CN101437886B - Derivatives of pyrimidines as flame retardants - Google Patents

Derivatives of pyrimidines as flame retardants Download PDF

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CN101437886B
CN101437886B CN2007800158475A CN200780015847A CN101437886B CN 101437886 B CN101437886 B CN 101437886B CN 2007800158475 A CN2007800158475 A CN 2007800158475A CN 200780015847 A CN200780015847 A CN 200780015847A CN 101437886 B CN101437886 B CN 101437886B
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butyl
ester
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CN101437886A (en
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M·罗思
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BASF Schweiz AG
Ciba SC Holding AG
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    • 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
    • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
    • C08K5/3462—Six-membered rings
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/016—Flame-proofing or flame-retarding additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0066—Flame-proofing or flame-retarding additives

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Abstract

The present invention pertains to a composition comprising an organic polymer, a derivative of a pyrimidine and a further flame retardant. The present invention also pertains to a process for flame retarding an organic polymer by applying thereto or incorporating therein a derivative of a pyrimidine, optionally in combination with a further flame retardant.

Description

Pyrimidine derivatives as fire retardant
The present invention relates to a kind of composition that includes organic polymer, pyrimidine derivatives and further fire retardant.The present invention also relates to a kind of flame resistant method of organic polymer, comprise to its use or mix therein a kind of pyrimidine derivatives, randomly with a kind of further flame retardant combination.
WO-A-03/082967 discloses the pyrimidine derivatives as the stablizer in the polyester, for example 6-amino uracil, 6-amino-1-6-Methyl Uracil or 6-amino-1,3-dimethyl uracil.EP-A-1,304,352, WO-A-00/12,608, EP-A-0 has described nuclear alkali (nucleobases) derivative as fire retardant in the polymkeric substance in 661,342 and EP-A-1,630,203.
US-A-5,925,696 have described the chlorine-containing polymer stabilizer blend.
US-A-5,859,100 disclose and have used N, the N-dimethyl-stable hard PVC of 6-amino uracil.
US-A-4,656,209 have described with the stable chlorinated thermoplastic plastics of amino uracil.
EP-A-65,934 also disclose with the stable chlorine-containing thermoplastic resin of amino uracil.
US-A-6,156,830 relate to as the 5-replacement-6-amino uracil of halogenated polymer with stablizer.
US-A-5,373,038 have described the plastics of anti-combustion that contain barbituric acid guanidine or thiobarbituricacid guanidine.
The compound of formula (I)～(XII) can advantageously be used as fire retardant, is particularly useful in the organic polymer.They can have improved thermostability and less or do not have a corrosion behavior.They especially can be used for making fire-retardant injection molded article, for example, are used for appliance applications or electronic application person.Fire retardant of the present invention especially can tolerate hydrolysis, therefore, contacts with water and may not reduce its fire retardancy.Dripping of said composition dropped down and can significantly be reduced when the composition that comprises fire retardant of the present invention was met fire.The The compounds of this invention of formula (I)～(XII) can replace halogenated flame, antimony compounds and/or filler, or the The compounds of this invention of formula (I)～(XII) can make its quantity reduce at least.
Useful is a kind of composition that comprises following ingredients
A) a kind of organic polymer, prerequisite are that this organic polymer is different from vinyl chloride-base polymer or vinyl chloride copolymer,
B) compound of formula (I)～(XII) and
C) a kind of further fire retardant,
Figure G2007800158475D00021
(I)
Figure G2007800158475D00022
(II)
Figure G2007800158475D00023
(III)
Figure G2007800158475D00024
(IV)
(V)
Figure G2007800158475D00026
(VI)
Figure G2007800158475D00027
(VII) (VIII)
Figure G2007800158475D00029
(IX)
Figure G2007800158475D000210
(X)
(XI)
Figure G2007800158475D000212
(XII)
In the formula
N is 1 or 2,
X is O, S or NH,
Z-is a kind of negatively charged ion of mineral acid,
R 1And R 2Be H, glycidyl, COO-R independently of one another 8, OCO-R 9, CO-R 9, CO-NR 8R 10Or a kind of nothing that is selected from a group of following composition replaces or substituted radical: C is arranged 1-C 18Alkyl, C 3-C 18Thiazolinyl, C 3-C 6Alkynyl, C 5-C 8Cycloalkyl, C 5-C 8Cycloalkenyl group, C 6-C 12Aryl, C 7-C 14Aralkyl, C 8-C 12Arylalkenyl, C 8-C 12Sweet-smelling alkynyl, C 1-C 18Alkoxyl group, C 3-C 18Alkene oxygen base, C 3-C 6Alkynyloxy group, C 6-C 12Aryloxy, and C 7-C 14Aralkoxy,
R 3And R 5Same independently of one another R 1Definition,
NR 3R 5And R 4Can also lump together the part of the 5 Yuans ring systems of oedoeagus (anellated) that become formula (XIIIa)～(XIIIe),
(XIIIa)
Figure G2007800158475D00032
(XIIIb)
Figure G2007800158475D00033
(XIIIc) (XIIId)
(XIIIe)
Be under 1 the situation at n,
R 4Be halogen, NO, CN, NR 3R 5, NHR 3R 5 +Z -, furanonyl or same R 1Definition,
Be under 2 the situation at n,
R 4Be that a kind of nothing that is selected from a group of following composition replaces or replacement double-basis: C arranged 1-C 18Alkylidene group and C 7-C 14Inferior aralkyl,
R 6Same R 1Definition,
R 7Same R 2Definition,
R 8And R 10Be H or same R independently of one another 9Definition;
R 9Be that a kind of nothing that is selected from a group of following composition replaces or substituted radical: C arranged 1-C 18Alkyl, C 3-C 18Thiazolinyl, C 3-C 6Alkynyl, C 5-C 8Cycloalkyl, C 5-C 8Cycloalkenyl group, C 6-C 12Aryl, C 7-C 14Aralkyl, C 8-C 12Arylalkenyl and C 8-C 12Sweet-smelling alkynyl,
Replaced by one or more groups that are selected from following a group of forming by the alkylidene group, inferior aralkyl, alkyl, thiazolinyl, alkynyl, cycloalkyl, cycloalkenyl group, aryl, aralkyl, arylalkenyl, sweet-smelling alkynyl, alkoxyl group, alkene oxygen base, alkynyloxy group, aryloxy and the aralkoxy that replace: halogen, hydroxyl, nitro, cyano group, COO-R 13, CONR 13R 14, OCO-R 15, NR 13CO-R 15, NR 13R 14, COR 15, and O-R 15,
Or be to replace by one or more groups that are selected from following a group of forming on the aryl: C by the inferior aralkyl, aryl, aralkyl, arylalkenyl, sweet-smelling alkynyl, aryloxy and the aralkoxy that replace 1-C 18Alkyl, C 3-C 18Thiazolinyl, and C 3-C 6Alkynyl,
R 11' be H, C 1-C 18Alkyl, C 3-C 18Thiazolinyl, C 3-C 6Alkynyl, C 5-C 8Cycloalkyl, C 5-C 8Cycloalkenyl group, C 6-C 12Aryl, C 7-C 14Aralkyl, C 8-C 12Arylalkenyl, C 8-C 12Sweet-smelling alkynyl, COO-R 13, CONR 13R 14, OCO-R 15, NR 13CO-R 15, NR 13R 14Or CO-R 15,
R 11And R 12Be O-R independently of one another 15Or same R 11' definition,
R 13And R1 4Be H or same R independently of one another 15Definition,
R 15Be C 1-C 18Alkyl, C 3-C 18Thiazolinyl, C 3-C 6Alkynyl, C 5-C 8Cycloalkyl, C 5-C 8Cycloalkenyl group, C 6-C 12Aryl, C 7-C 14Aralkyl, C 8-C 12Arylalkenyl, or C 8-C 12Sweet-smelling alkynyl.
Be preferably a kind of composition, wherein the weight with this organic polymer is benchmark, and the amount of the compound of formula (I)～(XII) is 0.1～25.0%, is preferably 0.1～20%, and the amount of this further fire retardant is 0.5～45.0%.
Composition b) with composition c) weight ratio better be 1:10～10:1.
Better, the compound of formula (I)～(XII) is the compound of formula (I)～(X), the compound of formula (I) especially.
Examples for compounds, quantity, priority and the processing of formula (I)～(XII) can be summarized as follows.
Definition that below provides and example are applicable to all such terms herein.
For example, Z -Be a kind of inorganic anion, for example HSO 4 -, HSO 3 -, H 2PO 4 -, H 2BO 3 -, HBO 2 -, Cl -, Br -, ClO 4 -, two C 1-C 6The alkyl phosphinic acid root, the methylphosphine acid group, the Phenylphosphine acid group, the polyphosphoric acid root, pyrophosphate, or other place is defined herein.
This term of alkyl comprises, for example, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, the 2-ethyl-butyl, n-pentyl, isopentyl, the 1-methyl amyl, 1, the 3-dimethylbutyl, n-hexyl, 1-methyl hexyl, n-heptyl, the 2-methylheptyl, 1,1,3, the 3-tetramethyl butyl, the 1-methylheptyl, the 3-methylheptyl, n-octyl, the 2-ethylhexyl, 1,1,3-trimethylammonium hexyl, 1,1,3,3-tetramethyl-amyl group, n-nonyl, positive decyl, the n-undecane base, 1-methyl undecyl, dodecyl, the Pentadecane base, n-hexadecyl and Octadecane base.
For example, cycloalkyl is cyclopentyl, cyclohexyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, suberyl or ring octyl group.In the compound of formula (I)～(XII), cycloalkyl is not preferably.
The example of thiazolinyl is an allyl group, and the branched isomer of butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonene base, decene base, undecenyl and dodecenyl succinic and non-branching isomer.This term of thiazolinyl also include more than one can conjugation or the residue of unconjugated pair of key, for example can comprise a two key.
For example, cycloalkenyl group is cyclopentenyl, cyclohexenyl, methyl cyclopentene base, dimethylcyclopentene base or methyl cyclohexane thiazolinyl.Cycloalkenyl group can comprise more than one can conjugation or unconjugated pair of key, for example can comprise a two key.Cycloalkenyl group is not preferably.
The example of alkynyl is 1-proyl, 2-propynyl, butynyl, pentynyl, hexin base, heptyne base, octyne base, n-heptylacetylene base, decynyl, hendecyne base and dodecyne base.This term of alkynyl includes the one or more triple bonds and the residue of one or more pairs of keys randomly, and wherein this unsaturated link(age) can be a conjugated or unconjugated, for example comprises a triple bond.Alkynyl is not preferably.
Aryl is, for example, and phenyl or naphthyl, better phenyl.
Aralkyl is, for example, and benzyl, 1-or 2-phenylethyl, 3-phenyl propyl or 1,1-dimethyl benzyl, better benzyl.
The example of arylalkenyl is the 2-phenyl vinyl, and the example of sweet-smelling alkynyl is a 2-phenylacetylene base.
This term of alkoxyl group comprises, for example, methoxyl group and oxyethyl group, and propoxy-, butoxy, pentyloxy, hexyloxy, heptan oxygen base, octyloxy, the ninth of the ten Heavenly Stems oxygen base, the last of the ten Heavenly stems oxygen base, undecane oxygen base, dodecyloxy, tridecane oxygen base, tetradecyloxyaniline, pentadecane oxygen base, n-Hexadecane oxygen base, heptadecane oxygen base and octadecane oxygen base.
For example, cycloalkyloxy means that the cycloalkyl of above definition is connected with O.
For example, alkene oxygen base system refers to that the thiazolinyl of above definition is connected with O.Alkene oxygen base is not preferably.
For example, alkynyloxy group means that the alkynyl of above definition is connected with O.Alkynyloxy group is not preferably.
For example, aryloxy means that the aryl of above definition is connected with O.
For example, aralkoxy means that the aralkyl of above definition is connected with O.
The example of halogen is F, Cl, Br and I, especially Cl and Br, particularly Cl.
The example of alkylidene group is a methylene radical, ethylidene, propylidene, isopropylidene, inferior normal-butyl, inferior sec-butyl, isobutylidene, the inferior tertiary butyl, 2-ethyl butylidene, inferior n-pentyl, isopentylidene, 1-methyl pentylidene, 1,3-dimethyl butylidene, inferior n-hexyl, 1-methyl hexylidene, inferior n-heptyl, the inferior heptyl of 2-methyl, 1,1,3,3-tetramethyl-butylidene, the inferior heptyl of 1-methyl, the inferior heptyl of 3-methyl, inferior n-octyl, 2-ethyl hexylidene, 1,1,3-trimethylammonium hexylidene, 1,1,3,3-tetramethyl-pentylidene, nonamethylene, inferior decyl, inferior undecyl, inferior undecyl of 1-methyl and inferior dodecyl.
The example of cycloalkylidene is cyclopentylidene, 1-methyl cyclopentylidene, cyclohexylidene, 1-methyl cyclohexylidene, inferior suberyl, the inferior suberyl of 2-methyl, the inferior suberyl of 1-methyl, the inferior suberyl of 3-methyl, inferior ring octyl group, 2-ethyl cyclohexylidene, 1,1,3-trimethylammonium cyclohexylidene, 1,1,3,3-tetramethyl-cyclopentylidene, inferior ring nonyl, inferior ring decyl, inferior ring undecyl, 1-methyl inferior ring undecyl and inferior cyclo-dodecyl.
The example of inferior cycloalkenyl group is cyclopentenylidene, 1-methyl cyclopentenylidene, phenylidene, 1-methyl phenylidene, inferior cycloheptenyl, the inferior cycloheptenyl of 2-methyl, the inferior cycloheptenyl of 1-methyl, the inferior cycloheptenyl of 3-methyl, inferior cyclooctene base, 2-ethyl phenylidene, 1,1,3-trimethylammonium phenylidene, 1,1,3,3-tetramethyl-cyclopentenylidene, inferior cyclonoene base, inferior cyclodecene base, inferior ring undecenyl, 1-methyl inferior ring undecenyl and inferior ring dodecenyl succinic.
Inferior aralkyl is, for example, and benzylidene, 1-or 2-phenyl ethylidene, 3-phenyl propylidene or 1,1-dimethyl benzylidene, better benzylidene.
Arylidene is, for example, and phenylene.
Alkarylene is, for example, and methylphenylene or dimethyl phenylene.
Better, this further fire retardant is selected from a group of following composition: phosphonium flame retardant contains nitrogen combustion inhibitor, halogenated flame, and inorganic combustion inhibitor, especially phosphonium flame retardant and contain nitrogen combustion inhibitor.
Best, this further fire retardant is selected from a group of following composition: melamine flame retardant, sterically hindered alkoxylamine compound, the luxuriant and rich with fragrance oxide compound of dihydro oxa-phosphorus, organophosphate, the salt of organic phospho acid, with the salt of organic diphosphinic acid, the perhaps salt of phospho acid or diphosphinic acid.
Useful is a kind of so further fire retardant, and melamine flame retardant for example is as sterically hindered alkoxylamine compound, as the luxuriant and rich with fragrance oxide compound of dihydro oxa-phosphorus, as organic phosphoric acid ester, as the salt of organic phospho acid, as the salt of organic diphosphinic acid, the perhaps salt of phospho acid or diphosphinic acid.
Further example, quantity, priority and the processing of fire retardant are summarized as follows.
Also useful is a kind of composition that also comprises at least a further additive.
Better, this further additive is selected from a group of following composition: antioxidant, ultraviolet ray (UV) absorption agent, photostabilizer, metal passivator, phosphite, phosphinates, azanol class, nitrone class, sulfo-synergism compound, peroxide breakdown compound, polyamine stabilizers, the alkaline auxiliary stablizer, nucleating agent, filler, toughener, softening agent, lubricant, emulsifying agent, pigment, rheological additives, catalyzer, mobile activator, white dyes, antistatic agent, whipping agent, benzofuranone and dihydroindole ketone.
Further example, quantity, priority and the processing of additive are summarized as follows.
Useful is a kind of flame resistant method of organic polymer, comprises to wherein using or mix therein a kind of formula (I)～(XII) compound.
It better is above such composition.
Useful especially is a kind of flame resistant method of organic polymer, comprises to the compound of wherein using or mix therein a kind of formula (I)～(XII) as fire retardant, wherein
N is 1 or 2,
X is O, S or NH,
Z-is HSO 4 -, 1/2SO 4 2-, HSO 3 -, 1/2SO 3 2-, H 2PO 4 -, 1/2HPO 4 2-, 1/3PO 4 3-, H 3P 2O 7 -, 1/2H 2P 2O 7 2-, 1/3HP 2O 7 3-, 1/4P 2O 7 4-, H 4P 3O 10 -, 1/2H 3P 3O 10 2-, 1/3H 3P 3O 10 3-, 1/4H 3P 3O 10 4-, 1/5H 3P 3O 10 5-, H 5P 4O 13 -, 1/2H 4P 4O 13 2-, 1/3H 3P 4O 13 3-, 1/4H 2P 4O 13 4-, 1/5HP 4O 13 5-, 1/6P 4O 13 6-, H 2PO 2 -, H 2PO 3 -, 1/2HPO 3 2-, H 2BO 3 -, HBO 2 -, Cl -, Br -, I -, ClO 4 -, (C 1-C 6Alkyl) 2PO 2 -, (C 1-C 6Alkyl) HPO 3 -Or 1/2 (C 1-C 6Alkyl) PO 3 2-,
R 1And R 2Be H independently of one another, glycidyl, COO-R 8, OCO-R 9, CO-R 9, CO-NR 8R 10Or be selected from a kind of nothing replacement of one group of following composition or substituted radical: C is arranged 1-C 18Alkyl, C 3-C 18Thiazolinyl, C 5-C 8Cycloalkyl, C 5-C 8Cycloalkenyl group, C 6-C 12Aryl, C 7-C 14Aralkyl, C 8-C 12Arylalkenyl, C 1-C 18Alkoxyl group, C 3-C 18Alkene oxygen base, C 6-C 12Aryloxy and C 7-C 14Aralkoxy,
R 3And R 5Same independently of one another R 1Definition,
NR 3R 5And R 4Can also become the part of 5 Yuans ring systems of oedoeagus of formula (XIIIa)～(XIIIe) together,
Figure G2007800158475D00071
(XIIIa)
Figure G2007800158475D00072
(XIIIb)
Figure G2007800158475D00073
(XIIIc) (XIIId)
(XIIIe)
Be under 1 the situation at n,
R 4Be halogen, NO, CN, NR 3R 5, NHR 3R 5 +Z -, furanonyl, or same R 1Definition,
Be under 2 the situation at n,
R 4Be that a kind of nothing that is selected from a group of following composition replaces or replacement double-basis: C arranged 1-C 18Alkylidene group and C 7-C 14Inferior aralkyl,
R 6Same R 1Definition,
R 7Same R 2Definition,
R 8And R 10Be H or same R independently of one another 9Definition;
R 9Be that a kind of nothing that is selected from a group of following composition replaces or substituted radical: C arranged 1-C 18Alkyl, C 3-C 18Thiazolinyl, C 5-C 8Cycloalkyl, C 5-C 8Cycloalkenyl group, C 6-C 12Aryl, C 7-C 14Aralkyl and C 8-C 12Arylalkenyl,
Should be replaced by one or more groups that are selected from following a group of forming by the alkylidene group, inferior aralkyl, alkyl, thiazolinyl, cycloalkyl, cycloalkenyl group, aryl, aralkyl, arylalkenyl, alkoxyl group, alkene oxygen base, aryloxy and the aralkoxy that replace: halogen, hydroxyl, nitro, cyano group, COO-R 13, CONR 13R 14, OCO-R 15, NR 13CO-R 15, NR 13R 14, CO-R 15And O-R 15,
Or be to replace by one or more groups that are selected from following a group of forming on the aryl: C by the aryl, inferior aralkyl, aralkyl, arylalkenyl, aryloxy and the aralkoxy that replace 1-C 18Alkyl and C 3-C 18Thiazolinyl,
R 11' be H, C 1-C 18Alkyl, C 3-C 18Thiazolinyl, C 5-C 8Cycloalkyl, C 5-C 8Cycloalkenyl group, C 6-C 12Aryl, C 7-C 14Aralkyl, C 8-C 12Arylalkenyl, COO-R 13, CONR 13R 14, OCO-R 15, NR 13CO-R 15, NR 13R 14Or CO-R 15,
R 11And R 12Be O-R independently of one another 15Or same R 11' definition,
R1 3And R 14Be H or same R independently of one another 15Definition,
R 15Be C 1-C 18Alkyl, C 3-C 18Thiazolinyl, C 5-C 8Cycloalkyl, C 5-C 8Cycloalkenyl group, C 6-C 12Aryl, C 7-C 14Aralkyl or C 8-C 12Arylalkenyl.
Useful especially is a kind of flame resistant method of organic polymer, comprises to the compound of wherein using or mix therein formula (I)～(XII), wherein
N is 1 or 2,
X is O or NH,
Z -Be HSO 4 -, 1/2SO 4 2-, HSO 3 -, 1/2SO 3 2-, H 2PO 4 -, 1/2HPO 4 2-, 1/3PO 4 3-, H 2PO 2 -, H 2PO 3 -, 1/2HPO 3 2-, Cl -, Br -, I -, (C 1-C 6Alkyl) 2PO 2 -, (C 1-C 6Alkyl) HPO 3-or 1/2 (C 1-C 6Alkyl) PO 3 2-,
R 1And R 2Be H independently of one another, glycidyl, COO-R 8, OCO-R 9, CO-R 9, or be selected from one group nothing replacement of following composition or substituted radical: C is arranged 1-C 18Alkyl, C 3-C 6Thiazolinyl, C 6Aryl, C 7-C 14Aralkyl, C 1-C 18Alkoxyl group, C 6-C 12Aryloxy and C 7-C 14Aralkoxy,
R 3And R 5Same independently of one another R 1Definition,
NR 3R 5And R 4Can also lump together a part that becomes 5 Yuans ring systems of the oedoeagus of formula (XIIIa)～(XIIIe),
Figure G2007800158475D00091
(XIIIa)
Figure G2007800158475D00092
(XIIIb)
Figure G2007800158475D00093
(XIIIc)
Figure G2007800158475D00094
(XIIId)
Figure G2007800158475D00095
(XIIIe)
Be under 1 the situation at n,
R 4Be halogen, NO, CN, NR 3R 5, NHR 3R 5 +Z -, furanonyl or same R 1Definition,
Be under 2 the situation at n,
R 4Be to be selected from one group nothing replacement of following composition or replacement double-basis: C is arranged 1-C 18Alkylidene group and C 7-C 14Inferior aralkyl,
R 6And R 7Be H,
R 8Be H or same R 9Definition;
R 9Be to be selected from one group nothing replacement of following composition or substituted radical: C is arranged 1-C 18Alkyl, C 3-C 6Thiazolinyl, C 6Aryl and C 7-C 14Aralkyl,
Replaced by one or more groups that are selected from following a group of forming by the alkylidene group, inferior aralkyl, alkyl, thiazolinyl, aryl, aralkyl, alkoxyl group, aryloxy and the aralkoxy that replace: halogen, hydroxyl, nitro, cyano group, COO-R 13, OCO-R 15, NR 13R 14, CO-R 15And O-R 15,
Or be selected from by one or more that following one group the group of forming replaces: C on aryl by the aryl, inferior aralkyl, aralkyl, aryloxy and the aralkoxy that replace 1-C 18Alkyl and C 3-C 6Thiazolinyl,
R 11' be H, C 1-C 18Alkyl, C 3-C 6Thiazolinyl, C 6Aryl, C 7-C 14Aralkyl, COO-R 13, OCO-R 15, NR 13R 14Or CO-R 15,
R 11And R 12Be O-R independently of one another 15Or same R 11' definition,
R 13And R 14Be H or same R independently of one another 15Definition,
R 15Be C 1-C 18Alkyl, C 3-C 6Thiazolinyl, C 6Aryl or C 7-C 14Aralkyl.
Further useful is a kind of flame resistant method of organic polymer, comprises to the compound of wherein using or mix therein formula (I)～(X), wherein
N is 1,
X is O or NH,
Z -Be H 2PO 4 -, HSO 4 -, 1/2SO 4 2-, Cl -Or Br -,
R 1And R 2Be H or a kind of unsubstituted group of one group that is selected from following composition: C independently of one another 1-C 18Alkyl and C 3-C 6Thiazolinyl,
R 3And R 5Independently of one another with the definition of R1,
R 4Be NR 3R 5, NHR 3R 5 +Z -Or same R 1Definition,
R 6And R 7Be H.
Useful very especially is a kind of flame resistant method of organic polymer, comprises to wherein using or mix therein formula (I) compound, wherein
N is 1,
X is 0,
R 1And R 2Be H or C independently of one another 1-C 6Alkyl and
R 3, R 4And R 5Same independently of one another R 1Definition.
Useful more especially is a kind of flame resistant method of organic polymer, comprises to wherein using or mix therein formula (I) compound, wherein
N is 1,
X is 0,
R 1And R 2Be H or C independently of one another 1-C 6Alkyl and
R 3, R 4And R 5Be H.
Specifically, useful is the compound of formula (I)～(XII), and this is corresponding to following various (comprising such as its tautomeric form):
　　
Figure G2007800158475D00102
　　
Figure G2007800158475D00103
　　　
The 6-amino uracil; The 5-amino uracil; 1-methyl-6-amino uracil; 1,3-dimethyl-6-amino uracil;
Figure G2007800158475D00111
　　　　　　
Figure G2007800158475D00112
　　
Figure G2007800158475D00113
1-allyl group-6-amino uracil; 5,6-diamino uridylic 2,5,6-triamino-4-pyrimidone;
Figure G2007800158475D00114
Figure G2007800158475D00115
　　　　　　
Figure G2007800158475D00116
2,6-diamino-4-pyrimidone; 1,3-dimethyl-4,5-diamino uridylic; 2,6-diamino uridylic;
　　　　
Figure G2007800158475D00118
　　　
Figure G2007800158475D00119
5,6-diamino uridylic vitriol; 5,6-diamino uridylic 4-hydroxyl-2,5,6-Triaminopyrimidine vitriol.
Hydrochloride;
Good especially is 6-amino uracil, 5-amino uracil, 6-amino-1,3-dimethyl uracil or 6-amino uracil phosphoric acid salt.
For example, formula (I)～(XII) compound is known compound, commercially available product, maybe can obtains with currently known methods.
Be preferably a kind of organic polymer flame resistant method, comprise to formula (I)～(XII) compound of wherein using or mixing therein with at least a further flame retardant combination.
For example, this further fire retardant is selected from a group of following composition: phosphonium flame retardant contains nitrogen combustion inhibitor, halogenated flame, and inorganic combustion inhibitor, especially phosphonium flame retardant and contain nitrogen combustion inhibitor.Compare with other further fire retardant, halogenated flame is less useful.
Better, this further fire retardant is a kind of melamine or urea flame retardant, sterically hindered alkoxylamine compound, dicumyl compounds, the luxuriant and rich with fragrance oxide compound of dihydro oxa-phosphorus, organophosphate, the salt of organic phospho acid, the salt of organic diphosphinic acid or the salt of phospho acid or diphosphinic acid.
Useful is so further fire retardant, and melamine flame retardant for example is as sterically hindered alkoxylamine compound, as the luxuriant and rich with fragrance oxide compound of dihydro oxa-phosphorus, as organic phosphoric acid ester, as the salt of organic phospho acid, as the salt of organic diphosphinic acid.
This further fire retardant can be a compound known, commercially available, also can obtain with currently known methods.
This phosphonium flame retardant advantageously melamine or its condensation product and a kind of phosphorated acid is a kind of monobasic phosphorated acid phosphoric acid of for example all having only an acid equivalent under each situation, phosphonic acids or better phospho acid; More particularly, the phosphonate ester of being considered, better alkyl phosphinates.Cation constituent is, for example, and the more senior condensation product of melamine, melam, melem or melamine, better melamine or melam.For example EP-A-363 is seen in such salt and preparation thereof, 321 and WO-A-01/57051.
Being particularly suitable for being used as what contain the phosphine fire retardant is the salt of organic phospho acid or diphosphinic acid, especially the salt of formula (100) and (101)
Figure G2007800158475D00121
Figure G2007800158475D00122
In the formula
E 1And E 2Identical or different, be H, C 1-C 6Alkyl, C especially 1-C 4Alkyl or C 6-C 10Aryl;
E 3Be C 1-C 10Alkylidene group, C 6-C 10Arylidene, C 6-C 10Alkyl arylene or C 6-C 10Aryl alkylene;
M is the condenses of magnesium, calcium, aluminium, zinc, melamine or melamine,
m 1Be 1,2 or 3;
n 1Be 1 or 3 and
X is 1 or 2.
M better is Zn, Al, melamine, melam or melem, especially Zn or Al.Aryl and arylidene, alkyl arylene and aryl alkylene comprise, for example, phenyl, naphthyl, tolyl, xylyl, ethylbenzene base,
Figure G2007800158475D0012154509QIETU
Base, propyl phenyl or trimethylphenylmethane base and phenylene, naphthylidene, methylphenylene, ethyl phenylene or tertiary butyl phenylene, methyl naphthylidene, ethyl naphthylidene, tertiary butyl naphthylidene, Ben Yajiaji, benzene propylidene and corresponding tolyl and xylyl analogue.
For example, phosphonium flame retardant is the luxuriant and rich with fragrance oxide compound of dihydro oxa-phosphorus, especially following various person is arranged
Figure G2007800158475D00141
Figure G2007800158475D00142
Or
Figure G2007800158475D00143
For example, phosphonium flame retardant is for example bisphosphate four phenyl ester resorcinol, bisphosphate four phenyl ester dihydroxyphenyl propane esters, bisphosphate four phenyl esters 4 of organophosphate, 4 '-dihydroxybiphenyl ester, triphenylphosphate, resorcinol diphosphate oligopolymer (RDP), bisphosphate dihydroxyphenyl propane ester oligomer (BBP), bisphosphate 4,4 '-dihydroxybiphenyl ester oligomer, resorcinol diphosphate (RDP), trioctyl phosphate or Tritolyl Phosphate.
The example of phosphonium flame retardant also has: sulfuration four (methylol) Phosphonium, N, N-two (2-hydroxyethyl) amino methyl phosphonic acid diethyl ester, the hydroxyalkyl of phosphoric acid, ammonium polyphosphates (APP), or phosphonitrile fire retardant and bisphosphate quadrol (EDAP).
For example, containing nitrogen combustion inhibitor is melamine flame retardant, isocyanuric acid ester fire retardant or sterically hindered alkoxylamine compound.
The melamine flame retardant is, for example, is selected from one group of following composition: the acid of cyanogen urea melamine, melamine borate, melamine phosphate, polyphosphoric acid melamine, melamine pyrophosphate, polyphosphoric acid melamine ammonium and melamine pyrophosphate ammonium.
For example, the isocyanuric acid ester fire retardant is a polyisocyanurate, the ester of isocyanuric acid or isocyanuric acid ester.Representative example is an isocyanide urea carboxylic hydroxyalkyl, for example isocyanuric acid three (2-hydroxy methacrylate), isocyanuric acid three (hydroxyl methyl esters), isocyanuric acid three (3-hydroxyl n-propyl) or isocyanuric acid three (glycidyl ester).
Sterically hindered alkoxylamine compound is corresponding to for example formula (102)
Figure G2007800158475D00151
G in the formula 1And G 2Be C independently of one another 1-C 8Alkyl, or to lump together be pentamethylene or hexa-methylene, and each all better is C 1-C 4Alkyl, methyl especially,
Z 1And Z 2Each all is a methyl, or Z 1And Z 2Lumping together is a bridging group that is particularly useful for finishing 5 Yuans rings or 6 Yuans better piperidine rings of ring, can be not have to replace for resulting N-heterocycle, perhaps has ester group, ether, amide group, amino, carboxyl or urethano to replace,
E is that alkoxyl group, alkene oxygen base, cycloalkyloxy, aralkoxy, aryloxy or O-T-(OH) b and T are C 1-C 18Alkylidene group, C 5-C 18Cycloalkylidene, C 5-C 18Inferior cycloalkenyl group or have phenyl to replace or 1 or 2 C is arranged 1-C 4The C that the phenyl that alkyl replaces replaces 1-C 4Alkylidene group, b be 1,2 or 3 and b be not more than the number of carbon atom among the T, and each hydroxyl all is bonded on the different carbon atoms when b is 2 or 3.
E better is C 1-C 18Alkoxyl group, C 5-C 6Cycloalkyloxy or the C that has 1～3 OH base to replace 1-C 18Alkoxyl group.
The example of the sterically hindered alkoxylamine of formula (102) can be consulted US-A-4983737, US-A-5047489 and US-A-5077340, and GB-A-2373507 (especially walks to the 31st page of the 1st row for the 7th page the 1st; Walk to the 52nd page of countdown line 3 for the 48th page the 10th) and WO-A-03/050175 (especially the 11st page of inverse the 2nd walks to the 37th page of last column; Walk to countdown line 3 for the 54th page the 9th; The 61/62nd page of compound N OR1～NOR12).The part of being mentioned will be considered as the integral part of present patent application.
Representative halogenated flame is, for example:
Many bromos phenyl ether, decabromo-diphenyl oxide, tricresyl phosphate [3-bromo-2,2-two (brooethyl) propyl ester], tricresyl phosphate (2,3-dibromo propyl ester), tricresyl phosphate (2,3-dichloro propyl ester), chlorendic acid, tetrachlorophthalic acid, tetrabromophthalate, many-β-chloroethyl tri methylene phosphonic acid ester mixture, tetrabromo-bisphenol two (2,3-dibromopropyl ether), brominated epoxy resin, second two (tetrabromo phthalimide), two (hexachlorocyclopentadiene also) cyclooctane, chloro paraffin, octabromodiphenyl ether, the hexachlorocyclopentadiene derivative, 1,2-two (tribromophenoxy) ethane, tetrabromo-bisphenol, second two (dibromo norbornane dicarboximide), two (chlordene cycloentadeno) cyclooctane, PTFE, isocyanuric acid three (2,3-dibromo propyl ester), with second two (tetrabromo phthalimide).
Common and the inorganic oxide synergistic agent combination of above-mentioned fire retardant.This purposes is modal to be zinc oxide or weisspiessglanz, as Sb 2O 3Or Sb 2O 5Boron compound also is suitable for.
The example of inorganic combustion inhibitor is metal hydroxides, metal oxide, aluminum compound fire retardant, boron compound, silicate, vitriol and carbonate, for example magnesium hydroxide, zinc oxide, molybdic oxide, Sb 2O 5, Sb 2O 3, silica, alumina trihydrate, alumina oxygen oxyhydroxide (boehmite), zinc borate, Calucium Silicate powder, Magnesium Silicate q-agent, calcium sulfate and magnesiumcarbonate.
The usage quantity of above-mentioned further fire retardant advantageously this organic polymer 0.5～45.0wt%, for example 1.0～25.0wt%, as 1.0～15.0wt%, 3.0～15.0wt% especially.
For example, this organic polymer is a kind of synthetic organic polymer, especially a kind of thermoplasticity or thermoset, particularly thermoplastic polymkeric substance.
Good especially organic polymer is a kind of polymeric amide, polyester or polycarbonate, and each all randomly contains a kind of toughener.
The example of organic polymer is:
1. the polymkeric substance of monoene and diene, for example polypropylene, polyisobutene, polybutene-1, poly--4-methylpentene-1, polyvinyl eyclohexane, polyisoprene or polyhutadiene, and the cycloolefin polymkeric substance of cyclopentenes or norbornylene for example; Also has polyethylene (randomly can be crosslinked), for example high density polyethylene(HDPE) (HDPE), HMW (high molecular weight)-high density polyethylene (HDPE-HMW), ultra-high molecular weight high density polyethylene(HDPE) (HDPE-UHMW), medium-density polyethylene (MDPE), new LDPE (film grade) (LDPE) and LLDPE (LLDPE), (VLDPE) and (ULDPE).
Polyolefine, the polymkeric substance of monoolefine is illustrational as epimere in other words, and especially polyethylene and polypropylene can in all sorts of ways, especially prepare in order to the below method:
A) with radical polymerization (usually under high pressure and high temperature);
B) use catalyzer, contain the catalyzer of one or more metals of IVb family, Vb family, VIb family or VIII family usually.These metals generally have one or more parts, for example oxide compound, halogenide, alcoholate, ester, ether, amine, alkyl, thiazolinyl and/or aryl, and these can be π coordinate or σ coordinate.Such metal complex can be a free, also can be fixed on the carrier, for example is fixed to active magnesium chloride, titanium chloride (III), aluminum oxide or silicon oxide.Such catalyzer can dissolve in or be insoluble in this polymerisation medium.This catalyzer can be to be exactly active originally in this polymerization, also can use further activator, for example metal alkyl, metal hydride, metal alkyl halides, metal alkyl oxide compound or metal alkyl oxygen alkane, this metal is the element of Ia family, IIa family and/or IIIa family.This activator can, for example, with further ester group, ether, amido or the modification of silicomethane ether.Such catalyst system abbreviates Phillips usually as, Standard Oil Indiana, Ziegler (Natta), TNZ (DuPont), metallocenes or single-point catalyst (SSC).
2. the 1st mixture of polymers of mentioning, for example mixture of polypropylene and polyisobutene, the mixture of polypropylene and polyethylene (for example PP/HDPE, PP/LDPE) and the mixture of dissimilar polyethylene (for example LDPE/HDPE).
Monoene and diene 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), propene/but-1-ene-1 multipolymer, propylene/isobutylene copolymers, ethylene/butylene-1 multipolymer, the ethylene/hexene multipolymer, ethene/methylpentene multipolymer, ethene/heptene multipolymer, ethylene/octene, ethylene/vinyl basic ring hexane multipolymer, ethene/cyclic olefine copolymer is ethene/norbornene copolymer (COC) for example, ethene/1-olefin copolymer wherein 1-alkene is an in-situ preparing, propylene/butadienecopolymer, iso-butylene/isoprene copolymer, ethylene/vinyl basic ring hexene copolymer, the ethylene/acrylic acid alkyl ester copolymer, the ethylene/methacrylic acid alkyl ester copolymer, ethylene, ethylene/acrylic acid copolymer and salt thereof (ionomer), and ethene and propylene and a kind of diene hexadiene for example, the terpolymer of dicyclopentadiene or inclined to one side ethylidene norbornene; And such multipolymer each other mixture or with the 1st mixture of polymers of mentioning, polypropylene-ethylene/propylene copolymer for example, the LDPE-ethylene, the LDPE-ethylene/acrylic acid copolymer, the LLDPE-ethylene, the LLDPE-ethylene/acrylic acid copolymer and alternately or the polyolefine-carbon monoxide multipolymer of random structure and with other polymkeric substance mixture of polymeric amide for example.
4. polystyrene, poly-(p-methylstyrene), poly-(alpha-methyl styrene).
5. from following vinyl aromatic monomers deutero-aromatic series homopolymer and multipolymer: vinylbenzene for example, alpha-methyl styrene, all isomer of Vinyl toluene are for example to Vinyl toluene, all isomer of ethyl styrene, propylstyrene, vinyl biphenyl, vinylnaphthalene, ethene anthracene and composition thereof; Homopolymer and multipolymer can have syndiotaxy, isotaxy, half isotaxy or atactic; Giving preferential is unregulated polymer.What also comprise is stereo-block polymer.
6a. comprise already mentioned vinyl aromatic monomers and the multipolymer that is selected from following comonomer: ethene, propylene, diene, nitrile, acids, maleic anhydride, toxilic acid acid amides, vinyl-acetic ester, acrylic acid derivative and composition thereof, phenylethylene/butadiene for example, styrene/acrylonitrile, styrene/ethylene (multipolymer), styrene/methacrylic acid alkane ester, phenylethylene/butadiene/alkyl acrylate and alkyl methacrylate, phenylethylene/maleic anhydride, styrene/acrylonitrile/methyl acrylate; By styrol copolymer and the another kind of polymkeric substance high impact mixture formed of polyacrylic ester, diene polymer or ethylene/propene/diene terpolymer for example; And cinnamic segmented copolymer, styrene/butadiene/styrene for example, styrene/isoprene/styrene, styrene/ethylene-butylene/styrene, or styrene/ethylene-propylene/styrene.
6b. the hydrogenation aromatic polymer of the hydrogenation preparing by the 6th polymkeric substance of mentioning, especially poly-cyclohexyl ethene (PCHE) often also abbreviates polyvinyl eyclohexane (PVCH) as, is the hydrogenation preparing by random isotactic polystyrene.
6c. the hydrogenation aromatic polymer of the hydrogenation preparing of the polymkeric substance of mentioning by the 6a item.
Homopolymer and multipolymer can have syndiotaxy, isotaxy, half isotaxy or atactic; Giving preferential is nonstereospecific polymer.What also comprise is stereoblock polymer.
7. the graft copolymer of vinyl aromatic monomers, for example styrene-grafted is in polyhutadiene, and styrene-grafted is in polyhutadiene/vinylbenzene or polybutadiene/acrylonitrile, and 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 be in acrylate/butadiene copolymers, and for example be known as those mixture such as so-called ABS, MBS, ASA or AES polymkeric substance with the 6th multipolymer of mentioning.
8. from α, beta-unsaturated acid and derivative derived polymers thereof, for example polyacrylic ester and polymethacrylate, or polymethylmethacrylate, polyacrylamide and with the impact-resistant modified polyacrylonitrile of butyl acrylate.
The 8th monomer of mentioning each other multipolymer or with the multipolymer of other unsaturated monomer, acrylonitrile/butadiene multipolymer for example, vinyl cyanide/alkyl acrylate ester copolymer, vinyl cyanide/alkyl acrylate oxyalkyl ester multipolymer, vinyl cyanide/halogen ethylene copolymer or vinyl cyanide/alkyl methacrylate/butadiene terpolymer.
10. from unsaturated alcohol and amine or its acyl derivative or acetal derived polymers, polyvinyl alcohol for example, polyvinyl acetate, stearic acid vinyl ester, vinyl benzoate or toxilic acid vinyl acetate, polyvinyl butyral, poly-O-phthalic allyl propionate, polyene propyl group melamine; And with the multipolymer of the 1st alkene of mentioning.
11. the homopolymer of cyclic ethers and multipolymer, for example multipolymer of polyalkylene glycol, polyethylene oxide, poly(propylene oxide) or itself and diglycidyl ether.
12. polyacetal, polyoxymethylene for example, and those contain for example polyoxymethylene of oxyethane of comonomer; Polyacetal with thermoplastic polyurethane, acrylate or MBS modification.
13. polyphenylene oxide, polyphenylene sulfide and with the mixture of styrene polymer or polymeric amide.
14. 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 is from m-xylene diamine and hexanodioic acid deutero-aromatic polyamide; Polyamide 6/I (poly-isophthaloyl hexamethylene-diamine), MXD (m-xylene diamine); From hexamethylene-diamine and m-phthalic acid and/or terephthalic acid and randomly a kind of elastomerics polymeric amide, for example poly-paraphenylene terephthalamide-2,4,4-trimethylhexamethylenediamine or poly as the properties-correcting agent preparation.Above-mentioned polymeric amide and polyolefine, olefin copolymer, ionomer or chemical bonding or grafted elastomerics or with polyethers for example with the segmented copolymer of polyoxyethylene glycol, polypropylene glycol or polytetramethylene glycol.The polymeric amide or the copolyamide of also useful EPDM or ABS modification; Polymeric amide (" RIM " polymeric amide) with condensation during the processing.
The example of operable polymeric amide and copolyamide is from such as ε-Ji Neixianan, hexanodioic acid, sebacic acid, dodecanedioic acid, m-phthalic acid, terephthalic acid, hexamethylene-diamine, tetramethylene-diamine, 2-methyl pentamethylene diamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, m-xylene diamine or two (3-methyl-4-aminocyclohexyl) methane deutero-;
And be semiaromatic polyamide composition, for example for example it consists of 70～95% polyamide 6s/6 and 5～30% polyamide 6s/I to polyamide 66/6I-; And terpolymer, wherein replaced the part of polyamide 6/6, for example it consists of 60～89% polyamide 6s/6,5～30% polyamide 6s/I and 1～10% another kind of fatty polyamide; The latter can be made up of for example polyamide 6, polymeric amide 11, polymeric amide 12 or polyamide 6/Unit 12.Such terpolymer can be specified according to this polyamide 66/6I/6, polyamide 66/6I/11, polyamide 66/6I/12, polyamide 66/6I/610 or polyamide 66/6I/612.
15. polyureas, polyimide, polyamidoimide, polyetherimide, polyester-imide, poly-glycolylurea and polybenzimidazole.
16. from dicarboxylic acid and glycol and/or from hydroxycarboxylic acid or corresponding lactone deutero-polyester, for example polyethylene terephthalate, Poly(Trimethylene Terephthalate), polybutylene terephthalate, poly terephthalic acid 1,4-methylol cyclohexyl, poly-naphthalic acid alkylidene diol ester (PAN) and poly-hydroxybenzoate, and from the polyethers deutero-segmented polyetherester of terminal hydroxy group is arranged; The polyester of also useful polycarbonate or MBS modification.
17. polycarbonate and polyestercarbonate.
18. above-mentioned mixture of polymers (alloyed polymer), for example PP/EPDM, polymeric amide/EPDM or ABS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, 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.
19. unsaturated polyester resin, for example the polycondensation product of making together with glycol from saturated and undersaturated dicarboxylic acid or from these acid anhydrides is at copolymerisable monomer, the better solution vinylbenzene or the methyl methacrylate.Unsaturated polyester resin can solidify by the radical polymerization of using initiator (for example superoxide) and promotor.But the two keys in the polyester chain can react with the two keys in the copolymerization solvent monomer.The most important dicarboxylic acid that is used to prepare this polyester is maleic anhydride, fumaric acid and terephthalic acid.The most frequently used glycol is 1, the 2-propylene glycol.What also use is ethylene glycol, glycol ether and neopentyl glycol etc.The most suitable cross-linkable monomer is a vinylbenzene.Vinylbenzene can be fully miscible with this resin, and copolymerization easily.Styrene content normally 25～40% in the unsaturated polyester resin.Can be used for replacing cinnamic monomer is methyl methacrylate.
20. Resins, epoxy, for example the polyaddition reaction by a kind of Resins, epoxy composition and a kind of bridging property (stiffening agent) composition prepare those.Employed Resins, epoxy composition is the many glycidyl esters of aromatic series, the for example acid of dihydroxyphenyl propane 2-glycidyl, Bisphenol F 2-glycidyl ester or many glycidyl esters of phenol formaldehyde resin or Cresol Formaldehyde Resin, or many glycidyl esters of phthalic acid, m-phthalic acid or terephthalic acid or trimellitic acid, the N-glycidyl compound of aromatic amine or heterocyclic nitrogenous bases, perhaps two or multi-shrinking glyceryl compound of polyhydric aliphatic family alcohol.Operable stiffening agent is a polyamines, for example for example Tetra hydro Phthalic anhydride, hexahydro phthalic anhydride or methyltetrahydro Tetra hydro Phthalic anhydride or phenol of Triethylenetetramine (TETA), aminoethyl piperazine or isophorone diamine, multiamide base amine, polyprotonic acid or these acid anhydride.This is crosslinked also can to take place via the polymerization of using suitable catalyzer.
21. urethane can obtain by making the promptly many alcohol of the polyethers, polyester and the polyhutadiene that contain terminal hydroxyl and aliphatics or aromatic polyisocyanate reaction.
It is a kind of that useful is or not the organic polymer of polymer containing halogen.Polymer containing halogen is any for example polymkeric substance of F, Cl, Br, I of one or more halogen radicals that contains.
Useful is a kind of synthetic organic polymer, promptly such as the 1st, 2 and 3 polyolefine of mentioning and multipolymer thereof, and such as the 24th urethane that obtains, such as the 15th polymeric amide of mentioning or copolyamide, or such as the 17th polyester of mentioning.Giving preferential is polymeric amide, copolyamide or polyester, especially polymeric amide or polyester, for example polymeric amide, for example polyester.
Better, be benchmark with the weight of this organic polymer, the usage quantity of the compound of formula (I)～(XII) is 0.1%～25.0%, especially 0.4～15.0%, better 0.4%～10.0%, particularly 1.0%～15.0%.
Also useful is a kind of flame resistant method of organic polymer, comprises to the compound of wherein using or mixing therein with the formula (I)～(XII) of at least a further additive combination.
Further the example of additive is:
1. antioxidant
1.1. alkylation monophenolFor example 2, the 6-di-tert-butyl-4-methy phenol, 2-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, the nonylphenol of line style nonylphenol or side chain top set, for example 2,6-dinonyl-4-methylphenol, 2,4-dimethyl-6-(phenol of 1 '-methyl undecane-1 '-yl), 2,4-dimethyl-6-(phenol of 1 '-methyl heptadecane-1 '-yl), 2,4-dimethyl-6-(1 '-methyl tridecane-1 ' base) 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-methylphenols, 2,6-two (dodecane thiomethyl)-4-nonylphenol.
1.3. quinhydrones and alkylation quinhydronesFor 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 sulfo-phenyl etherFor 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, the 6-di-tert-pentyl phenol), 4,4 '-two (2,6-dimethyl-4-hydroxy phenyl) disulphide.
1.6. inclined to one side alkylidene group biphenolFor 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 '-partially ethylene (4, the 6-DI-tert-butylphenol compounds), 2,2 '-partially ethylene (the 6-tertiary butyl-4-isobutyl-phenol), 2,2 '-methylene radical two [6-(α-Jia Jibianji)-4-nonylphenol], 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, ethylene glycol bisthioglycolate [3,3-two (3 '-tertiary butyl-4 '-hydroxy phenyl) butyric ester], two (3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) dicyclopentadiene, terephthalic acid two [2-(3 '-tertiary butyl-2 '-hydroxyl-5 '-the methyl-benzyl)-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 compoundsFor 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 esterFor 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, [4-(1,1 for propanedioic acid two for 2-two (3, the 5-di-tert-butyl-4-hydroxyl benzyl), 3, the 3-tetramethyl-) phenyl ester].
1.9. acrinyl aromatics, 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 sulfenyl-6-(3,5-di-t-butyl-4-hydroxybenzene amido)-1; 3, the 5-triazine; the hot sulfenyl-4 of 2-, 6-two (3,5-di-t-butyl-4-hydroxybenzene amido)-1; 3, the 5-triazine; the hot sulfenyl-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; 2, the 3-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-t-butyl-4-hydroxyl benzyl ethyl)-1,3; the 5-triazine; 1,3,5-three (3; 5-di-t-butyl-4-hydroxybenzene propionyl) six hydrogen-1,3,5-triazines; isocyanuric acid-1; 3,5-three (3,5-dicyclohexyl-4-hydroxyl benzyl ester).
1.11. benzyl phosphonic acid esterFor example 2,5-di-t-butyl-4-hydroxyl benzyl dimethyl phosphonate, 3,5-di-t-butyl-4-hydroxyl benzyl diethyl phosphonate, 3,5-di-t-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-t-butyl-4-hydroxyl benzyl phosphonic acids mono ethyl ester calcium salt.
1.12. amide group phenol, for example 4-hydroxyl lauroyl aniline, 4-hydroxyl stearanilide, N-(3, the 5-di-tert-butyl-hydroxy phenyl) carboxylamine monooctyl ester.
1.13. β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid and following monohydroxy-alcohol or polyvalent alcohol EsterFor example: methyl alcohol, ethanol, n-Octanol, isooctyl alcohol, 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 (hydroxyl ethyl ester), N, N '-two (hydroxyethyl) oxalyl amine, 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.
1.14. β-(5-tertiary butyl-4-hydroxy-3-aminomethyl phenyl) propionic acid and following monohydroxy-alcohol or polyvalent alcohol EsterFor example: methyl alcohol, ethanol, n-Octanol, isooctyl alcohol, 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 (hydroxyl ethyl ester), N, N '-two (hydroxyethyl) oxalyl amine, 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; 3, and 9-two [2-{3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy }-1, the 1-dimethyl ethyl]-2,4,8,10-four oxaspiros [5.5] undecane.
1.15. β-(3,5-dicyclohexyl-4-hydroxy phenyl) propionic acid and following monohydroxy-alcohol or polyvalent alcohol EsterFor 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 (hydroxyl ethyl ester), N, N '-two (hydroxyethyl) oxalyl amine, 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.
1.163, the ester of 5-di-t-butyl-4-hydroxyl phenylacetic acid and following monohydroxy-alcohol or polyvalent alcoholFor 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 (hydroxyl ethyl ester), N, N '-two (hydroxyethyl) oxalyl amine, 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 acidN for example, N '-two (3,5-di-t-butyl-4-hydroxybenzene propionyl) hexamethylene-diamine, N, N '-two (3,5-di-t-butyl-4-hydroxybenzene propionyl) trimethylene diamines, N, N '-two (3,5-di-t-butyl-4-hydroxybenzene propionyl) hydrazine, N, and N '-two [2-(3-[3,5-di-tert-butyl-hydroxy phenyl] propionyloxy) ethyl] oxamide
Figure G2007800158475D00241
XL-1 can be available from Uniroyal company).
1.18. xitix (vitamins C)
1.19. amine type antioxidantN for example, N '-di-isopropyl Ursol D, N, N '-di-sec-butyl-p-phenyl enediamine, N, N '-two (1, the 4-3,5-dimethylphenyl) Ursol D, N, N '-two (1-ethyl-3-aminomethyl phenyl) Ursol D, N, N '-two (1-aminomethyl phenyl) 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, N-cyclohexyl-N '-diphenyl-para-phenylene diamine, 4-(tolysulfonyl amido) 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) six methylene diamines, 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 absorption agent and photostabilizer
(2.1.2-2 '-hydroxy phenyl) benzotriazole2-(2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole for example, 2-(3 ', 5 '-di-t-butyl-2 '-hydroxy phenyl) benzotriazole, 2-(5 '-tertiary butyl-2 '-hydroxy phenyl) benzotriazole, 2-(2 '-hydroxyl-5 '-(1,1,3, the 3-tetramethyl butyl) benzotriazole 2-(3 ' phenyl), 5 '-di-t-butyl-2 '-hydroxy phenyl)-the 5-chlorobenzotriazole, 2-(3 '-tertiary butyl-2 '-hydroxyl-5 '-aminomethyl phenyl)-5-chlorobenzotriazole, 2-(3 '-sec-butyl-the 5 '-tertiary butyl-2 '-hydroxy phenyl) benzotriazole, 2-(2 '-hydroxyl-4 '-octyloxyphenyl) benzotriazole, 2-(3 ', 5 '-two tert-pentyls-2 '-hydroxy phenyl) benzotriazole, 2-(3 ', 5 '-two (α, α-Er Jiajibianji)-2 '-and hydroxy phenyl) benzotriazole, 2-(3 '-tertiary butyl-2 '-hydroxyl-5 '-(the hot oxygen carbonyl of 2-ethyl) phenyl)-5-chlorobenzotriazole, 2-(3 '-tertiary butyl-5 '-[2-(2-ethyl hexyl oxy) carbonyl ethyl]-2 '-hydroxy phenyl)-5-chlorobenzotriazole, 2-(3 '-tertiary butyl-2 '-hydroxyl-5 '-(2-methoxycarbonyl ethyl) phenyl)-5-chlorobenzotriazole, 2-(3 '-tertiary butyl-2 '-hydroxyl-5 '-(2-methoxycarbonyl ethyl) phenyl) benzotriazole, 2-(3 '-tertiary butyl-2 '-hydroxyl-5 '-(the hot oxygen carbonyl of 2-ethyl) phenyl) benzotriazole, 2-(3 '-tertiary butyl-5 '-[2-(the own oxygen carbonyl of 2-ethyl) ethyl]-2 '-hydroxy phenyl) benzotriazole, 2-(3 '-dodecyl-2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole, 2-(3 '-tertiary butyl-2 '-hydroxyl-5 '-(the different hot oxygen carbonyl ethyl of 2-) phenyl) benzotriazole, 2, [4-(1 for 2 '-methylene radical two, 1,3, the 3-tetramethyl butyl)-6-benzotriazole-2-base phenol]; The 2-[3 '-tertiary butyl-5 '-(2-methoxycarbonyl ethyl)-2 '-hydroxy phenyl] ester exchange offspring of benzotriazole and Liquid Macrogol;
Figure G2007800158475D0025091250QIETU
R=3 ' in the formula-tertiary butyl-4 '-hydroxyl-5 '-2H-benzotriazole-2-base phenyl; 2-[2 '-hydroxyl-3 '-(α, α-Er Jiajibianji)-5 '-(1,1,3, the 3-tetramethyl butyl) phenyl] benzotriazole; 2-[2 '-hydroxyl-3 '-(1,1,3, the 3-tetramethyl butyl)-5 '-(α, α-Er Jiajibianji) phenyl] 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, 4-dodecyloxy, 4-benzyloxy, 4,2 ', 4 '-trihydroxy-or 2 '-hydroxyl-4,4 '-dimethoxy derivative.
2.3. there is not the ester that replaces or substituted benzoic acid is arrangedFor example Whitfield's ointment 4-tertiary butyl phenyl ester, salol, Whitfield's ointment octyl octylphenyl, dibenzoyl resorcinol, two (4-tert.-butylbenzene formyl) 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. acrylateAlpha-cyano-β for example, β-diphenyl-ethyl acrylate or different monooctyl ester, α-methoxycarbonyl methyl cinnamate, alpha-cyano-Beta-methyl p-methoxycinnamic acid methyl esters or butyl ester, α-methoxycarbonyl p-methoxycinnamic acid methyl esters, N-(beta-methoxy-carbonyl-beta-cyano vinyl)-2-methyl indoline.
2.5. nickel compoundFor example 2, [4-(1 for 2 '-sulphur two, 1,3, the 3-tetramethyl butyl) phenol] nickel complex for example 1:1 or 1:2 complex compound, other part for example n-Butyl Amine 99, trolamine or N-cyclohexyl diethanolamine are randomly arranged, nickel dibutyl dithiocarbamate, 4-hydroxyl-3,5-di-t-butyl benzylphosphonic acid list alkane ester be the nickel salt of methyl esters or ethyl ester for example, and ketoxime is the nickel complex of 2-hydroxy-4-methyl phenyl undecyl ketoxime for example, the nickel complex of 1-phenyl-4-lauroyl and hydroxypyrazoles randomly has other part.
2.6. sterically hindered amines, for example sebacic acid two (2,2,6,6-tetramethyl piperidine-4-ester), succsinic acid two (2,2,6,6-tetramethyl piperidine-4-ester), sebacic acid two (1,2,2,6,6-pentamethyl-piperidines-4-ester), sebacic acid two (1-octyloxy-2,2,6,6-tetramethyl piperidine-4-ester), normal-butyl-3,5-di-tert-butyl-4-hydroxyl benzyl propanedioic acid two (1,2,2,6,6-pentamethyl-piperidines ester), 1-hydroxyethyl-2,2,6, the condensation product 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-s-triazine or cyclic condensation product, nitrilotriacetic acid(NTA) three (2,2,6,6-tetramethyl--4-piperidines ester), 1,2,3,4-butane tetracid four (2,2,6,6-tetramethyl--4-piperidines ester), 1,1 '-(1,2-second two bases) two (3,3,5,5-tetramethyl-piperazine ketone), 4-benzoyl-2,2,6, the 6-tetramethyl piperidine, the stearic oxygen base-2 of 4-, 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] last of the ten Heavenly stems-2, the 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 of 6-two chloro-1,3,5-triazines or cyclic condensation product, 2-chloro-4,6-two (4-n-butylamine-based-2,2,6, the 6-tetramethyl-piperidyl)-1,3,5-triazine and 1, the condensation product 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-triazine and 1, the condensation product of 2-two (the amino Propylamino of 3-) ethane, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl--1,3,8-thriazaspiro [4.5] last of the ten Heavenly stems-2, the 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-2,2 of 4-, 6, the mixture of 6-tetramethyl piperidine, N, N '-two (2,2,6,6-tetramethyl--4-piperidyl) hexamethylene-diamine and 4-cyclohexylamino-2, the condensation product of 6-two chloro-1,3,5-triazines, 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 condensation product of 6-tetramethyl piperidine (CAS accession number [136504-96-6]); 1 and 2,4,6-three chloro-1,3,5-triazines and N, N-dibutylamine and 4-butylamine base-2,2,6, the condensation product of 6-tetramethyl piperidine (CAS accession number [192268-64-7]); N-(2,2,6; 6-tetramethyl--4-piperidyl) dodecyl succinimide; N-(1,2,2; 6,6-pentamethyl--4-piperidyl) the 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-methoxyl group methylene radical propanedioic acid and 1,2; 2,6, the ester 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. oxalic acid diamideFor example 4,4 '-two octyloxy oxalyl pentanoic, 2,2 '-diethoxy oxalyl pentanoic, 2,2 '-two octyloxies-5,5 '-di-t-butyl oxalyl pentanoic, 2,2 '-two (dodecyloxy)-5,5 '-di-t-butyl oxalyl pentanoic, 2-oxyethyl group-2 '-ethyl oxalyl pentanoic, N, N '-two (3-dimethylamino-propyl) oxalyl pentanoic, 2-oxyethyl group-5-the tertiary butyl-2 '-ethyl oxalyl pentanoic, and with 2-oxyethyl group-2 '-ethyl-5, the mixture of 4 '-di-t-butyl oxalyl pentanoic, O-methoxy is arranged and methoxyl group two is replaced and adjacent oxyethyl group arranged and to the mixture of the dibasic oxalyl pentanoic of oxyethyl group.
(2.8.2-2-hydroxy phenyl)-1,3,5-triazinesFor example 2,4,6-three (2-hydroxyl-4-octyloxyphenyl)-1,3, the 5-triazine, 2-(2-hydroxyl-4-octyloxyphenyl)-4,6-two (2, the 4-3,5-dimethylphenyl)-1,3, the 5-triazine, 2-(2, the 4-dihydroxy phenyl)-4,6-two (2, the 4-3,5-dimethylphenyl)-1,3, the 5-triazine, 2,4-two (2-hydroxyl-4-propoxy-phenyl)-6-(2, the 4-3,5-dimethylphenyl)-1,3, the 5-triazine, 2-(2-hydroxyl-4-octyloxyphenyl)-4,6-two (4-aminomethyl phenyl)-1,3,5-triazines, 2-(2-hydroxyl-4-dodecyloxy phenyl)-4,6-two (2, the 4-3,5-dimethylphenyl)-1,3,5-triazines, 2-(2-hydroxyl-4-tridecane oxygen base phenyl)-4,6-two (2, the 4-3,5-dimethylphenyl)-1,3,5-triazines, 2-[2-hydroxyl-4-(2-hydroxyl-3-butoxy propoxy-) phenyl]-4,6-two (2, the 4-3,5-dimethylphenyl)-1,3,5-triazines, 2-[2-hydroxyl-4-(2-hydroxyl-3-octyloxy propoxy-) phenyl]-4,6-two (2, the 4-3,5-dimethylphenyl)-1,3,5-triazines, 2-[4-(dodecyloxy/tridecane oxygen base-2-hydroxyl propoxy-)-2-hydroxy phenyl]-4,6-two (2, the 4-3,5-dimethylphenyl)-1,3,5-triazines, 2-[2-hydroxyl-4-(2-hydroxyl-3-dodecyloxy propoxy-) phenyl]-4,6-two (2, the 4-3,5-dimethylphenyl)-1,3,5-triazines, 2-(2-hydroxyl-4-hexyloxy) phenyl-4,6-phenylbenzene-1,3, the 5-triazine, 2-(2-hydroxyl-4-p-methoxy-phenyl)-4,6-phenylbenzene-1,3, the 5-triazine, 2,4,6-three [2-hydroxyl-4-(3-butoxy-2-hydroxyl propoxy-) phenyl]-1,3, the 5-triazine, 2-(2-hydroxy phenyl)-4-(4-p-methoxy-phenyl)-6-phenyl-1,3,5-triazines, 2-{2-hydroxyl-4-[3-(2-ethylhexyl-1-oxygen)-2-hydroxyl propoxy-] phenyl }-4,6-two (2, the 4-3,5-dimethylphenyl)-1,3,5-triazines.
3. metal passivatorN for example, N '-phenylbenzene oxalic acid diamide, N-salicylic aldehyde-N '-salicylyl hydrazine, N, N '-two (salicylyl) hydrazine, N, N '-two (3,5-di-t-butyl-4-hydroxybenzene propionyl) hydrazine, 3-salicylamide base-1,2,4-triazole, two (benzylidene partially) oxalyl dihydrazide, oxalyl pentanoic, isopthalic dihydrazide, sebacoyl phenylhydrazine, N, N '-diacetyl adipic dihydrazide, N, N '-two salicylyl oxalyl dihydrazide, N, N '-two salicylyl sulphur propionic acid two hydrazides.
4. phosphorous acid ester and phosphinateTriphenyl phosphite for example, 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 (2,4-dicumyl 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 diphosphinic acid four (2,4-di-t-butyl phenyl ester), 6-isodecyl oxygen base-2,4,8,10-tetra-tert-12H-dibenzo [d, g]-1,3,2-two oxa-phosphorus stars, phosphorous acid two (2,4-di-t-butyl-6-methyl phenyl ester) methyl esters, two (2,4-di-t-butyl-6-methyl phosphorus star, 2,2 ', 2 "-nitrilo [triethyl three (3; 3 '; 5,5 '-tetrabutyl-1,1 '-biphenyl-2; 2 '-two bases) phosphorous acid ester]; phosphorous acid 2-ethylhexyl (3; 3 ', 5,5 '-tetrabutyl-1,1 '-biphenyl-2,2 '-diester), 5-butyl-5-ethyl-2-(2,4, the 6-tri-butyl-phenoxy)-1,3,2-two oxa-phosphirane.
5. azanolN for example, 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, from the N of hydrogenation tallow amine, N-dialkyl group azanol.
6. nitroneFor 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 the N by the preparation of hydrogenation tallow amine, N-dialkyl group azanol deutero-nitrone.
7. sulphur collaborative compound, for example thiodipropionic acid two lauryls or sulphur two acetone distearyl esters.
8. peroxide breakdown compoundThe for example ester of β-thiodipropionic acid such as lauryl, stearyl ester, myristin or tridecane ester, the zinc salt of mercaptobenzimidazole, 2-mercaptobenzimidazole, zinc dibutyl dithiocarbamate, curing two (octadecyl), four (β-dodecane sulfenyl) propionic acid pentaerythritol ester.
9. polymeric amide stablizer, the salt of mantoquita and iodide and/or phosphorus compound and usefulness and bivalent manganese for example.
10. alkaline auxiliary stablizer, for example calcium stearate, Zinic stearas, docosoic magnesium, Magnesium Stearate, natrium ricinoleicum, potassium palmitate, pyrocatechol antimony or pyrocatechol zinc of an alkali metal salt of melamine, Polyvinylpyrolidone (PVP), Dyhard RU 100, triallyl cyanurate, urea derivatives, hydrazine derivative, amine, polymeric amide, urethane, higher fatty acid and alkaline earth salt for example.
11. nucleating agent, inorganic substance for example are as talcum, metal oxide for example titanium dioxide or magnesium oxide, better phosphoric acid salt, carbonate or the vitriol of alkaline-earth metal; 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 is ionic multipolymer (" ionomer ") for example.Giving preferential especially is 1,3:2,4-two (the inclined to one side benzylidene of 3 ', 4 '-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 lime carbonate, silicate, glass fibre, granulated glass sphere, talcum, kaolin, mica, barium sulfate, metal oxide and oxyhydroxide, carbon black, graphite, wood powder, and the powder of other natural product and fiber, synthon.
13. other additive, for example softening agent, lubricant, emulsifying agent, pigment, rheological additives, catalyzer, activator, white dyes, static inhibitor, whipping agent flow.
14. benzofuranone and dihydroindole ketone, for example, as U.S.4,325,863; U.S.4,338,244; U.S.5,175,312; U.S.5,216,052; U.S.5,252,643; DE-A-4316611; DE-A-4316622; DE-A-4316876; Described in EP-A-0589839 or the EP-A-0591102, or 3-[4-(2-acetoxyethoxy) phenyl]-5,7-di-t-butyl benzo furans-2-ketone, 5,7-di-t-butyl-3-[4-(2-stearoyl keto base oxethyl) phenyl] benzofuran-2-ones, 3,3 '-two [5,7-di-t-butyl-3-(the 4-[2-hydroxyl-oxethyl] phenyl) benzofuran-2-ones], 5,7-di-t-butyl-3-(4-ethoxyl phenenyl) benzofuran-2-ones, 3-(4-oxyethyl group-3, the 5-3,5-dimethylphenyl)-5,7-di-t-butyl benzo furans-2-ketone, 3-(3,5-dimethyl-4-new pentane acyloxy phenyl)-5,7-di-t-butyl benzo furans-2-ketone, 3-(3, the 4-3,5-dimethylphenyl)-5,7-di-t-butyl benzo furans-2-ketone, 3-(2, the 3-3,5-dimethylphenyl)-5,7-di-t-butyl benzo furans-2-ketone.
Weight with this organic polymer is benchmark, and the interpolation concentration of this further additive is for example 0.01%～10%, especially 0.2%～5%.For filler and toughener, other concentration can be used as the following stated.
For example, this further additive is selected from a group of following composition; Antioxidant, UV light absorber, photostabilizer, metal passivator, phosphorous acid ester, phosphinate, azanol, nitrone, sulphur collaborative compound, peroxide breakdown compound, polymeric amide stablizer, alkaline auxiliary stablizer, nucleating agent, filler, toughener, softening agent, lubricant, emulsifying agent, pigment, rheological additives, catalyzer, mobile activator, white dyes, static inhibitor, whipping agent, benzofuranone and dihydroindole ketone.
For example, this further additive is selected from a group of following composition: filler and toughener, especially glass system and mineral are filler.The usage quantity of this filler or toughener is a benchmark with the weight of this organic polymer, can be 5%～60%, especially 10%～40%.
Mixing in this organic polymer can be such as carrying out like this: with usual in the industry method, sneak into therein or further fire retardant and/or further additive to the compound of wherein using formula (I)～(XII) and when wishing.This mix can be before forming operation or during carry out or by with dissolved or dispersive compound administration in this polymkeric substance and have or do not have subsequently a solvent evaporation.Under elastomeric situation, these also can be stablized and become latex.With above-mentioned compound mix further possibility in the polymkeric substance be before the corresponding monomeric polymerization, during or just finished after or before crosslinked, add them.In this scope, above-mentioned compound can former state add, and also can add with encapsulated form (for example using wax, oil or polymer encapsulated).
The compound of mentioning herein also can add with master batch form, and this masterbatch is benchmark, contains described compound with the concentration such as 2.5%～25% with the weight of this organic polymer.
The compound of mentioning herein can mix with following method advisably:
-as milk sap or dispersion liquid (for example mixing in latex or the emulsion polymerized thing),
-a kind of dry mixture during sneaking into as supplementary component or polymeric blends,
-directly import in this processing unit (plant) (for example extruding machine, Banbury mixer etc.),
-as solution or melt.
Such composition can with various forms adopt and/or processing to provide various products, for example as (to provide) laminate, printed circuit board (PCB), film, fiber, band, forming composition, section bar or as the base-material of coating, tackiness agent or putty.Such method can be extrusion molding, injection moulding, fiber sprinning or compression moulding.
Formula (I)～(XII) compound of above definition that useful is as fire retardant, be particularly useful for the purposes in the organic polymer.
More than Gai Shu all priority also are applicable to this purposes.
Percentage is wt%, unless otherwise stated.
Following examples explanation the present invention, but be not interpreted as limitation of the scope of the invention by any way.
Embodiment
Employed composition
Polybutylene terephthalate (PBT):
Figure G2007800158475D00311
S600F10, Du Pont deNemours GmbH, Germany;
Polymeric amide (PA6):
Figure G2007800158475D00312
B40E, Lanxess, Germany;
Glass fibre: Chop
Figure G2007800158475D00313
3786 (staple fiber ppd=4.5mm, Fibre diameters=10 μ m), PPG Industries
Phosphorus synergist (diethyl phospho acid Al salt):
Figure G2007800158475D00314
OP1230 or OP930, Clariant GmbH, Germany;
Figure G2007800158475D00316
MC25
Phospho acid Al, Anan Drug ﹠amp; Chemicals, India.
Estimate the test method of flame retardant resistance
" Flammability of Plastic Materials for Parts in Devices andAppliances ", 5 ThEdition, October29,1996 UL94 test.Grade according to the UL94V test is summarized in following table (being pointed out that the time of a sample in the table):
Grade The residual flame time The burning tear drop Burn anchor clamps
V-0 <10s Not Not
V-1 <30s Not Not
V-2 <30s Be Not
Failure <30s Be
Failure >30s Not
Standard program
In the table 1 and 2 listed flame retardant additives do mix, 90 ℃ of vacuum-dryings at least 12 hours.Resulting mixture is homodromal at one Melt compounded in the ZSK25WLE Bitruder, this extruding machine have 2 side feeders and exhaust unit.
The PBT work program: the zone 1～11=60,225,265,260 → 260,255 ℃, vacuum＜50mbar, speed of rotation=150rpm, extrusion capacity=8kg/h.
PA6 work program: zone 1～11=60,230,240,245,250
Figure G2007800158475D0032155009QIETU
250 ℃, vacuum＜200mbar, speed of rotation=200rpm, extrusion capacity=8kg/h.
Each fire retardant composition mixes in the polymer melt via the side feed unit, and glass fibre adds via the second side feed unit.With the polymkeric substance wire rod of homogenizing draw, in water-bath the cooling, pelletizing then.
After this pellet thorough drying (vacuum, 90 ℃, 12 hours), each prescription is at an injection moulding machine
Figure G2007800158475D00322
370S Allrounder) 240～275 ℃ melt temperature processing, provides test sample (UL strip, 1.6mm is thick) in.
After 24 hours, test sample is tested in the conditioning of 25 ℃ and 50% relative humidity, and according to UL94-V (Underwriter Laboratories) test classification.
Unless otherwise stated, otherwise all experiments of each series all are that (for example interpolation of temperature distribution, screw rod geometrical shape, flame retardant additives, injection molding parameter etc.) carry out under the same conditions, to have comparability.All quantity are all explained with wt%, and are benchmark with the plastic shaping composition that comprises fire retardant and enhancement additive all.
Table 1 glass fibre enhanced PBT prescription
Figure G2007800158475D00331
The no enhanced PA6 prescription of table 2
Figure G2007800158475D00332
Can see from above-mentioned result, provide excellent fire retardant agent and self-gravitation performance to polymkeric substance according to prescription of the present invention.

Claims (9)

1. organic-polymer composition, wherein polymeric constituent is different from polymer containing halogen, and said composition comprises following ingredients:
A) a kind of organic polymer, this organic polymer is different from polymer containing halogen,
B) compound of formula (I)～(XII) and
C) a kind of further fire retardant,
Figure FSB00000523095100011
Figure FSB00000523095100021
In the formula
N is 1 or 2,
X is O, S or NH,
Z -Be a kind of negatively charged ion of mineral acid,
R 1And R 2Be H, glycidyl, COO-R independently of one another 8, OCO-R 9, CO-R 9, CO-NR 8R 10Or a kind of nothing that is selected from a group of following composition replaces or substituted radical: C is arranged 1-C 18Alkyl, C 3-C 18Thiazolinyl, C 3-C 6Alkynyl, C 5-C 8Cycloalkyl, C 5-C 8Cycloalkenyl group, C 6-C 12Aryl, C 7-C 14Aralkyl, C 8-C 12Arylalkenyl, C 8-C 12Sweet-smelling alkynyl, C 1-C 18Alkoxyl group, C 3-C 18Alkene oxygen base, C 3-C 6Alkynyloxy group, C 6-C 12Aryloxy, and C 7-C 14Aralkoxy,
R 3And R 5Same independently of one another R 1Definition,
NR 3R 5And R 4Can also lump together the part of the 5 yuan of ring systems of oedoeagus (anellated) that become formula (XIIIa)～(XIIIe),
Figure FSB00000523095100022
Be under 1 the situation at n,
R 4Be halogen, NO, CN, NR 3R 5, NHR 3R5 +Z -, furanonyl or same R 1Definition,
Be under 2 the situation at n,
R 4Be that a kind of nothing that is selected from a group of following composition replaces or replacement double-basis: C arranged 1-C 18Alkylidene group and C 7-C 14Inferior aralkyl,
R 6Same R 1Definition,
R 7Same R 2Definition,
R 8And R 10Be H or independently of one another with the definition of R9;
R 9Be that a kind of nothing that is selected from a group of following composition replaces or substituted radical: C arranged 1-C 18Alkyl, C 3-C 18Thiazolinyl, C 3-C 6Alkynyl, C 5-C 8Cycloalkyl, C 5-C 8Cycloalkenyl group, C 6-C 12Aryl, C 7-C 14Aralkyl, C 8-C 12Arylalkenyl and C 8-C 12Sweet-smelling alkynyl,
Replaced by one or more groups that are selected from following a group of forming by the alkylidene group, inferior aralkyl, alkyl, thiazolinyl, alkynyl, cycloalkyl, cycloalkenyl group, aryl, aralkyl, arylalkenyl, sweet-smelling alkynyl, alkoxyl group, alkene oxygen base, alkynyloxy group, aryloxy and the aralkoxy that replace: halogen, hydroxyl, nitro, cyano group, COO-R 13, CONR 13R 14, OCO-R 15, NR 13CO-R 15, NR 13R 14, COR 15, and O-R 15,
Or be to replace by one or more groups that are selected from following a group of forming on the aryl: C by the inferior aralkyl, aryl, aralkyl, arylalkenyl, sweet-smelling alkynyl, aryloxy and the aralkoxy that replace 1-C 18Alkyl, C 3-C 18Thiazolinyl, and C 3-C 6Alkynyl,
R 11' be H, C 1-C 18Alkyl, C 3-C 18Thiazolinyl, C 3-C 6Alkynyl, C 5-C 8Cycloalkyl, C 5-C 8Cycloalkenyl group, C 6-C 12Aryl, C 7-C 14Aralkyl, C 8-C 12Arylalkenyl, C 8-C 12Sweet-smelling alkynyl, COO-R 13, CONR 13R 14, OCO-R 15, NR 13CO-R 15, NR 13R 14Or CO-R 15,
R 11And R 12Be O-R independently of one another 15Or same R 11' definition,
R 13And R 14Be H or same R independently of one another 15Definition,
R 15Be C 1-C 18Alkyl, C 3-C 18Thiazolinyl, C 3-C 6Alkynyl, C 5-C 8Cycloalkyl, C 5-C 8Cycloalkenyl group, C 6-C 12Aryl, C 7-C 14Aralkyl, C 8-C 12Arylalkenyl, or C 8-C 12Sweet-smelling alkynyl.
2. according to the composition of claim 1, the amount of the compound of its Chinese style (I)～(XII) is 0.1%～25.0%, and further the amount of fire retardant is 0.5%～45.0%, and these are that weight with this organic polymer is benchmark.
3. according to the composition of claim 1, wherein composition (b) is 6-amino uracil, 5-amino uracil, 6-amino-1, the phosphoric acid salt of 3-dimethyl uracil or 6-amino uracil.
4. according to the composition of claim 1, wherein this further fire retardant is selected from a group of following composition: phosphonium flame retardant contains nitrogen combustion inhibitor, halogenated flame, and inorganic combustion inhibitor.
5. according to the composition of claim 1, wherein this further fire retardant is selected from a group of following composition: melamine or urea flame retardant, sterically hindered alkoxylamine compound, dicumyl compounds, the luxuriant and rich with fragrance oxide compound of dihydro oxa-phosphorus, organophosphate, the salt of organic phospho acid, the salt of the salt of organic diphosphinic acid and phospho acid or diphosphinic acid.
6. according to the composition of claim 1, also comprise at least a further additive.
7. according to the composition of claim 1, also comprise at least a one group the further additive that is selected from following composition: antioxidant, ultraviolet ray (UV) absorption agent, photostabilizer, metal passivator, phosphite, phosphinates, azanol class, nitrone class, sulfo-synergism compound, peroxide breakdown compound, polyamine stabilizers, the alkaline auxiliary stablizer, nucleating agent, filler, toughener, softening agent, lubricant, emulsifying agent, pigment, rheological additives, catalyzer, mobile activator, white dyes, antistatic agent, whipping agent, benzofuranone and dihydroindole ketone.
8. according to the composition of claim 1, composition b wherein) with composition c) weight ratio be 1: 10～10: 1.
9. according to the composition of claim 1, wherein this organic polymer is polymeric amide, polyester or polycarbonate, and each all randomly contains toughener.
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