CN103146152A - Flame retardant copolyether ester composition and product comprising same - Google Patents
Flame retardant copolyether ester composition and product comprising same Download PDFInfo
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Abstract
The invention discloses a flame retardant copolyether ester composition, comprising (a) at least one copolyether ester; (b) about 5-35 wt% of at least one halogen-free flame retardant; (c) about 0.1-20 wt% of at least one nitrogen-containing compound; (d) about 0.1-10 wt% of at least one aromatic phosphate ester, and (e) about 0.1-10 wt% of at least one phenoxy resin. The invention also discloses a product comprising parts prepared by the flame retardant copolyether ester composition.
Description
Technical field
The goods that the disclosure relates to fire-retardant copolyetherester compositions and comprises described copolyetherester compositions.
Background technology
For example, because the polymer composition based on conjugated polyether ester elastomer has excellent mechanical property (, tear strength, tensile strength, flexing life and wear resistance), they have been used to manufacture the parts of the vehicularized vehicles and electricity/electronic installation.But in the zone under the engine shield of the vehicles and electricity/electronic installation inside may form electric arc and high temperature usually.Therefore, when retaining its mechanical property, also wish that this composition based on copolyether ester can have low combustible and high thermal stability.
Various flame retardant systems have been developed and have been applied to for example, in polymeric material (polyester), to improve its flame retardant resistance.But, for the consideration of toxicity aspect, not halogen-containing fire retardant more receives publicity.In various not halogen-containing fire retardants, phosphorus compound (for example phosphinates or diphosphinic acid salt) the most often is used because of its stability and fire-retardant validity.Prior art has also shown that various synergistic compounds can be used as synergist and further maximize its fire-retardant validity together with phosphorus compound.For example, United States Patent (USP) 6,547,992 disclose and have used synthetic mineral compound, and for example carbonate, red phosphorus, zn cpds, aluminum compound or these the combination of silicon oxide compound, magnesium compound, periodictable the second main group metal, as fire retarding synergist; United States Patent (USP) 6,716,899 disclose the organic P contained compound of use as fire retarding synergist; United States Patent (USP) 6,365,071 discloses use nitrogenous compound (for example, melamine cyanurate, melamine phosphate, melamine pyrophosphate or trimeric cyanamide biborate) as fire retarding synergist; United States Patent (USP) 6,255,371 disclose the condensation product (for example, Melamine Polyphosphate (MPP)) of the reaction product of using phosphoric acid and trimeric cyanamide or trimeric cyanamide as fire retarding synergist.
Particularly, European patent publication EP1883081 and PCT patent announcement WO2009/047353 and WO2010/094560 disclose respectively for the insulation layer and/or the useful fire-retardant elastic composition of sheath that form electric wire or cable.In those are open, below a few class materials: (i) metal-salt of the metal-salt of phospho acid and/or diphosphinic acid, (ii) nitrogenous compound (for example, the trimeric cyanamide polyphosphate), (iii) combination of mineral compound (for example, zinc borate) is considered to preferred flame retardant combination.In addition, Korean Patent KR 2010038701 discloses flame retardant combination applicable in copolyether ester, and it comprises organic metal phosphinate, melamine cyanurate and aromatic phosphoric ester.But, shown in following examples, the applicant finds, when the flame retardant combination of described prior art is used in copolyetherester compositions, described fire retardant often along with time-shift to surface and cause and separate out.Therefore, the fire-retardant copolyetherester compositions that still needs exploitation not separate out.
Disclosure
The disclosure provides a kind of fire-retardant copolyetherester compositions, and it comprises: (a) at least one copolyether ester; (b) at least one not halogen-containing fire retardant of 5-35 % by weight; (c) at least one nitrogenous compound of 0.1-20 % by weight; (d) at least one aromatic phosphoric ester of 0.1-10 % by weight; (e) at least one phenoxy resin of 0.1-10 % by weight, the gross weight % of all components of wherein said copolyetherester compositions amounts to 100 % by weight, and wherein said at least one not halogen-containing fire retardant comprises at least one being selected from following group: the diphosphinic acid salt of the phosphinates of formula (I), formula (II) and combination or its polymkeric substance.
R wherein
1and R
2identical or different, and R
1and R
2be respectively hydrogen, the C of straight chain, cladodification or ring-type
1-C
6alkyl group, or C
6-C
10aryl; R
3the C of straight chain or cladodification
1-C
10alkylidene group, C
6-C
10arylene group, C
6-C
12alkyl-arylene group, or C
6-C
12aryl-alkylidene group; M is selected from calcium ion, aluminum ion, magnesium ion, zine ion, antimony ion, tin ion, germanium ion, titanium ion, iron ion, zirconium ion, cerium ion, bismuth ion, strontium ion, mn ion, lithium ion, sodium ion, potassium ion and combination thereof; And m, n and x are respectively the integer of identical or different 1-4.
In an embodiment of described fire-retardant copolyetherester compositions, the content of described at least one copolyether ester is the 15-95 % by weight, perhaps 40-95 % by weight, or 40-90 % by weight, the gross weight % of all components of wherein said copolyetherester compositions amounts to 100 % by weight.
In another embodiment of described fire-retardant copolyetherester compositions, in described at least one not halogen-containing fire retardant, R
1and R
2be respectively hydrogen, or described at least one not halogen-containing fire retardant is hypo-aluminum orthophosphate.
In another embodiment of described fire-retardant copolyetherester compositions, described at least one not the content of halogen-containing fire retardant be the 5-30 % by weight, perhaps 7.5-30 % by weight, the gross weight % of all components of wherein said copolyetherester compositions amounts to 100 % by weight.
In another embodiment of described fire-retardant copolyetherester compositions, described at least one nitrogenous compound is selected from (i) melamine cyanurate, (ii) condensation product of trimeric cyanamide, (iii) reaction product of phosphoric acid and trimeric cyanamide, (iv) reaction product of phosphoric acid and melamine condensation product, or described at least one nitrogenous compound is melamine cyanurate.
In another embodiment of described fire-retardant copolyetherester compositions, the content of described at least one nitrogenous compound is the 1-15 % by weight, or the 2-15 % by weight, and the gross weight % of all components of wherein said copolyetherester compositions amounts to 100 % by weight.
In another embodiment of described fire-retardant copolyetherester compositions, described at least one aromatic phosphoric ester is selected from: triaryl phosphate, tricresyl phosphate (alkylaryl) ester, and two or more combination, perhaps described at least one aromatic phosphoric ester is selected from: Triphenyl phosphate, tricresyl phosphate (4-aminomethyl phenyl) ester, tricresyl phosphate (2, the 6-3,5-dimethylphenyl) ester, tricresyl phosphate (2, 4, the 6-trimethylphenyl) ester, tricresyl phosphate (2, the 4-di-tert-butyl-phenyl) ester, tricresyl phosphate (2, the 6-di-tert-butyl-phenyl) ester, Resorcinol two (di(2-ethylhexyl)phosphate phenylester) (RDP), dihydroxyphenyl propane two (di(2-ethylhexyl)phosphate phenylester) (BDP), Resorcinol two (di(2-ethylhexyl)phosphate (xylyl) ester) (XDP), Resorcinol two (di(2-ethylhexyl)phosphate phenylester), Resorcinol two [two (2, the 6-3,5-dimethylphenyl) phosphoric acid ester], 4, two (di(2-ethylhexyl)phosphate-(2 of 4 '-xenyl, ester) and two or more combination the 6-3,5-dimethylphenyl).
In another embodiment of described fire-retardant copolyetherester compositions, described at least one phenoxy resin has the structure of formula (IV):
Wherein n is the integer of 30-100 or 50-90.
In another embodiment of described fire-retardant copolyetherester compositions, the content of described at least one phenoxy resin is the 0.1-7.5 % by weight, perhaps 0.1-5 % by weight, the gross weight % of all components of wherein said copolyetherester compositions amounts to 100 % by weight.
The disclosure also provides goods, and it comprises at least one parts that made by above-mentioned fire-retardant copolyetherester compositions, and preferably, described goods are selected from motorized vehicles parts and electricity/electronic installation.In one embodiment, described goods are selected from the electric wire and cable of insulation, and preferably, the electric wire and cable of described insulation comprises one or more layers insulation layer and/or insulating sheath of being made by above-mentioned fire-retardant copolyetherester compositions.
According to the disclosure, when with specific end points express ranges, should understand this scope and be included in any value in these two specific endpoints and any value that is at or about the arbitrary end points in these two end points.
Embodiment
This paper discloses fire-retardant copolyetherester compositions, and it comprises,
(a) at least one copolyether ester;
(b) at least one not halogen-containing fire retardant of about 5-35 % by weight;
(c) at least one nitrogenous compound of about 0.1-20 % by weight;
(d) at least one aromatic phosphoric ester of about 0.1-10 % by weight; With;
(e) at least one phenoxy resin of about 0.1-10 % by weight.
The copolyether ester that is suitable for composition disclosed herein can be multipolymer, and it contains a plurality of by the end to end repetition long-chain ester units of ester bond and repetition short-chain ester units, and described long-chain ester units is meaned by formula (I):
And described short-chain ester units is meaned by formula (II):
Wherein,
G is divalent group last from the polyether glycol of the about 400-6000 of number-average molecular weight is removed terminal hydroxyl group;
R be from number-average molecular weight approximately 300 or less di-carboxylic acid remove last divalent group carboxylic group;
D be from number-average molecular weight approximately 250 or less glycol remove last divalent group oh group, and
Wherein,
The described repetition long-chain ester units that described at least one copolyether ester comprises about 1-85 % by weight and the described repetition short-chain ester units of about 15-99 % by weight.
In one embodiment, the described repetition long-chain ester units that comprises about 5-80 % by weight for the copolyether ester of composition disclosed herein and the described repetition short-chain ester units of about 20-95 % by weight.
In another embodiment, the described repetition long-chain ester units that comprises about 10-75 % by weight for the copolyether ester of composition disclosed herein and the described repetition short-chain ester units of about 25-90 % by weight.
In another embodiment, the described repetition long-chain ester units that comprises about 40-75 % by weight for the copolyether ester of composition disclosed herein and the described repetition short-chain ester units of about 25-60 % by weight.
" long-chain ester units " described herein refers to by long chain diol and di-carboxylic acid and reacts resulting product.Suitable long chain diol is poly-(alkylene ether) dibasic alcohol that the number-average molecular weight that contains terminal hydroxy group is about 400-6000 or about 600-3000, includes but not limited to gather multipolymer and as the segmented copolymer of ethylene oxide-capped poly-(propylene oxide) dibasic alcohol and so on of (tetramethylene ether) dibasic alcohol, poly-(trimethylene ether) dibasic alcohol, poly(propylene oxide) dibasic alcohol, polyethylene oxide dibasic alcohol, above poly-(alkylene ether) dibasic alcohol.Described long chain diol can be also the mixture of two or more the above dibasic alcohol.In one embodiment, poly-(alkylene ether) dibasic alcohol for this is poly-(tetramethylene ether) dibasic alcohol.
" short-chain ester units " described herein refers to the reaction product of low molecular weight diols or its one-tenth ester derivative and di-carboxylic acid.Applicable low molecular weight diols is that number-average molecular weight is approximately 250 or lower, perhaps about 10-250, perhaps about 20-150, perhaps those of about 50-100, it comprises aliphatics dihydroxy compound, alicyclic dihydroxy compound without limitation, and aromatic dihydroxy compound (comprising bis-phenol).In one embodiment, for this low molecular weight diols, be the dihydroxy compound that contains 2-15 carbon atom, for example, ethylene glycol; Propylene glycol; The isobutyl glycol; BDO; 1,5-PD; 2,2-dimethyl propylene glycol; 1,6-hexylene glycol; Decamethylene-glycol; The dihydroxyl hexanaphthene; Cyclohexanedimethanol; Resorcinol; Resorcinol; 1,5-dihydroxy naphthlene etc.In another embodiment, the low molecular weight diols for this is the dihydroxy compound that contains 2-8 carbon atom.In another embodiment, for this low molecular weight diols, be BDO.The bis-phenol that is applicable to this comprise two (to hydroxyl) biphenyl, two (p-hydroxybenzene) methane and two (p-hydroxybenzene) propane with and two or more mixture.
For the one-tenth ester derivative of the low molecular weight diols of this paper, comprise derived from those of above-mentioned low molecular weight diols, for example the one-tenth ester derivative of ethylene glycol (for example, ethylene oxide or ethylene carbonate) or the one-tenth ester derivative (for example, resorcin diacetate) of Resorcinol.In this article, above-mentioned number-average molecular weight scope is only applicable to described low molecular weight diols.Therefore, belong to the one-tenth ester derivative of glycol and number-average molecular weight and be greater than 250 compound and also can be used for this paper, condition is that the number-average molecular weight of corresponding glycol is approximately 250 or less.
For " di-carboxylic acid " that with above-mentioned long chain diol or low molecular weight diols, react be those lower molecular weights (, number-average molecular weight approximately 300 or less, or about 10-300, or about 30-200, perhaps about 50-100) aliphatic, alicyclic, or aromatic di-carboxylic acid.
Term used herein " aliphatic dicarboxylic acid " refers to those carboxylic acids that contain each two carboxylic groups that are connected with saturated carbon atom.If the carbon atom be connected with carboxylic group is saturated and, in cycloaliphatic ring, this acid is called " alicyclic di-carboxylic acid ".Term used herein " aromatic binary carboxylic acid " refers to those di-carboxylic acid that contain each two carboxylic groups that are connected with carbon atom in the aromatic ring structure.Two carboxyl functional groups in described aromatic binary carboxylic acid not necessarily are connected to identical aromatic nucleus.When containing more than an aromatic nucleus, its can by one or more aliphatics or aromatic series divalent group or for example-O-or-SO
2-divalent group connect.
Aliphatics or alicyclic di-carboxylic acid for this paper comprise without limitation: sebacic acid; 1,3-cyclohexane diacid; Isosorbide-5-Nitrae-cyclohexane diacid; Hexanodioic acid; Pentanedioic acid; 4-hexanaphthene-1, the 2-dicarboxylic acid; 2-ethyl suberic acid; The ring pentanedioic acid; Decahydro-1, the 5-naphthalic acid; 4,4 '-dicyclohexyl dicarboxylic acid; Decahydro-NDA; 4,4 '-methylene-bis (cyclohexyl) formic acid; 3,4-furans diacid and two or more combination thereof.In one embodiment, the di-carboxylic acid for this paper is selected from cyclohexane diacid, hexanodioic acid and two or more combination thereof.
Aromatic binary carboxylic acid for this paper comprises without limitation: phthalic acid; Terephthalic acid; M-phthalic acid; Dibenzoic acid; The dicarboxylic acid compound that contains two benzene nucleus (for example, two (to carboxyphenyl) methane; P-Oxy-1, the 5-naphthalic acid; NDA; 2,7-naphthalic acid; Or 4,4 '-alkylsulfonyl dibenzoic acid); C with above-mentioned aromatic binary carboxylic acid
1-C
12the substitutive derivative of alkyl and ring (for example its halo, alkoxyl group and aryl derivatives).Aromatic binary carboxylic acid for this paper can also be that for example, alcohol acid, as p-(β-hydroxy ethoxy) phenylformic acid.
In an embodiment of composition disclosed herein, the di-carboxylic acid that is used for forming described copolyether ester component can be selected from aromatic binary carboxylic acid.In another embodiment, the aromatic binary carboxylic acid of optional self-contained 8-16 the carbon atom of having an appointment of described di-carboxylic acid.In another embodiment, described di-carboxylic acid can be independent terephthalic acid, or the mixture of terephthalic acid and phthalic acid and/or m-phthalic acid.
In addition, the di-carboxylic acid for this paper also can comprise the functional equivalent of di-carboxylic acid.When the described copolyether ester of preparation, the functional equivalent of di-carboxylic acid is reacted in basically identical with di-carboxylic acid mode with above-mentioned long-chain and low-molecular-weight glycol.The useful functional equivalent of di-carboxylic acid comprises the ester of di-carboxylic acid or becomes ester derivative, for example carboxylic acid halides and acid anhydrides.When this paper is used, above-mentioned number-average molecular weight scope is only applicable to corresponding di-carboxylic acid, is not suitable for its functional equivalent (for example its ester or one-tenth ester derivative).Therefore, belong to the functional equivalent of di-carboxylic acid and number-average molecular weight and be greater than 300 compound and also can be used for this paper, condition is that the number-average molecular weight of corresponding di-carboxylic acid is approximately 300 or less.In addition, described di-carboxylic acid also can comprise any substituted radical or its combination of basically preparation and the purposes generation of described copolyether ester in composition disclosed herein of described copolyether ester not being disturbed.
Long chain diol for the preparation of the copolyether ester component of composition disclosed herein can also be the mixture of two or more long chain diols.Similarly, low molecular weight diols and the di-carboxylic acid for the preparation of described copolyether ester component can also be respectively the mixture of two or more low molecular weight diols and the mixture of two or more di-carboxylic acid.In a preferred embodiment, with above formula (I) with (II), at least about the groups that meaned by R of 70 % by mole, be Isosorbide-5-Nitrae-phenylene, and the group meaned by D of at least 70 % by mole is the tetramethylene group in above formula (II).During for the preparation of described copolyether ester, preferably use the mixture of terephthalic acid and m-phthalic acid when two or more di-carboxylic acid, and, when using two or more low molecular weight diols, preferably use BDO and 1, the mixture of 6-hexylene glycol.
In fire-retardant copolyetherester compositions disclosed herein, at least one contained copolyether ester can also be the mixture of two or more copolyether esters.In described mixture, contained copolyether ester needn't meet the weight percent requirement of the above-mentioned ester units to short chain and long-chain separately.But the mixture of two or more copolyether esters must meet copolyether ester based on average weighted above-mentioned value.For example, in the mixture of two kinds of copolyether esters that comprise equivalent, for weighted mean in this mixture approximately for the described short-chain ester units of 45 % by weight, a kind of copolyether ester can comprise the approximately described short-chain ester units of 10 % by weight, and another kind of copolyether ester can comprise the approximately described short-chain ester units of 80 % by weight.
In one embodiment, the glycol (being BDO) of dicarboxylic esters by being selected from terephthalate, isophthalic acid ester and composition thereof of contained at least one copolyether ester component and lower molecular weight and long chain diol in fire-retardant copolyetherester compositions disclosed herein (i.e. poly-(tetramethylene ether) glycol or ethylene oxide-capped poly(propylene oxide) dibasic alcohol) carry out the copolymerization acquisition.In another embodiment, described at least one copolyether ester for example, obtains by terephthalate (, dimethyl terephthalate (DMT)) and BDO and poly-(tetramethylene ether) glycol copolymerization.
Copolyether ester for composition disclosed herein can, according to any applicable method preparation well known by persons skilled in the art, for example utilize conventional transesterification reaction to be prepared.
In one embodiment, described method is included in catalyzer and (for example has lower heating dicarboxylic esters, dimethyl terephthalate (DMT)) with the low molecular weight diols of poly-(alkylene ether) glycol and molar excess (for example, 1, the 4-butyleneglycol), then steam and remove the methyl alcohol that transesterification reaction forms, and continue heating until methyl alcohol discharges end.Depend on the selection of temperature and catalyst type and the consumption of described low molecular weight diols, copolymerization can complete in several minutes to a few hours, and caused forming low-molecular-weight prepolymer.This type of prepolymer also can make by many alternative esterifications or step of transesterification, for example, by long chain diol and short-chain ester homopolymer or multipolymer are reacted under catalyzer exists until randomization occur be prepared.Described short-chain ester homopolymer or multipolymer can be by above-mentioned dimethyl ester (for example, dimethyl terephthalate (DMT)) with low molecular weight diols (for example, 1, the 4-butyleneglycol) between, perhaps free acid (for example, terephthalic acid) with acetic acid diol ester (for example, BDO diacetate esters) between transesterify preparation.Perhaps, described short-chain ester homopolymer or multipolymer can be for example, by suitable acid (, terephthalic acid), acid anhydrides (for example, Tetra hydro Phthalic anhydride), or acyl chlorides (for example, p-phthaloyl chloride) and glycol (for example, BDO) direct esterification preparation.Perhaps, described short-chain ester homopolymer or multipolymer can be by any other applicable methods, and for example di-carboxylic acid and cyclic ethers or carbonate reaction, be prepared.
In addition, the prepolymer obtained as mentioned above can be converted to by distilling excessive low molecular weight diols the copolyether ester of high molecular.This type of step is called " polycondensation ".Transesterify in condensation polymerization step outside amount is increased molecular weight and is made the copolyetherester units random arrangement.Usually, in order to obtain optimum, polycondensation can be at the temperature of the pressure that is less than about 1mmHg and about 240-260 ℃, for example, at antioxidant (1,6-two [(3,5-di-t-butyl-4 hydroxybenzene) PAPP] normal hexane or 1,3,5-trimethylammonium-2,4,6-tri-[3,5-di-tert-butyl-4-hydroxyl benzyl] benzene) carry out under the existence, continue to be less than approximately 2 hours.The irreversibly thermolysis for fear of at high temperature continuing for a long time, it is favourable using catalyst for ester exchange reaction.Multiple catalysts can be used for this paper, it comprises without limitation: organic titanate (for example combination of independent butyl titanate or itself and magnesium acetate or lime acetate), titanic acid ester title complex (for example derivative of alkali metal alcoholates or alkaline-earth alkoxides and titanic acid ester), inorganic titanate (for example lanthanium titanate), lime acetate/antimony trioxide mixtures, lithium and the alkoxide of magnesium, inferior tin catalyst, and two or more mixture.
Copolyether ester for composition disclosed herein also can be from U.S. E.I.Du Pont De Nemours and Co. (E.I.du Pont de Nemours and Company) (hereinafter being called " Du Pont ") with trade(brand)name
commercially available.
Gross weight based on fire-retardant copolyetherester compositions disclosed herein, the content of described at least one copolyether ester can be about 25-95 % by weight, or about 40-95 % by weight, or about 40-90 % by weight.
The not halogen-containing fire retardant that is suitable for composition disclosed herein can be selected from the diphosphinic acid salt of the phosphinates of formula (I), formula (II), with and combination or polymkeric substance
R wherein
1and R
2can be identical or different, and R
1and R
2be respectively hydrogen, straight chain, C cladodification or ring-type
1-C
6alkyl group, or C
6-C
10aromatic yl group; R
3the C of straight chain or cladodification
1-C
10alkylidene group, C
6-C
10arylene group, C
6-C
12alkyl-arylene group or C
6-C
12aryl-alkylidene group; M is selected from calcium ion, aluminum ion, magnesium ion, zine ion, antimony ion, tin ion, germanium ion, titanium ion, iron ion, zirconium ion, cerium ion, bismuth ion, strontium ion, mn ion, lithium ion, sodium ion, potassium ion and combination thereof; Respectively the do for oneself integer of identical or different 1-4 of m, n and x.Preferably, R
1and R
2can be independently selected from hydrogen, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, the tertiary butyl, n-pentyl and phenyl; R
3can be selected from methylene radical, ethylidene, inferior n-propyl, isopropylidene, inferior normal-butyl, the inferior tertiary butyl, inferior n-pentyl, inferior n-octyl, inferior dodecyl, phenylene, naphthylidene, methylphenylene, ethyl phenylene, tertiary butyl phenylene, methyl naphthylidene, ethyl naphthylidene, tertiary butyl naphthylidene, phenylmethylene, phenyl ethylidene, phenyl propylidene and phenyl butylidene; And M can be selected from aluminum ion and zine ion.More preferably, at this, phosphinates used can be selected from methylethyl phospho acid aluminium, diethyl phospho acid aluminium and combination thereof.
Not halogen-containing fire retardant for this paper also can be from Switzerland Clariant company (Clariant International Ltd.) with trade(brand)name Exolit
tMoP is commercially available.
In another embodiment, not halogen-containing fire retardant used herein is hypo-aluminum orthophosphate, and it can anticipate specialization work company limited (Italmatch Chemicals) with trade(brand)name Phoslite from Italy
tMiP-A is commercially available.
Gross weight based on fire-retardant copolyetherester compositions disclosed herein, described at least one not the content of halogen-containing fire retardant can be about 5-35 % by weight, or about 5-30 % by weight, or about 7.5-30 % by weight.
Nitrogenous compound used herein can comprise for example United States Patent (USP) 6,365,071 and 7,255, those described in 814 without limitation.
In one embodiment, nitrogenous compound used herein is selected from: trimeric cyanamide, 2,4-diamino-6-phenyl-1,3,5-triazine, three (hydroxyethyl) isocyanuric acid ester, wallantoin, glycoluril, dicyanodiamide, guanidine and carbodiimide, with and derivative.
In another embodiment, nitrogenous compound used herein can be selected from melamine derivative, it comprises the reaction product of condensation product, (iii) phosphoric acid and the trimeric cyanamide of (i) melamine cyanurate, (ii) trimeric cyanamide without limitation, and (iv) reaction product of phosphoric acid and melamine condensation product.Applicable condensation product can comprise melem, melam and melon (melon) without limitation, with and higher derivative and mixture.The condensation product of trimeric cyanamide can for example, by any applicable method (, the PCT patent is announced those described in WO9616948) preparation.The reaction product of the reaction product of phosphoric acid and trimeric cyanamide or phosphoric acid and melamine condensation product is interpreted as compound in this article, its be by trimeric cyanamide and phosphoric acid react or the condensation product of trimeric cyanamide (for example, melem, melam, or melon (melon)) with reacting of phosphoric acid, obtain.Example comprises without limitation: two melamine phosphates, two melamine pyrophosphate, melamine phosphate, trimeric cyanamide polyphosphate, melamine pyrophosphate, trimeric cyanamide polyphosphate, melam polyphosphate, melon polyphosphate (melon polyphosphate) and melem polyphosphate, and as announcing described in W09839306 in for example PCT patent.
In another embodiment, at least one nitrogenous compound of this paper, be selected from melamine phosphate and melamine cyanurate.In another embodiment, at least one nitrogenous compound used herein is melamine cyanurate.
Gross weight based on fire-retardant copolyetherester compositions disclosed herein, the content of described at least one nitrogenous compound can be about 0.1-20 % by weight, or about 1-15 % by weight, or about 2-15 % by weight.
Aromatic phosphoric ester for this paper can be meaned by following general formula (III):
In formula (III), n means 0 or larger integer, and described compound can be the mixture with different Integer n.K and m respectively mean the integer of 0-2, and (k+m) are the integer of 0-2.Preferably, k and m are respectively 0 or 1 integer; More preferably, k and m are 1.Ar in formula (III)
1, Ar
2, Ar
3and Ar
4identical or different, and respectively mean phenyl group, or the phenyl group replaced by not halogen-containing organic group.Their specific examples includes but not limited to, phenyl group, tolyl group, xylyl group, isopropyl phenyl group, mesitylene base group, naphthyl group, indenyl group, anthracyl radical etc.Preferred phenyl group, tolyl group, xylyl group, isopropyl phenyl group and naphthyl group; More preferably phenyl group, tolyl group and xylyl group.Finally, the X in formula (III) means with lower any:
In these, R
2-R
9identical or different, and respectively mean hydrogen atom, or the alkyl group that contains 1-5 carbon atom.The specific examples of the alkyl group of the described 1-5 of a containing carbon atom is: methyl group, ethyl group, n-propyl group, isopropyl group, normal-butyl group, sec-butyl group, tertiary butyl groups etc.For these, preferably hydrogen atom, methyl group and ethyl group; Hydrogen atom more preferably.Y means key, O, S, SO
2, C (CH
3)
2, CH
2perhaps CHPh, wherein Ph means phenyl group.
The example that is used for the aromatic phosphoric ester of this paper comprises without limitation: triaryl phosphate (for example, triphenyl, trimethylphenyl phosphoric acid ester, three (3,5-dimethylphenyl) phosphoric acid ester, tolyl diphenyl phosphoester) and three (alkylaryl) phosphoric acid ester (for example, octyl group ester diphenyl phosphoester).Preferably, aromatic phosphoric ester for this is selected from: triphenyl, three (4-aminomethyl phenyl) phosphoric acid ester, three (2, the 6-3,5-dimethylphenyl) phosphoric acid ester, three (2, 4, the 6-trimethylphenyl) phosphoric acid ester, three (2, the 4-di-tert-butyl-phenyl) phosphoric acid ester, three (2, the 6-di-tert-butyl-phenyl) phosphoric acid ester, Resorcinol two (di(2-ethylhexyl)phosphate phenylester) (RDP), dihydroxyphenyl propane two (di(2-ethylhexyl)phosphate phenylester) (BDP), Resorcinol two (di(2-ethylhexyl)phosphate (xylyl) ester) (XDP), Resorcinol two (di(2-ethylhexyl)phosphate phenylester), Resorcinol two [two (2, the 6-3,5-dimethylphenyl) phosphoric acid ester], 4, two (di(2-ethylhexyl)phosphate-(2 of 4 '-xenyl, the 6-3,5-dimethylphenyl) ester) etc.
Aromatic phosphoric ester for this paper also can be from (the Daihachi Chemical Industry Co. of Japanese Daihachi Chemical Industry Co., Ltd., Ltd.) with trade(brand)name PX-200 (Resorcinol two [two (2, the 6-3,5-dimethylphenyl) phosphoric acid ester]), No. CAS: 139189-30-3) or PX-202 (4, two (di(2-ethylhexyl)phosphate-(2 of 4 '-xenyl, the 6-3,5-dimethylphenyl) ester), No. CAS: 147263-99-8) commercially available.
Gross weight based on fire-retardant copolyetherester compositions disclosed herein, the content of described at least one aromatic phosphoric ester can be about 0.1-10 % by weight, or about 0.1-7.5 % by weight, or about 0.1-5 % by weight.
For the phenoxy resin of this paper, be the thermoplasticity condensation product of high molecular of dihydroxyphenyl propane and epoxy chloropropane and their derivative.In one embodiment, the phenoxy resin for this paper has following basic form (IV)
In formula (IV), n is the integer of 30-100 or 50-90.
Phenoxy resin for this paper also can change into from Japanese Dongdu (Tohto Kasei Co., Ltd.) with trade(brand)name Phenotohto
tMyP-50, Phenotohto
tMyP-50S, Phenotohto
tMyP-55, Phenotohto
tMyP-70 or FX280; Perhaps, from Japanese Japan Epoxy Resins Co., Ltd. is with trade(brand)name JER1256, JER4250 or JER4275; Perhaps commercially available with trade(brand)name PKHB, PKHC, PKHH, PKHJ, PKFE, PKHP-200, PKHP-80, PKHB-100 or PKHB-300 from American I nChem Corporation.
Gross weight based on fire-retardant copolyetherester compositions disclosed herein, the content of described at least one phenoxy resin can be about 0.1-10 % by weight, or about 0.1-7.5 % by weight, or about 0.1-5 % by weight.
Fire-retardant copolyetherester compositions disclosed herein also can comprise other additive, for example, tinting material, antioxidant, UV stabilizer, uv-absorbing agent, thermo-stabilizer, lubricant, toughner, impact properties-correcting agent, toughener, viscosity modifier, nucleator, softening agent, releasing agent, scratch and damage modifier, emulsifying agent, pigment, optical brightener, static inhibitor, weighting agent, and two or more combination.Applicable weighting agent can be selected from calcium carbonate, silicate, talcum, carbon black and two or more combination thereof.Gross weight based on composition disclosed herein, the content of the additive that this type of is extra can be about 0.01-20 % by weight, or about 0.01-10 % by weight, or about 0.2-5 % by weight, or about 0.5-2 % by weight.
Copolyetherester compositions disclosed herein is molten mixed mixture, among wherein all described polymeric constituents are scattered in each other well, and all described non-polymeric ingredients are scattered in equably and are confined in described polymeric matrix, thereby this mixture forms unified integral body.Any molten mixing method can be used to mix polymeric constituent and the non-polymeric ingredients of composition disclosed herein.
Just as described in the background section, when not halogen-containing flame-retardant additives is used for copolyetherester compositions, this flame-retardant additives often migrates to the surface of the finished product.PCT patent application WO2011/120225 instruction, in the thermoplastic polyurethanes elastomerics, add solid-state phosphorus acid esters (as XDP or Resorcinol two [two (2,6-3,5-dimethylphenyl) phosphoric acid ester]) and can solve to replace liquid phosphorus acid esters (as BDP or RDP) problem of separating out.But, as shown in the embodiment hereinafter provided, even add Resorcinol in copolyether ester, two [two (2,6-3,5-dimethylphenyl) phosphoric acid ester, still can not prevent from separating out.Yet, find to add phenoxy resin and can solve the problem of separating out.
This paper also discloses goods, it comprises one or more parts that made by fire-retardant copolyetherester compositions disclosed herein, and wherein said goods comprise the vehicularized vehicles, electricity/electronic installation, furniture, footwear, roof construction, outdoor clothes, water management system etc. without limitation.
In one embodiment, described goods are selected from the vehicularized vehicles.In this type of embodiment, fire-retardant copolyetherester compositions disclosed herein can be used to manufacture component, for example, and air intake duct, universal constant speed joint (CVJ) cover etc.
In another embodiment, described goods are selected from electricity/electronic installation.In this type of embodiment, fire-retardant copolyetherester compositions disclosed herein can be used to manufacture insulation layer or the sheath of electric wire and cable.More specifically, described goods can be selected from electric wire and cable, and it comprises insulation layer and/or the sheath made by fire-retardant copolyetherester compositions disclosed herein.For example, described goods can be electric wire or the cables of insulation, it comprises two or three conductive core, two-layer or three-layer insulated layer is respectively around one of described conductive core, and optionally insulating sheath is around described conductive core and described insulation layer, and wherein said insulation layer and/or insulating sheath are made by fire-retardant copolyetherester compositions disclosed herein.
embodiment
material:
.
copolyether ester-1:from Du Pont with trade(brand)name
3078 conjugated polyether ester elastomers that obtain;
.
copolyether ester-2: fromdu Pont is with trade(brand)name
the conjugated polyether ester elastomer that G4074 obtains;
.
aO-1:from BASF Aktiengesellschaft (BASF) with trade(brand)name Irganox
tM1010 phenol antioxidant that are obstructed that obtain;
.
aO-2:from BASF AG with trade(brand)name Irgafos
tMthe 168 triaryl phosphites processing stabilizers that obtain;
.
fR: the fire retardant masterbatch, its hypo-aluminum orthophosphate that comprises 60 % by weight is (from meaning specialization work company limited with trade(brand)name Phoslite
tMiP-A obtains) and the copolyether ester of 40 % by weight (from Du Pont with trade(brand)name
3078 obtain);
.
mC: the melamine cyanurate obtained with trade(brand)name JLS-MC15 from Chinese Hangzhou JLS Flame Retardants Chemical Co., Ltd.
.
aromatic phosphoric ester: from Daihachi Chemical Industry Co., Ltd. with trade(brand)name
pX-200 obtainsresorcinol two [two (2,6-3,5-dimethylphenyl) phosphoric acid ester]
;
.
phenoxy resin: the phenoxy resin obtained with trade(brand)name PKHB from InChem Corporation.
comparative example CE1 and embodiment E 1
In each comparative example and embodiment, be prepared as follows the copolyetherester compositions resin: by appropriate copolyether ester, fire retardant and other additive at the ZSK26 twin-screw extruder (purchased from Coperion Werner; Pfleiderer GmbH & Co., Germany) middle dry, pre-mixing, and molten mixed, wherein the Temperature Setting of extrusion machine is 190-210 ℃, and rotating speed is 300rpm, and extruding output is 20kg/hr.
In each embodiment, use the wire of the standby insulation of the above resin obtained, wherein each insulated conductor has circular cross section, and diameter is about 2mm, and wherein each insulated conductor has by copolyetherester compositions and makes and, around the insulating sheath of conductive core, this conductive core is made by 91 strands of copper cash.According to UL1581, measure combustibility (VW-1), tensile strength and the elongation limit of the insulated conductor made thus, and list shows result in following table 1.
In each embodiment, make the model (molding plaque) of 100 * 100 * 2mm by injection moulding, wherein the Temperature Setting of injection molding machine is 190-210 ℃, and the temperature of mould is 50 ℃.Then, measure the hardness of model according to ISO868, and list shows result in table 1.
Finally, in each embodiment, in being set as the controlled climatic chamber of 65 ℃ and 95% relative humidity (RH), model is placed 3 days.Whether model place after with visual inspection separated out thereafter.
Result shows, when not halogen-containing flame-retardant additives, during for copolyetherester compositions, this flame-retardant additives often migrates to the surface of the finished product.But, find to add phenoxy resin and can solve the problem of separating out.In addition, when described copolyetherester compositions is used for preparing insulating sheath, its VW-1 flammability rating (according to UL1581) also is improved because adding phenoxy resin.
Table 1
1y: observe the settling like powder or quasi-liquid material;
2n: do not observe the settling like powder or quasi-liquid material.
Claims (11)
1. fire-retardant copolyetherester compositions, it comprises:
(a) at least one copolyether ester;
(b) at least one not halogen-containing fire retardant of 5-35 % by weight;
(c) at least one nitrogenous compound of 0.1-20 % by weight;
(d) at least one aromatic phosphoric ester of 0.1-10 % by weight; With
(e) at least one phenoxy resin of 0.1-10 % by weight,
The gross weight % of all components of wherein said copolyetherester compositions amounts to 100 % by weight, and the phosphinates that wherein said at least one not halogen-containing fire retardant comprises the formula of being selected from (I), the diphosphinic acid salt of formula (II), and at least one of combination or polymkeric substance:
R wherein
1and R
2identical or different, and R
1and R
2be respectively hydrogen, straight chain, cladodification, or the C of ring-type
1-C
6alkyl group, or C
6-C
10aryl; R
3the C of straight chain or cladodification
1-C
10alkylidene group, C
6-C
10arylene group, C
6-C
12alkyl-arylene group, or C
6-C
12aryl-alkylidene group; M is selected from calcium ion, aluminum ion, magnesium ion, zine ion, antimony ion, tin ion, germanium ion, titanium ion, iron ion, zirconium ion, cerium ion, bismuth ion, strontium ion, mn ion, lithium ion, sodium ion, potassium ion and combination thereof; And m, n and x are respectively the integer of identical or different 1-4.
2. the fire-retardant copolyetherester compositions of claim 1, the content of wherein said at least one copolyether ester is the 15-95 % by weight, perhaps 40-95 % by weight, or 40-90 % by weight, the gross weight % of all components of wherein said copolyetherester compositions amounts to 100 % by weight.
3. claim 1 or 2 fire-retardant copolyetherester compositions, wherein, in described at least one not halogen-containing fire retardant, R
1and R
2be respectively hydrogen, or described at least one not halogen-containing fire retardant is hypo-aluminum orthophosphate.
4. the fire-retardant copolyetherester compositions of any one in claim 1-3, wherein said at least one not the content of halogen-containing fire retardant be the 5-30 % by weight, perhaps 7.5-30 % by weight, the gross weight % of all components of wherein said copolyetherester compositions amounts to 100 % by weight.
5. the fire-retardant copolyetherester compositions of any one in claim 1-4, wherein said at least one nitrogenous compound is selected from: (i) melamine cyanurate, (ii) condensation product of trimeric cyanamide, (iii) reaction product of phosphoric acid and trimeric cyanamide, (iv) reaction product of phosphoric acid and melamine condensation product, perhaps wherein, described at least one nitrogenous compound is melamine cyanurate.
6. the fire-retardant copolyetherester compositions of any one in claim 1-5, the content of wherein said at least one nitrogenous compound is the 1-15 % by weight, perhaps 2-15 % by weight, the gross weight % of all components of wherein said copolyetherester compositions amounts to 100 % by weight.
7. the fire-retardant copolyetherester compositions of any one in claim 1-6, wherein said at least one aromatic phosphoric ester is selected from triaryl phosphate, three (alkylaryl) phosphoric acid ester, with and two or more combination, perhaps wherein, described at least one aromatic phosphoric ester is selected from triphenyl, three (4-aminomethyl phenyl) phosphoric acid ester, three (2, the 6-3,5-dimethylphenyl) phosphoric acid ester, three (2, 4, the 6-trimethylphenyl) phosphoric acid ester, three (2, the 4-di-tert-butyl-phenyl) phosphoric acid ester, three (2, the 6-di-tert-butyl-phenyl) phosphoric acid ester, Resorcinol two (di(2-ethylhexyl)phosphate phenylester) (RDP), dihydroxyphenyl propane two (di(2-ethylhexyl)phosphate phenylester) (BDP), Resorcinol two (di(2-ethylhexyl)phosphate (xylyl) ester) (XDP), Resorcinol two (di(2-ethylhexyl)phosphate phenylester), Resorcinol two [two (2, the 6-3,5-dimethylphenyl) phosphoric acid ester], 4, two (di(2-ethylhexyl)phosphate-(2 of 4 '-xenyl, ester) and two or more combination the 6-3,5-dimethylphenyl).
8. the fire-retardant copolyetherester compositions of any one in claim 1-7, wherein said at least one phenoxy resin has the structure of formula (IV):
Wherein n is the integer of 30-100 or 50-90.
9. the fire-retardant copolyetherester compositions of any one in claim 1-8, the content of wherein said at least one phenoxy resin is the 0.1-7.5 % by weight, perhaps 0.1-5 % by weight, the gross weight % of all components of wherein said copolyetherester compositions amounts to 100 % by weight.
10. goods, it comprises the parts that the fire-retardant copolyetherester compositions of at least one any one in claim 1-9 makes, described goods preferably are selected from motorized vehicles parts and electricity/electronic installation.
11. the goods of claim 10, wherein said goods are selected from the electric wire and cable of insulation, preferably, the electric wire and cable of described insulation comprises insulation layer and/or the insulating sheath that the fire-retardant copolyetherester compositions of one or more layers any one in claim 1-9 makes.
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| CN2011104029999A CN103146152A (en) | 2011-12-07 | 2011-12-07 | Flame retardant copolyether ester composition and product comprising same |
| JP2014545929A JP2015501866A (en) | 2011-12-07 | 2012-11-24 | Flame retardant copolyetherester composition and articles containing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108291053A (en) * | 2015-10-09 | 2018-07-17 | 萨索尔（美国）公司 | Phosphate-ester composition and purposes |
| CN111201579A (en) * | 2017-07-14 | 2020-05-26 | 杜邦聚合物公司 | Low smoke flame retardant cable |
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| CN1599775A (en) * | 2001-11-30 | 2005-03-23 | 宝理塑料株式会社 | Flame-retardant resin composition |
| US20080027167A1 (en) * | 2006-07-26 | 2008-01-31 | General Electric Company | Elastomer blends containing polycarbonates and copolyetheresters derived from polyethylene terephthalate, method of manufacture, and articles therefrom |
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| CN1599776A (en) * | 2001-11-30 | 2005-03-23 | 宝理塑料株式会社 | Flame-retardant resin composition |
| CN1599775A (en) * | 2001-11-30 | 2005-03-23 | 宝理塑料株式会社 | Flame-retardant resin composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108291053A (en) * | 2015-10-09 | 2018-07-17 | 萨索尔（美国）公司 | Phosphate-ester composition and purposes |
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| CN111201579A (en) * | 2017-07-14 | 2020-05-26 | 杜邦聚合物公司 | Low smoke flame retardant cable |
| CN111201579B (en) * | 2017-07-14 | 2022-07-19 | 杜邦聚合物公司 | Low smoke flame retardant cable |
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