkyl group azanol deutero-nitrone.
7. sulphur synergist, for example, thiodipropionic acid two lauryls or thiodipropionic acid distearyl ester.
8. peroxide scavenger, for example, the ester of β-thiodipropionic acid is lauryl, stearyl ester, myristin or tridecane ester for example, the zinc salt of mercaptobenzimidazole or 2-mercaptobenzimidazole, zinc dibutyl dithiocarbamate, curing two (octadecyl), four (β-dodecane sulfenyl) propionic acid pentaerythritol ester.
9. polymeric amide stablizer, for example, with iodide and/or the mantoquita of phosphorus compound combination and the salt of bivalent manganese.
10. alkaline auxiliary stablizer, for example, melamine, Polyvinylpyrolidone (PVP), Dyhard RU 100, triallyl cyanurate, urea derivatives, hydrazine derivative, amine, polymeric amide, urethane, the an alkali metal salt of higher fatty acid and alkaline earth salt, for example calcium stearate, Zinic stearas, docosoic magnesium, Magnesium Stearate, natrium ricinoleicum, potassium palmitate, pyrocatechol antimony or pyrocatechol zinc.
11. nucleator, for example, inorganic substance, as talcum, metal oxides such as titanium dioxide or magnesium oxide, the phosphoric acid salt of alkaline-earth metal etc., carbonate or vitriol; Organic compound is monocarboxylic acid or poly carboxylic acid and salt thereof for example, for example 4-p t butylbenzoic acid, hexanodioic acid, diphenyl acetic acid, sodium succinate or Sodium Benzoate; Polymer compound, for example ionic multipolymer (iolon).Specific examples is 1,3:2,4-two (3 ', 4 '-the inclined to one side benzylidene of dimethyl) Sorbitol Powder, 1,3:2,4-two (to methyl two inclined to one side benzylidenes) Sorbitol Powder and 1,3:2,4-two (benzylidene partially) Sorbitol Powder.
12. filler and toughener, for example: the powder of lime carbonate, silicate, glass fibre, glass envelope, asbestos, talcum, kaolin, mica, barium sulfate, metal oxide and oxyhydroxide, carbon black, graphite, wood powder and other natural product or fiber, synthon.
13. other additive, for example, softening agent, lubricant, emulsifying agent, pigment, rheologic additive, catalyzer, flow control agent, optical brightener, fire prevention reagent, static inhibitor and whipping agent.
14. benzofuranone and indolinones for example are disclosed in the following patent those: the U.S. 4,325,863; 4,338,244; 5,175,312; 5,216,052; 5,252,643; DE-A-4316611; DE-A-4316622; DE-A-4316876; EP-A-0589839 or EP-A-0591102, perhaps 3-[4-(2-acetoxyethoxy)-phenyl]-5,7-two-tertiary butyl-benzofuran-2-ones, 5,7-two-tertiary butyl-3-[4-(2-stearoyl keto base oxethyl) phenyl] benzofuran-2-ones, 3,3 '-two [5,7-two-tertiary butyl-3-(the 4-[2-hydroxyl-oxethyl] phenyl) benzofuran-2-ones], 5,7-two-tertiary butyl-3-(4-phenelyl) benzofuran-2-ones, 3-(4-acetoxy-3, the 5-3,5-dimethylphenyl)-5,7-two-tertiary butyl-benzofuran-2-ones, 3-(3,5-dimethyl-4-new pentane acyloxy phenyl)-5,7-two-tertiary butyl-benzofuran-2-ones, 3-(3, the 4-3,5-dimethylphenyl)-5,7-two-tertiary butyl-benzofuran-2-ones, 3-(2, the 3-3,5-dimethylphenyl)-5,7-two-tertiary butyl-benzofuran-2-ones.
15. amine oxide, for example, U.S. Patent bulletin No.5, disclosed amine oxide derivative in 844,029 and 5,880,191, didecyl methylamine oxide compound, three decyl amine oxide compounds, tridodecylamine oxide compound and three (hexadecyl) amine oxide.U.S. Patent bulletin No.5,844,029 and 5,880,191 disclose the stable purposes that saturated hydroxylamine is used for thermoplastic resin.It discloses thermoplastic compounds can further comprise stablizer or stabilizer blend, and they are selected from phenolic antioxidant, hindered amine as light stabilizer, UV light absorber, organo phosphorous compounds, alkali metal fatty acid salt and sulfo-synergist.Not illustrating the shared of amine oxide and other stablizer can stabilization of polyolefins.
The specific examples of additive be phenolic antioxidant (the 1st in inventory), other space hindered amine (the 2.6th in inventory), benzotriazole and/or o-hydroxy-phenyl triazines photostabilizer (inventory the 2.1st and 2.8), phosphorous acid ester and phosphinate (the 4th in inventory) and can destroy the compound (the 5th in inventory) of superoxide.
The other particular instance of additive (stablizer) is a benzofuran-2-ones, for example is described in US-A-4, those in 325,863, US-A-4,338,244 or US-A-5,175,312.
The present composition can also contain further, is selected from one group the ultraviolet radiation absorption agent molecule that s-triazine, oxanilide, dihydroxy benaophenonel, benzoic ether and α-Qing Jibingxisuanzhi are formed.Specifically, the present composition can also contain at least a other 2-hydroxy phenyl-2H-benzotriazole, another kind of triaryl-s-triazine or hindered amine or its mixture of stabilizing effective amount.For example, extra composition be selected from pigment, dyestuff, softening agent, oxidation inhibitor, thixotropic agent, leveling auxiliary agent, alkaline co-stabilizer, further photostabilizer such as UV light absorber and/or space hindered amine, metal passivator, metal oxide, organo phosphorous compounds, azanol, and composition thereof, especially pigment, phenol oxidation inhibitor, calcium stearate, Zinic stearas, 2-(2 '-hydroxy phenyl) benzotriazole and 2-(2-hydroxy phenyl)-1,3, the UV light absorber of 5-triazines and space hindered amine.
Additive of the present invention and optional further composition can be individually or are added in this polymkeric substance with being mixed with each other.If wish, each single component can be in mixing this polymkeric substance before by mix such as doing, compaction or fusion be mixed with each other.
Advantageously, the present composition can comprise acid scavenger.
Therefore, another theme of the present invention is the flame retardant polymeric electrical parts composition, and it comprises:
(a) thermoplastic resin,
(b) synergistic mixt of the effective flame retardance volume of following material:
(i) at least a sterically hindered alkoxylamine stablizer and
(ii) at least a conventional organic halogen fire retardant and
(c) acid scavenger.
Acid scavenger is for example hydrotalcite and amorphous alkaline aluminium carbonate magnesium, USP4 for example, and those that describe in 427,816,5,106,898 and 5,234,981, relevant disclosing wherein is hereby incorporated by.Hydrotalcite also claims hycite or DHT4A.
Hydrotalcite is natural or synthetic.Natural hydrotalcite has structure
Mg 6Al 2(OH) 16CO 3·4H 2O。
The typical empirical formula of synthetic hydrotalcite is
Al 2Mg 4.35OH 11.36CO 3(1.67)·xH 2O。
The example of sintetics comprises:
Mg 0.7Al 0.3(OH) 2(CO 3) 0.15·0.54H 2O，
Mg 4.5Al 2(OH) 13CO 33.5H 2O and
Mg 4.2Al(OH) 12.4CO 3。
Acid scavenger is that about 0.1% level to about 1.0% weight is present in the polymer composition with the weight based on component (a).For example, acid scavenger of the present invention is that about 0.2% to about 0.8% or about 0.4% amount to about 0.6% weight exists with the weight based on component (a).For example, acid scavenger of the present invention is based on component (a) weight to be about 0.1% to about 0.8%, about 0.1% to about 0.6%, about 0.1% to the about 0.4% or about 0.1% amount existence to about 0.2% weight.For example, acid scavenger of the present invention is based on component (a) weight to be about 0.2% to about 1.0%, about 0.4% to about 1.0%, about 0.6% to the about 1.0% or about 0.8% amount existence to about 1.0% weight.
Acid scavenger is favourable for color, smell and the stability of the present composition.
Composition of the present invention can comprise the nanoscale filler.The nanoscale filler also is called as " nanoclay ", is disclosed in for example USP5, and 853,886 and 6,020,419, wherein relevant disclosing is hereby incorporated by.
Nanoscale filler of the present invention is for example layered silicate or smectic clays, the mixture of for example close organic layered silicate, naturally occurring layered silicate, layered silicate synthesis or this class layered silicate.Nanoscale filler of the present invention is for example polynite, wilkinite, beidellite, hectorite, saponite or humite.
For example, the nanoscale polynite has " tabular " or platelets structure.Platelets generally has the following thickness of about 2 nanometers.Platelets or particle generally have about 20 mean diameters and about 30,000 that arrive between about 30,000 nanometers: the long-width ratio between 1 to 20: 1.The commercially available nanoscale polynite that gets with this class formation is Nanomer  1.42E, can derive from Nanocor and Cloisite  30B, can derive from Southern Clay.
The nanoscale filler has great surface and high surface energy.Therefore, compare with common microscale filler, the compatibilized of the deactivation of surface energy and nanoscale filler and polymkeric substance is even is prior, assembles and obtain the dispersion of excellence to avoid the nanoscale filler in polymkeric substance.The nanoscale filler is as layered silicate, by ion-exchange, for example carry out ion-exchange with alkylammonium salt and make and have close organic property.The organic layered silicate of this class nanoscale parent be more swellable and be dispersed in polymeric matrix easily.
The nanoscale filler of handling also is called as " layered clay material of processing " or " organic clay ".
The nanoscale filler is about 0.1% to about 10% weight, for example about 1% to about 9 weight %, for example about 3% to about 7% weight, for example the concentration of about 5% weight is present in the present composition with the weight based on component (a).
The present composition can comprise the melamine based flameproofing.The melamine based flameproofing for example is:
Melamine cyanurate,
The melamine borate,
Melamine phosphate,
The melamine poly-phosphate,
The melamine pyrophosphate salt,
Melamine ammonium poly-phosphate and
Melamine ammonium pyrophosphate salt.
The melamine based flameproofing can be the about 0.5% amount existence of arriving about 15% weight to about 15% weight, about 1% to about 15%, about 3% to about 15% or about 5% based on the weight of component (a).For example, the melamine based flameproofing is about 0.5% to about 12%, about 0.5% to about 10%, about 0.5% to about 8% or about 0.5% to use to about 6% weight with the weight based on component (a).
The embodiment of the invention is not understood that it is any restriction to any aspect.
The effective flame retardance volume of component (b) is the amount that shows that flame retardant efficiency needs, and this flame retardant efficiency is measured by one of standard method of being used to estimate flame retardant resistance.These comprise: test UL1694, UL94 and NFPA701; Test the UL1694 test of little polymer element material combustion, 2002; NFPA 701 standard methods of the fire test of flame retardant textiles and film (NFPA 701 StandardMethods of Fire Tests for Flame-Resistant Textiles and Films), 1989 and 1996 and 1999 editions; The flammable UL94 experiment of the plastic material of parts (UL94 Test for Flammability of Plastic Materials for Parts in Devicesand Appliances) in test set and the instrument, the 5th edition, on October 29th, 1996, the grade such as the following table of .UL94V test were listed:
Grade Combustion time The burning drippage Be burned to anchor clamps
V-0 ＜10s Not Not
V-1 ＜30s Not Not
V-2 ＜30s Be Not
Defective ＜30s Be
Defective ＞30s Not
Embodiment 1: the polypropylene electrical isolation
Prepared the polypropylene homo matter sample, it comprises one of the N-cyclohexyl oxygen base bulky amine (a)-(f) and three [3-bromos-2 of 15% weight, two (brooethyl) propyl group of 2-] mixture of phosphoric acid ester, wherein the weight ratio of each of N-cyclohexyl oxygen base bulky amine and conventional organic bromine fire retardant is 1: 14.Weight percentage is based on polymkeric substance.
Every kind of prescription all satisfy (by) UL1694 standard (the combustibility test of little polymer element material).
Embodiment 2: the polyethylene electric component
Polyethylene electric component, HDPE and LDPE have been prepared, it comprises each and three [3-bromos-2 of the N-cyclohexyl oxygen base bulky amine (a)-(f) of 8% weight, two (brooethyl) propyl group of 2-] mixture of phosphoric acid ester, wherein the weight ratio of each N-cyclohexyl oxygen base bulky amine and conventional organic bromine fire retardant is 1: 14.
Every kind of prescription satisfy (by) NFPA 701 tests.
Embodiment 3: the polystyrene electric component
Repeat embodiment 2 with the polystyrene electric component.Every kind of prescription is all by UL 94 and UL1694 test.
Embodiment 4: acid scavenger
Repeat embodiment 1-3, wherein also add about 0.1% to about 1.0% acid scavenger of the present invention.Obtained the excellent fire retardant result.The acid scavenger of the present invention that further adds 0.6% weight (based on polymkeric substance) has improved color, smell and the stability of flame-retardant polymer.
Embodiment 5:
Repeat front embodiment, with two (2,3-dibromopropyl ether) replacement three [3-bromo-2, two (brooethyl) propyl group of 2-] phosphoric acid ester of tetrabromo-bisphenol.Two (2,3-dibromopropyl ether) of tetrabromo-bisphenol are being about 9% to about 15% weight, for example the level of about 10%, 12% or 14% weight is used based on the weight of thermoplastic resin for example.In this case, the weight ratio of sterically hindered alkoxylamine and conventional organic bromine fire retardant is for example about 1: 25 to about 1: 70, about 1: 30 to about 1: 50, for example about 1: 40 or 1: 50.Antimonous oxide can be that about 2% level to about 6% weight exists based on thermoplastic resin.For example, the level of antimony existence is about 3%, 4%, 5% or 6% weight.The melamine based flameproofing also is favourable.For example, melamine based flameproofing of the present invention is being about 5% to about 15% weight, for example the amount of about 6%, 7%, 8%, 9% or 10% weight exists based on thermoplastic resin.
This prescription is by UL 1694.

Claims (14)

1. flame retardant polymeric electrical parts composition, it comprises
(a) thermoplastic resin and
(b) synergistic mixt of Yi Xia effective flame retardance volume:
(i) at least a sterically hindered alkoxylamine stablizer and
(ii) at least a organic halogen fire retardant; With
(c) acid scavenger.
2. the composition of claim 1, the wherein described alkoxylamine stablizer of component (i) compound that is following general formula:
Figure C2003801016340002C1
G wherein 1And G 2Being the alkyl of 1 to 8 carbon atom independently, perhaps is pentamethylene together,
Z 1And Z 2Each is methyl, perhaps Z naturally 1And Z 2Form the connection portion together, its be not substituted or in addition by ester, ether, acid amides, amino, carboxyl or carbamate groups replaces and
E is the cycloalkyloxy of the alkoxyl group of 1 to 18 carbon atom, 5 to 12 carbon atoms or the aralkoxy of 7 to 15 carbon atoms, or E is-O-T-(OH) b,
T is the alkylidene group of 1 to 4 carbon atom of the ring alkenylene of the cycloalkylidene of the alkylidene group of 1 to 18 carbon atom of straight chain or side chain, 5 to 18 carbon atoms, 5 to 18 carbon atoms, the straight chain that replaces by phenyl or by the phenyl that is replaced by the alkyl group of one or two 1 to 4 carbon atom or side chain;
B is 1,2 or 3, and condition is that b can not surpass the carbonatoms among the T, and when b was 2 or 3, each oh group was connected to the different carbon atom of T.
3. the composition of claim 2, wherein E be 1 to 18 carbon atom alkoxyl group, cyclohexyl oxygen base or-O-T-(OH) b, wherein b be 1 and T be C 2-C 8Alkylidene group or cyclohexylidene.
4. the composition of claim 2, wherein the alkoxylamine of component (i) is selected from:
1-cyclohexyl oxygen base-2,2,6,6-tetramethyl--4-octadecyl amino piperidine;
Two (1-octyloxy-2,2,6,6-tetramethyl piperidine-4-yl) sebate;
2, two [(1-cyclohexyl oxygen base-2,2,6,6-tetramethyl piperidine-4-yl) the butyl amino]-6-(2-hydroxyl-ethylamino-s-s-triazine of 4-;
Two (1-cyclohexyl oxygen base-2,2,6,6-tetramethyl piperidine-4-yl) adipic acid ester;
2, two [(1-cyclohexyl oxygen base-2,2,6,6-tetramethyl piperidine-4-yl) butyl the amino]-6-chloro-s-triazines of 4-;
1-(2-hydroxy-2-methyl propoxy-)-4-hydroxyl-2,2,6, the 6-tetramethyl piperidine;
1-(2-hydroxy-2-methyl propoxy-)-4-oxo-2,2,6, the 6-tetramethyl piperidine;
1-(2-hydroxy-2-methyl propoxy-)-4-octadecane acyl-oxygen base-2,2,6, the 6-tetramethyl piperidine;
Two (1-(2-hydroxy-2-methyl propoxy-)-2,2,6,6-tetramethyl piperidine-4-yl) sebate;
Two (1-(2-hydroxy-2-methyl propoxy-)-2,2,6,6-tetramethyl piperidine-4-yl) adipic acid ester;
2,4-pair N-[1-(2-hydroxy-2-methyl propoxy-)-2,2,6,6-tetramethyl piperidine-4-yl]-N-butyl amino }-6-(2-hydroxyethyl amino)-s-triazine;
2, two [(1-cyclohexyl oxygen base-2,2,6,6-tetramethyl piperidine-4-yl) butyl amino]-6-chloro-s-triazine and the N of 4-, N '-two (3-aminopropyl) quadrol) reaction product;
2, two [(1-cyclohexyl oxygen base-2,2,6,6-tetramethyl piperidine-4-yl) the butyl amino]-6-(2-hydroxyl-ethylamino-s-s-triazine of 4-;
Oligomeric compound, it is 4,4 '-hexa-methylene-two (amino-2,2,6, the 6-tetramethyl piperidine) and 2,4-two chloro-6-[(1-cyclohexyl oxygen bases-2,2,6,6-tetramethyl piperidine-4-yl) butyl amino]-condensation product of s-triazine, it is with 2-chloro-4, two (the dibutylamino)-s-triazine end-blockings of 6-; With
The compound of following general formula
Wherein, n is 1 to 15.
5. the composition of claim 1, wherein the organic halogen fire retardant (ii) is selected from:
The chlorine alkyl phosphate,
Three (2-chloroethyl) phosphoric acid ester,
Many bromos phenyl ether,
Decabromodiphynly oxide,
Three [3-bromo-2, two (monobromethane) propyl group of 2-] phosphoric acid ester,
Three (2, the 3-dibromopropyl) phosphoric acid ester,
Three (2,3-two chloropropyls) phosphoric acid ester,
Chlorendic acid,
Tetrachlorophthalic acid,
Tetrabromophthalate,
It is two-(N, N '-hydroxyethyl) tetrachlorobenzene diamines,
It is poly--β-chloroethyl tri methylene phosphonic acid ester mixture,
Two (2,3-dibromopropyl ether) of tetrabromo-bisphenol,
Brominated epoxy resin,
Ethylidene-two (tetrabromo phthalimide),
Two (hexachlorocyclopentadiene base) cyclooctane,
Clorafin,
Octabromodiphenyl ether,
The hexachlorocyclopentadiene derivative,
1, two (tribromophenoxy) ethane of 2-,
Tetrabromo-bisphenol,
Ethylenebis-(two bromo-norbornane dicarboximides),
It is two-(hexachlorocyclopentadiene base) cyclooctane,
PTFE
Three-(2, the 3-dibromopropyl)-isocyanuric acid ester and
Ethylidene-two-tetrabromo phthalimide.
6. the composition of claim 1, wherein the organic halogen fire retardant (ii) is the organic bromine fire retardant.
7. the composition of claim 1, wherein thermoplastic resin (a) is polypropylene, polyethylene, propylene/ethylene copolymer or polystyrene.
8. the composition of claim 1, wherein component (i) is 1: 5 to 1: 200 with component weight ratio (ii).
9. the composition of claim 1, wherein the synergistic mixt of component (b) is that the amount of 5% to 20% weight exists with the weight based on component (a).
10. the composition of claim 1, it also comprises the melamine based flameproofing.
11. the composition of claim 1, it comprises based on the weight of component (a) filler less than 3% weight.
12. the composition of claim 1, wherein acid scavenger is selected from natural or synthetic hydrotalcite and amorphous alkaline aluminium carbonate magnesium.
13. the composition of claim 1, wherein acid scavenger is that 0.1% to 1.0% weight exists with the weight based on component (a).
14. the electric component composition of claim 1, it is plug, socket or wire insulation material.
CNB2003801016346A 2002-10-17 2003-10-09 Flame retardant polymeric electrical parts Expired - Lifetime CN100352852C (en)

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