CN102952391B - Fire-resistant polyamide composite and goods prepared therefrom - Google Patents
Fire-resistant polyamide composite and goods prepared therefrom Download PDFInfo
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- CN102952391B CN102952391B CN201110235736.3A CN201110235736A CN102952391B CN 102952391 B CN102952391 B CN 102952391B CN 201110235736 A CN201110235736 A CN 201110235736A CN 102952391 B CN102952391 B CN 102952391B
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Abstract
Disclosed herein is retardant polyamide composition, and it is substantially free of nitrogenous compound, and it is substantially composed of the following components: (a) at least one aromatic poly amide; At least one halogen-free flame retardants of (b) about 5-30 % by weight; The sheet mica of (c) about 0.1-10 % by weight; Be up at least one toughener of about 45 % by weight with optional (d), it is selected from glass fibre, sheet glass and combination thereof, and in wherein said composition, the total weight percent of all components is 100 % by weight.Also the goods comprising above-mentioned composition are disclosed at this.
Description
Technical field
The disclosure relates to flame retardant resistance aromatic polyamide composition and comprises its goods.
Background technology
Polymeric amide has desirable chemical resistant properties and processing characteristics, and this makes polymeric amide be specially adapted to electrical/electronic application.For electrical/electronic application polymeric amide needed for another critical nature be flame retardant resistance.Develop various fire retardant systems and for polymeric amide.For the worry of the toxicity to halogen containing flame-retardant, halogen-free flame retardants is just obtaining increasing concern now.Wherein, based on its stability and flame retardant effect, use at most phosphorus compound (as the salt of phospho acid or diphosphinic acid (diphosphinicacid), see such as European patent application EP 0792912 and U.S. Patent Publication US2007/0072970).Prior art is also verified, and multiple compounds can be used as synergist and is combined with described phosphorus compound, maximizes to make its flame retardant effect further.Such as, US Patent No. 6,547,992 disclose and utilize the mineral compound of synthesis if the metal carbonate of the oxide compound of silicon, magnesium compound, the periodic table of elements second main group metal, red phosphorus, zn cpds or aluminum compound are as fire retarding synergist, US Patent No. 6,365,071 discloses and utilizes nitrogenous compound (such as, melamine cyanurate, melamine phosphate, melamine pyrophosphoric ester or trimeric cyanamide diborate) as fire retarding synergist, US Patent No. 6,255,371 disclose the reaction product (such as, Melamine polyphosphate (MPP)) of the condensation product utilizing phosphoric acid and trimeric cyanamide or trimeric cyanamide as fire retarding synergist, with US Patent No. 7, 294, 661 disclose and utilize Si oxide (such as silicon-dioxide), metal oxide (such as boehmite, aluminum oxide, ferric oxide, titanium dioxide, manganese oxide, magnesium oxide, zirconium white, zinc oxide, molybdenum oxide, cobalt oxide, bismuth oxide, chromic oxide, stannic oxide, weisspiessglanz, nickel oxide, cupric oxide or Tungsten oxide 99.999), metal-powder (such as aluminium, iron, titanium, manganese, zinc, molybdenum, cobalt, bismuth, chromium, tin, antimony, nickel, copper or tungsten), or metal-salt (such as zinc borate, zinc metaborate, barium metaborate, zinc carbonate, magnesiumcarbonate, calcium carbonate or barium carbonate) as fire retarding synergist.
But find, add described various fire retarding synergist and be combined with described halogen-free flame retardants and usually have side effect to some other mechanical properties (as shock strength) of composition.Still need to develop a kind of additive system at present, it can be used for daiamid composition does not have negative impact to its other desirable character to improve its flame retardant resistance.
Summary of the invention
Object of the present disclosure is to provide a kind of halogen-free flame retardants to combine, and it can be used for daiamid composition does not have negative impact to its shock strength to improve its flame retardant resistance.Described fire-resistant polyamide composite is substantially free of nitrogenous compound, and based on said composition total weight, said composition is substantially composed of the following components: at least one aromatic poly amide of (a) 15-90 % by weight; At least one halogen-free flame retardants of (b) 5-30 % by weight; The sheet mica of (c) 0.1-10 % by weight; Be up at least one toughener of 45 % by weight with optional (d), it is selected from glass fibre and sheet glass, and in wherein said composition, the total weight percent of all components is 100 % by weight,
And described at least one halogen-free flame retardants is selected from the phosphinates of formula (I), the diphosphinic acid salt of formula (II), and the combination of described phosphinates and/or diphosphinic acid salt and polymkeric substance:
Wherein R
1and R
2identical or different, and R
1and R
2each hydrogen naturally, the C of straight chain, side chain or ring-type
1-C
6alkyl, or C
6-C
10aryl; R
3straight or branched C
1-C
10alkylidene group, C
6-C
10arylidene, C
6-C
12alkyl-arylene, or C
6-C
12aryl-alkylidene group; M is selected from calcium ion, magnesium ion, aluminum 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 two or more combination above-mentioned; And m, n and x are identical or different, the integer of their each 1-4 naturally.
In an embodiment of described fire-resistant polyamide composite, described composition is substantially free of boehmite.
In another embodiment of described fire-resistant polyamide composite, described at least one aromatic poly amide is selected from polyamide 6,6/6, T; Polyamide 6, T/6,6; Polyamide 6, T/D, T; Polyamide 6, I/6, T; Polymeric amide 9, T; Polymeric amide 10, T; Polymeric amide 12, T; With two or more combination above-mentioned.Or described at least one aromatic poly amide can be polyamide 6, T/6,6.
In another embodiment of described fire-resistant polyamide composite, described at least one aromatic poly amide is the mixture of two or more aromatic poly amide.Or this mixture is selected from polyamide 6,6/6, T and polyamide 6, the mixture of I/6, T; Polyamide 6, T/6,6 and polyamide 6, the mixture of I/6, T; And polyamide 6, T/6,6 and polyamide 6, the mixture of T/D, T.
In another embodiment of described fire-resistant polyamide composite, described at least one halogen-free flame retardants is selected from aluminum diethylphosphinate, methylethyl phospho acid aluminium and combination thereof.
In another embodiment of described fire-resistant polyamide composite, described sheet mica is selected from the sheet of phlogopite, white mica and composition thereof.
In the another one embodiment of described fire-resistant polyamide composite, described composition is substantially composed of the following components: the described at least one aromatic poly amide of (a) 25-75 % by weight; The described at least one halogen-free flame retardants of (b) 8-20 % by weight; The described sheet mica of (c) 0.3-8 % by weight; (d) the described at least one toughener of 15-40 % by weight, in wherein said composition, the total weight percent of all components is 100 % by weight.Or described composition is substantially composed of the following components: the described at least one aromatic poly amide of (a) 35-64 % by weight; The described at least one halogen-free flame retardants of (b) 10-15 % by weight; The described sheet mica of (c) 0.5-6 % by weight; (d) the described at least one toughener of 25-35 % by weight, in wherein said composition, the total weight percent of all components is 100 % by weight.
In the another one embodiment of described fire-resistant polyamide composite, described composition optionally also comprises and is up to 5 % by weight, or 0.1-2 % by weight, or the zinc borate of 0.2-0.5 % by weight, in wherein said composition, the total weight percent of all components is 100 % by weight.
Additionally provide a kind of goods at this, it is disclosed described fire-resistant polyamide composite above comprising.Described goods can be moulded product or extruded product, its UL-94 flammability rating (use the test bar of 0.8 mm thick carry out measure) is V-0, and its otch charpy impact intensity (measuring according to ISO179/1eA), compared to comprising substantially not containing moulded product or the extruded product of the comparable fire-resistant polyamide composite of sheet mica, low less than 17% or low less than 13%.Or the otch charpy impact intensity of this moulded product or extruded product (measuring according to ISO179/1eA) can be at least 7KJ/m
2or at least 7.3KJ/m
2.Or described moulded product or extruded product are selected from electrical cnnector, connector shell, interrupter envelope and relay1 case.
According to herein, when providing a scope with two concrete end points, described scope should be understood and comprise any value be in described two concrete end points and any value of any one be at or about in described two end points.
Embodiment
At this, a kind of fire-resistant polyamide composite is disclosed, described retardant polyamide composition is substantially free of nitrogenous compound, and based on the total weight of described composition, described composition is substantially composed of the following components: (a) at least one aromatic poly amide; At least one halogen-free flame retardants of (b) about 5-30 % by weight; The sheet mica of (c) about 0.1-10 % by weight; Be up at least one toughener of about 45 % by weight with optional (d), it is selected from glass fibre, sheet glass and combination thereof, and in wherein said composition, the total weight percent of all components is 100 % by weight." being substantially free of ... " refer to composition absolutely not containing or only containing certain component being less than about 0.001 % by weight." substantially by ... composition " refer to, composition is formed primarily of listed component, optional is can not comprise additional component in described composition, and condition is that the existence of this additional component does not have negative impact to the flame retardant resistance of described composition and other desirable character (as shock strength).
Polymeric amide is the condenses of (a) one or more dicarboxylic acid and one or more diamines, or the condenses of (b) one or more aminocarboxylic acids, or the open chain polymerisate of (c) one or more cyclic lactames.Described aromatic poly amide can be the polymkeric substance of homopolymer, multipolymer, terpolymer or more the unit comprising at least one aromatic monomer component as used herein.Such as, aromatic poly amide can obtain as follows: use aliphatic dicarboxylic acid and aromatic diamine, or uses aromatic dicarboxylic acid and aliphatic diamine as starting material, and makes their polycondensations.
The diamines be applicable to as used herein can be selected from aliphatic diamine, alicyclic diamine, and aromatic diamine.The exemplary diamines be suitable at this includes but not limited to: tetramethylene-diamine; Hexamethylene-diamine; 2-methyl pentamethylene diamine; Nine methylene diamine; 11 methylene diamine; Ten dimethylene diamines; 2,2,4-trimethylhexamethylenediamine; 2,4,4-trimethylhexamethylenediamine; 5-methyl nine methylene diamine; 1,3-bis-(amino methyl) hexanaphthene; Isosorbide-5-Nitrae-two (amino methyl) hexanaphthene; 1-amino-3-amino methyl-3,5,5-trimethyl-cyclohexane; Two (4-aminocyclohexyl) methane; Two (3-methyl-4-aminocyclohexyl) methane; 2,2-bis-(4-aminocyclohexyl) propane; Two (aminopropyl) piperazine; Aminoethylpiperazine; Two (to aminocyclohexyl) methane; 2-methyloctamethylenediamine; Trimethylhexamethylenediamine; 1,8-diamino-octane; 1,9-diamino nonane; 1,10-diamino decane; 1,12-diamino dodecane; M-xylylene amine; To xylylene amine etc., and its derivative.
Be applicable to dicarboxylic acid as used herein and can be selected from aliphatic dicarboxylic acid, alicyclic dicarboxylic acid and aromatic dicarboxylic acid.The exemplary dicarboxylic acid be suitable at this includes but not limited to: hexanodioic acid; Sebacic acid; Nonane diacid; Dodecanedioic acid; Terephthalic acid; M-phthalic acid; Phthalic acid; Pentanedioic acid; Pimelic acid; Suberic acid; Isosorbide-5-Nitrae-cyclohexane dicarboxylic acid; Naphthalene dicarboxylic acids etc., and its derivative.
Exemplary aromatic polymeric amide includes but not limited to as used herein: poly-(an xylylene adipoyl diamines) (polymeric amide MXD, 6); Poly-(ten dimethylene terephthalamides) (polymeric amide 12, T); Poly-(11 methylene radical terephthalamide) (polymeric amide 11, T); Poly-(decamethylene terephthalamide) (polymeric amide 10, T); Poly-(nine methylene radical terephthalamides) (polymeric amide 9, T); Poly-(hexa-methylene terephthalamide) (polyamide 6, T); Hexamethylene adipamide/hexa-methylene terephthalamide copolyamide (polyamide 6, T/6,6, namely in its repeating unit at least about 50 % by mole derived from polyamide 6, the polyamide 6 of T, T/6,6); Hexa-methylene terephthalamide/hexamethylene adipamide copolyamide (polyamide 6,6/6, T, namely in its repeating unit at least about 50 % by mole derived from polyamide 6, the polyamide 6 of 6,6/6, T); Hexa-methylene terephthalamide/hexa-methylene isophtalamide copolyamide (polyamide 6, T/6, I, namely in its repeating unit at least about 50 % by mole derived from polyamide 6, the polyamide 6 of T, T/6, I); Hexa-methylene terephthalamide/2-methyl pentamethylene terephthalamide copolyamide (polyamide 6, T/D, T); Hexamethylene adipamide/hexa-methylene terephthalamide/hexa-methylene isophtalamide copolyamide (polyamide 6,6/6, T/6, I); Poly-(hexanolactam-hexa-methylene terephthalamide) (polyamide 6/6, T); Poly-(hexa-methylene isophtalamide/hexa-methylene terephthalamide) (polyamide 6, I/6, T, namely in its repeating unit at least about 50 % by mole derived from polyamide 6, the polyamide 6 of I, I/6, T); Poly-(hexa-methylene isophtalamide) (polyamide 6, I); Poly-(xylylene isophtalamide/hexa-methylene isophtalamide) (polymeric amide MXD, I/6, I); Poly-(an xylylene isophtalamide/xylylene terephthalamide/hexa-methylene isophtalamide) (polymeric amide MXD, I/MXD, T/6, I); Poly-(an xylylene isophtalamide/ten dimethylene isophtalamide) (polymeric amide MXD, I/12, I); Poly-(an xylylene isophtalamide) (polymeric amide MXD, I); Poly-(dimethyl diamino two cyclohexyl methane isophtalamide/dodecane acid amides) (polymeric amide MACM, I/12); Poly-(dimethyl diamino two cyclohexyl methane isophtalamide/dimethyl diamino two cyclohexyl methane terephthalamide/dodecane acid amides) (polymeric amide MACM, I/MACM, T/12); Poly-(hexa-methylene isophtalamide/dimethyl diamino two cyclohexyl methane isophtalamide/dodecane acid amides) (polyamide 6, I/MACM, I/12); Poly-(hexa-methylene isophtalamide/hexa-methylene terephthalamide/dimethyl diamino two cyclohexyl methane isophtalamide/dimethyl diamino two cyclohexyl methane terephthalamide) (polyamide 6, I/6, T/MACM, I/MACM, T); Poly-(hexa-methylene isophtalamide/hexa-methylene terephthalamide/dimethyl diamino two cyclohexyl methane isophtalamide/dimethyl diamino two cyclohexyl methane terephthalamide/dodecane acid amides) (polyamide 6, I/6, T/MACM, I/MACM, T/12); Poly-(dimethyl diamino two cyclohexyl methane isophtalamide/dimethyl diamino two cyclohexyl methane dodecane acid amides) (polymeric amide MACM, I/MACM, 12) etc.
In one embodiment, described at least one aromatic poly amide is selected from polyamide 6,6/6, T; Polyamide 6, T/6,6; Polyamide 6, T/D, T; Polyamide 6, I/6, T; Polymeric amide 9, T; Polymeric amide 10, T; Polymeric amide 12, T; With two or more combination above-mentioned.In another embodiment, described at least one aromatic poly amide is polyamide 6, T/6,6.In addition, the described at least one polymeric amide be included in described daiamid composition disclosed herein can be the mixture of two or more aromatic poly amide, as polyamide 6, and 6/6, T and polyamide 6, the mixture of I/6, T; Polyamide 6, T/6,6 and polyamide 6, the mixture of I/6, T; Or polyamide 6, T/6,6 and polyamide 6, the mixture of T/D, T.The described at least one polymeric amide be included in described daiamid composition disclosed herein also can be the mixture of one or more aromatic poly amide and one or more aliphatic polyamides, as polyamide 6, I/6, T and polyamide 6, the mixture of 6, condition is, with the total weight of described mixture, the content of described aramid components is about 80 % by weight or higher.
The aromatic poly amide be suitable at this can business's purchased from American E.I.Du Pont De Nemours and Co. (E.I.duPontdeNemoursandCompany) (being hereafter called " E.I.Du Pont Company "), and trade mark is Zytel
?hTN501, Zytel
?hTN502, Zytel
?hTN502HF or Zytel
?hTN503.
According to the disclosure, the content of described at least one polymeric amide in described daiamid composition disclosed herein can be about 15-90 % by weight, or about 25-75 % by weight, or about 35-64 % by weight, and the total weight percent of wherein said composition is 100 % by weight.
Described halogen-free flame retardants is selected from the phosphinates of one or more formulas (I), the diphosphinic acid salt of formula (II) as used herein, and the combination of described phosphinates and/or diphosphinic acid salt and polymkeric substance:
Wherein R
1and R
2identical or different, and R
1and R
2each hydrogen naturally, the C of straight chain, side chain or ring-type
1-C
6alkyl, or C
6-C
10aryl; R
3straight or branched C
1-C
10alkylidene group, C
6-C
10arylidene, C
6-C
12alkyl-arylene, or C
6-C
12aryl-alkylidene group; M is selected from calcium ion, magnesium ion, aluminum 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 two or more combination above-mentioned; And m, n and x are identical or different, the integer of their each 1-4 naturally.Preferably, R
1and R
2can independently selected from hydrogen, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, the tertiary butyl, n-pentyl and phenyl; R
3methylene radical, ethylidene, sub-n-propyl, isopropylidene, sub-normal-butyl, the sub-tertiary butyl, sub-n-pentyl, sub-n-octyl, sub-dodecyl, phenylene, naphthylidene, methylene radical naphthylidene, ethyl naphthylidene, tert-butylphenylene, tertiary butyl naphthylidene, methyinaphthylene, tetrabutyl naphthylidene, phenylmethylene, phenyl-ethylene, phenylpropylene and phenyl butylidene can be selected from; M can be selected from aluminum ion, zine ion and combination thereof.More preferably, described phosphinates can be selected from methylethyl phospho acid aluminium, aluminum diethylphosphinate and combination thereof as used herein.
The halogen-free flame retardants be suitable at this also can be purchased from Clariant Corporation of Switzerland (ClariantInternationalLtd.), and trade mark is Exolit
tMoP.
Based on the total weight of described fire-resistant polyamide composite disclosed herein, the content of described at least one halogen-free flame retardants is about 5-30 % by weight, or about 8-20 % by weight, or about 10-15 % by weight, the total weight percent of wherein said composition is 100 % by weight.
According to the disclosure, described sheet mica is introduced into as fire retarding synergist in described fire-resistant polyamide composite, maximizes to make the flame retardant effect of described halogen-free flame retardants.Mica is a kind of known crystallization mineral silicate, and it obtains with various monoclinic in form, can easily be divided into very thin page or sheet.The exemplary mica useful at this includes but not limited to:
● chemical formula K (Mg, Fe, Mn)
3(AlSi
3o
10) (F, OH)
2the phlogopite (having another name called magnesium mica) represented;
● chemical formula K (Mg, Fe)
3(AlSi
3o
10) (F, OH)
2the biotite (having another name called iron mica or biotite) represented;
● chemical formula KLiFeAl (AlSi
3) O
10(OH, F)
2the zinnwaldite represented;
● chemical formula KLi
2al (Al, Si)
3o
10(F, OH)
2the rubellan (having another name called lithionite) represented;
● chemical formula KAl
2(AlSi
3o
10) (F, OH)
2the white mica (comprising calcining white mica) represented;
● chemical formula NaAl
2[(OH)
2alSi
3o
10] paragonite that represents;
● chemical formula Ca (Mg, Al)
3(Al
3si) O
10(OH)
2the xanthophyllite represented;
● chemical formula KMg
3(AlSi
3o
10) F
2the synthetic mica represented.
In one embodiment, the described sheet mica be included in described fire-resistant polyamide composite disclosed herein is selected from the sheet of following mica: phlogopite, biotite, zinnwaldite, rubellan, white mica, paragonite, xanthophyllite, synthetic mica and two or more combination above-mentioned.In another embodiment, described sheet mica is selected from the sheet of phlogopite, white mica or its mixture as used herein.
The various sheet micas useful at this are available commercially.Such as, the phlogopite sheet be applicable to or white clouds master slice can purchased from rice Nanogram Corp. of Sweden (Minelco) or Shijiazhuang Chen Xing Industrial Co., Ltd.s.
With the total weight of described fire-resistant polyamide composite disclosed herein, the content of described sheet mica can be about 0.1-10 % by weight, or about 0.3-8 % by weight, or about 0.5-6 % by weight, and wherein said composition total weight per-cent is 100 % by weight.
The described optional at least one toughener be included in described fire-resistant polyamide composite disclosed herein is selected from glass fibre, sheet glass and combination thereof.Preferably, described toughener is glass fibre as used herein.
With the total weight of described fire-resistant polyamide composite disclosed herein, the content of described optional toughener can for being up to about 45 % by weight, or about 15-40 % by weight, or about 25-35 % by weight, and the total weight percent of wherein said composition is 100 % by weight.
In addition, described fire-resistant polyamide composite disclosed herein optionally can also comprise other extra fire retarding synergist, it includes but not limited to: silicone, metal oxide is (as silicon-dioxide, ferric oxide, titanium dioxide, manganese oxide, magnesium oxide, zirconium white, zinc oxide, molybdenum oxide, cobalt oxide, bismuth oxide, chromic oxide, stannic oxide, weisspiessglanz, nickel oxide, cupric oxide or Tungsten oxide 99.999), metal-powder is (as aluminium, iron, titanium, manganese, zinc, molybdenum, cobalt, bismuth, chromium, tin, antimony, nickel, copper or tungsten), with metal-salt (as zinc borate, zinc metaborate, barium metaborate, zinc carbonate, magnesiumcarbonate, calcium carbonate or barium carbonate), with two or more combination above-mentioned.In one embodiment, the described extra fire retarding synergist be included in described fire-resistant polyamide composite disclosed herein is selected from aluminum oxide, zinc borate and its mixture.In another embodiment, the described extra fire retarding synergist be included in described fire-resistant polyamide composite disclosed herein is zinc borate.Described extra fire retarding synergist (such as, zinc borate) content in described fire-resistant polyamide composite disclosed herein is for being up to about 5 % by weight, or about 0.1-2 % by weight, or about 0.2-0.5 % by weight, the total weight percent of wherein said composition is 100 % by weight.
But according to the disclosure, described fire-resistant polyamide composite is substantially free of nitrogenous compound, this refers to described composition and absolutely not contains or comprise the nitrogenous compound being less than about 0.001 % by weight.In addition, according to the disclosure, described nitrogenous compound comprises the derivative of trimeric cyanamide, benzoguanamine, three (hydroxyethyl) isocyanuric acid ester, wallantoin, glycoluril (glycouril), Dyhard RU 100, guanidine, carbodiimide and above-mentioned any one.More particularly, described nitrogenous compound comprises (i) melamine cyanurate, (ii) the condenses of trimeric cyanamide, (iii) the reaction product of phosphoric acid and trimeric cyanamide, and the reaction product of the (iv) condenses of phosphoric acid and trimeric cyanamide.More particularly, the condenses of trimeric cyanamide can comprise melem, melam and melon, and their higher derivative and mixture; The reaction product of the condenses of the reaction product of phosphoric acid and trimeric cyanamide or phosphoric acid and trimeric cyanamide can comprise two melamine phosphate, two melamine pyrophosphate, melamine phosphate, Melamine polyphosphate, melamine pyrophosphoric ester, Melamine polyphosphate, melam polyphosphate, melon polyphosphate, and melem polyphosphate.
In addition, according to the disclosure, described fire-resistant polyamide composite disclosed herein is also substantially free of boehmite, and this refers to described composition and absolutely not contains or comprise the boehmite being less than about 0.001 % by weight.
Described fire-resistant polyamide composite disclosed herein optionally can also comprise other extra additive, as other polymkeric substance, impact modifier, UV light stabilizing agent, thermo-stabilizer, antioxidant, FLOW IMPROVERS, processing aid, lubricant, tinting material (comprising dyestuff, pigment, carbon black etc.) and two or more combination above-mentioned.
In one embodiment, described fire-resistant polyamide composite disclosed herein is substantially composed of the following components: the described at least one aromatic poly amide of (a) about 15-90 % by weight; The described at least one halogen-free flame retardants of (b) about 5-30 % by weight; The described sheet mica of (c) about 0.1-10 % by weight; (d) be up to the described at least one toughener of about 45 % by weight, in wherein said composition, the total weight percent of all components is 100 % by weight.In another embodiment, described fire-resistant polyamide composite disclosed herein is substantially composed of the following components: the described at least one aromatic poly amide of (a) about 25-75 % by weight; The described at least one halogen-free flame retardants of (b) about 8-20 % by weight; The described sheet mica of (c) about 0.3-8 % by weight; (d) the described at least one toughener of about 15-40 % by weight, in wherein said composition, the total weight percent of all components is 100 % by weight.In another one embodiment, described fire-resistant polyamide composite disclosed herein is substantially composed of the following components: the described at least one aromatic poly amide of (a) about 35-64 % by weight; The described at least one halogen-free flame retardants of (b) about 10-15 % by weight; The described sheet mica of (c) about 0.5-6 % by weight; (d) the described at least one toughener of about 25-35 % by weight, in wherein said composition, the total weight percent of all components is 100 % by weight.
Described retardant polyamide composition disclosed herein can use any currently known methods to be prepared by component described in melt blending.Melting mixer such as list or twin screw extruder, kneader, blending machine, Banbury mixer (such as, Banbury Banbury mixer) etc. can be used to be mixed to produce described composition by constituent materials.Or, a part of constituent materials can be mixed in melting mixer, then all the other constituent materialss be added and melting mixing, until reach even.
As embodiment proves below, when at aromatic poly amide (such as polyamide 6,6/6, T and polyamide 6, I/6, T) in be used alone halogen-free flame retardants (such as aluminum diethylphosphinate), and when not adding fire retarding synergist (as boehmite, Melamine polyphosphate (MPP) or mica), the non-constant of UL-94 flammability rating (being V-1, as shown in CE1) of described composition.After adding boehmite, the UL flammability rating of described composition is improved as V-0(as shown in CE2).But interpolation boehmite also causes shock strength to reduce about 25%(and is reflected in otch charpy impact intensity measurements).On the contrary, add sheet mica and not only the UL-94 flammability rating of described composition is brought up to V-0, it also makes the shock strength of described composition obtain maintenance (see such as E1-E9).In addition, as CE3 proves, MPP is added also undesirable as fire retarding synergist, because it causes during molding process, mold deposits occurs.
Described fire-resistant polyamide composite disclosed herein can use any known melt-processed means to form goods, as pressing mold, injection moulding, blowing, roational molding, transfer mould, thermoforming, extrudes.
Therefore, also disclosed herein a kind of goods formed by described fire-resistant polyamide composite disclosed herein.The moulded product that this goods are preferably formed by described fire-resistant polyamide composite disclosed herein or extruded product.Further, the UL-94 flammability rating (use the test bar of 0.8 mm thick carry out measure) of this moulded product or extruded product is V-0.In addition, this moulded product or extruded product, its otch charpy impact intensity (measuring according to ISO179/1eA) is compared to comprising substantially not containing moulded product or the extruded product of the comparable fire-resistant polyamide composite of sheet mica, low less than about 17% or low less than about 13%.Or this moulded product or extruded product otch charpy impact intensity are at least about 7KJ/m
2or at least about 7.3KJ/m
2.The example of moulded product disclosed herein or extruded product includes but not limited to: electrical cnnector, connector shell, interrupter envelope and relay1 case.
Embodiment
Material:
● PA6T/66: the Zytel deriving from E.I.Du Pont Company
?hTN502 polyamide resin;
● PA6I/6T: the Zytel deriving from E.I.Du Pont Company
?hTN503 polyamide resin;
● PA66/6T: a kind of partially aromatic polyamide, it is 1 years old, the mol ratio of 6-adipic acid and terephthalic acid is 75:25, and its preparation process is as follows: the polyamide 6 T salts solution (1327.21 kilograms) of to be polyamide 66 salts solution (1781.71 kilograms) and the pH of 8.1 51.7 % by weight by pH be 7.6 25.2 % by weight, add reactor with 100 grams of conventional defoamers, 20 grams of sodium hypophosphites, 220 grams of sodium bicarbonates, 80% hexanediamine (HMD) aqueous solution of 2476 grams together with 1584 grams of Glacial acetic acid.Then heated by described solution, simultaneously authorized pressure rises to 18 normal atmosphere, is 18 normal atmosphere, and continues to heat until the temperature of batch of material reaches 250 DEG C in this discharged steam to keep pressure.Then slowly decompression, to 0.4 normal atmosphere, allows batch temperature to rise to 280-290 DEG C more simultaneously.Then keep pressure at 0.4 normal atmosphere, and temperature is kept 20 minutes at 280-290 DEG C.Finally, polymer melt is extruded into slice, cools and be cut into pill;
● FR: a kind of halogen-free flame retardants based on aluminum diethylphosphinate, available from Clariant Corporation, trade mark is called Exolit
tMoP1230;
● mica-1:PW30 phlogopite, available from rice Nanogram Corp.;
● mica-2:PW80 phlogopite, available from rice Nanogram Corp.;
● mica-3: white mica, available from Shijiazhuang Chen Xing Industrial Co., Ltd.;
● BMT: boehmite, available from Japanese He He lime Industrial Co., Ltd (KawaiSekkaiKogyoK.K.), trade mark is called Celasule
tMbMT-33;
● MPP: Melamine polyphosphate, available from BASF Aktiengesellschaft (BASF), trade mark is called Melapur
tM200/70;
● GF:E-glass fibre, available from Nippon Electric Glass Co., Ltd (NipponElectricGlass);
● ZB: zinc borate, available from United States Borax Inc. (USBorax), trade mark is called Firebrake
tMzB;
● lubricant-1: montanic acid calcium, available from Clariant Corporation, trade mark is called Licomont
tMcaV102;
● lubricant-2: stearyl erucamide, available from standing grain major company of Britain (Croda), trade mark is called Crodamide212;
● tinting material: PAM (F) 25420 carbon black enriched material, available from Japanese Dainichiseika Color Chem (DainiSeikaCo., Ltd.);
● flowing agent: Tetra hydro Phthalic anhydride, available from Chinese lark prestige Science and Technology Ltd. (J & KScientificLtd.).
Test method:
● tensile strength and extension at break amount are measured according to ISO527-1/2;
● flexural strength and modulus in flexure are measured according to ISO178-1/2;
● otch charpy impact intensity (NotchedCharpyimpactstrength) is measured according to ISO179/1eA;
● UL-94 flammability rating (UnderwritersLaboratory) is that the test bar of use 0.8 mm thick carries out measuring;
● mold deposits by carrying out visual control to determine after molding process.
Comparative example CE1-CE3 and embodiment E 1-E9:
Comparative example CE1-CE3 and embodiment E 1-9 each in, by compound in the ZSK twin screw extruder of 26 millimeters, prepare daiamid composition (all components row in Table 1).All components is blended together and adds the rear portion of described forcing machine, except being added from the side by glass fibre except in the machine barrel of downstream.Barrel zone temperature is set to about 260-330 DEG C.After discharging described forcing machine, blended composition cools is cut into pill.Then the montanic acid calcium of the pellet surface coating 0.1 % by weight of CE1-CE3 and E1-E9 will be used for.
Subsequently; for the preparation of measurement tensile strength, extension at break amount, flexural strength, modulus in flexure, otch charpy impact intensity and the flammable moulded product of UL-94 on Sumitomo (Sumitomo) 100T injector, wherein barrel temperature is set to about 280-310 DEG C and molding temperature is set to about 90-100 DEG C.
Then, to each sample measurement tensile strength, extension at break amount, flexural strength, modulus in flexure, otch charpy impact intensity and UL-94 flammability rating, and visual control mold deposits.All results make table 1.
As wherein shown, when being used alone aluminum diethylphosphinate in the mixture at PA66/6T and PA6I/6T, and when not adding fire retarding synergist (as boehmite (BMT), Melamine polyphosphate (MPP) or mica), the non-constant of UL-94 flammability rating (being V-1, as shown in CE1) of described composition.After adding BMT, the UL flammability rating of described composition is improved as V-0(as shown in CE2).But interpolation BMT also causes shock strength to reduce about 25%(and is reflected in otch charpy impact intensity measurements).On the contrary, add sheet mica and not only raise the UL-94 flammability rating of described composition to V-0, it also maintains the shock strength (see such as E1-E9) of described composition.In addition, as CE3 proves, MPP is added also undesirable as fire retarding synergist, because it causes during molding process, mold deposits occurs.
Comparative example CE4-CE6 and embodiment E 10-E11:
Prepare CE4-CE6 and E10-E11 blend composition separately (composition as listed that each composition comprises in table 2) in the same manner as described above.
Tensile strength, elongation at break, flexural strength, modulus in flexure, otch charpy impact intensity and UL-94 flammability rating are measured to each moulded product manufactured by each blend composition, and makes table 2.
Show equally, in the blend of PA66/6T and PA6I/6T, add sheet mica improves described composition flame retardant resistance as fire retarding synergist, and do not make its shock strength reduce.
Table 2
Claims (15)
1. a fire-resistant polyamide composite, it is substantially free of nitrogenous compound, and wherein based on said composition total weight, said composition is substantially composed of the following components:
At least one aromatic poly amide of (a) 15-90 % by weight;
At least one halogen-free flame retardants of (b) 5-30 % by weight;
The sheet mica of (c) 0.1-10 % by weight; With optional
D () is up at least one toughener of 45 % by weight, it is selected from glass fibre and sheet glass,
In wherein said composition, the total weight percent of all components is 100 % by weight,
And described at least one halogen-free flame retardants is selected from the phosphinates of formula (I), the diphosphinic acid salt of formula (II), and the combination of described phosphinates and/or diphosphinic acid salt and polymkeric substance:
Wherein R
1and R
2identical or different, and R
1and R
2each hydrogen naturally, the C of straight chain, side chain or ring-type
1-C
6alkyl, or C
6-C
10aryl; R
3straight or branched C
1-C
10alkylidene group, C
6-C
10arylidene, C
6-C
12alkyl-arylene, or C
6-C
12aryl-alkylidene group; M is selected from calcium ion, magnesium ion, aluminum 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 two or more combination above-mentioned; And m, n and x are identical or different, the integer of their each 1-4 naturally.
2. fire-resistant polyamide composite according to claim 1, it is substantially free of boehmite.
3. fire-resistant polyamide composite according to claim 1, wherein said at least one aromatic poly amide is selected from polyamide 6,6/6, T; Polyamide 6, T/6,6; Polyamide 6, T/D, T; Polyamide 6, I/6, T; Polymeric amide 9, T; Polymeric amide 10, T; Polymeric amide 12, T; With two or more combination above-mentioned.
4. fire-resistant polyamide composite according to claim 3, wherein said at least one aromatic poly amide is polyamide 6, T/6,6.
5. fire-resistant polyamide composite according to claim 3, wherein said at least one aromatic poly amide is the mixture of two or more aromatic poly amide.
6. fire-resistant polyamide composite according to claim 5, wherein said at least one aromatic poly amide is selected from polyamide 6,6/6, T and polyamide 6, the mixture of I/6, T; Polyamide 6, T/6,6 and polyamide 6, the mixture of I/6, T; And polyamide 6, T/6,6 and polyamide 6, the mixture of T/D, T.
7. the fire-resistant polyamide composite according to any one of claim 1-3, wherein said at least one halogen-free flame retardants is selected from aluminum diethylphosphinate, methylethyl phospho acid aluminium and combination thereof.
8. the fire-resistant polyamide composite according to any one of claim 1-3, wherein said sheet mica is selected from the sheet of phlogopite, white mica and composition thereof.
9. the fire-resistant polyamide composite according to any one of claim 1-3, it is substantially composed of the following components: the described at least one aromatic poly amide of (a) 25-75 % by weight; The described at least one halogen-free flame retardants of (b) 8-20 % by weight; The described sheet mica of (c) 0.3-8 % by weight; (d) the described at least one toughener of 15-40 % by weight, in wherein said composition, the total weight percent of all components is 100 % by weight.
10. fire-resistant polyamide composite according to claim 9, it is substantially composed of the following components: the described at least one aromatic poly amide of (a) 35-64 % by weight; The described at least one halogen-free flame retardants of (b) 10-15 % by weight; The described sheet mica of (c) 0.5-6 % by weight; (d) the described at least one toughener of 25-35 % by weight, in wherein said composition, the total weight percent of all components is 100 % by weight.
11. the fire-resistant polyamide composite according to any one of claim 1-3, it optionally also comprises and is up to 5 % by weight, or 0.1-2 % by weight, or the zinc borate of 0.2-0.5 % by weight, in wherein said composition, the total weight percent of all components is 100 % by weight.
12. goods comprising the fire-resistant polyamide composite according to any one of claim 1-11.
13. goods according to claim 12, it is moulded product or extruded product, the test bar of 0.8 mm thick is used to measure, its UL-94 flammability rating is V-0, and measure according to ISO179/1eA, its otch charpy impact intensity is compared to comprising substantially not containing moulded product or the extruded product of the comparable fire-resistant polyamide composite of sheet mica, low less than 17% or low less than 13%.
14. goods according to claim 13, measure according to ISO179/1eA, and the otch charpy impact intensity of described moulded product or extruded product is at least 7KJ/m
2or at least 7.3KJ/m
2.
15. goods according to claim 14, described moulded product or extruded product are selected from electrical cnnector, connector shell, interrupter envelope and relay1 case.
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| CN104177821B (en) * | 2013-05-27 | 2017-09-08 | 杜邦公司 | Fire-resistant polyamide composite with improved impact resistance |
| CN105331099B (en) * | 2014-08-12 | 2018-02-23 | 杜邦公司 | Fire-resistant polyamide composite |
| DE102017212098A1 (en) * | 2017-07-14 | 2019-01-17 | Clariant Plastics & Coatings Ltd | Flame retardant polyamide compositions with high heat resistance and their use |
| CN107417977B (en) * | 2017-07-19 | 2019-07-12 | 广州铂钡信息科技有限公司 | A kind of additive and preparation method thereof for polymer |
| US11965093B2 (en) | 2018-12-06 | 2024-04-23 | Basf Se | Polyamide composition |
| CN116200030A (en) * | 2022-12-19 | 2023-06-02 | 金发科技股份有限公司 | Flame-retardant polyamide composite material and preparation method and application thereof |
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| JP2004292531A (en) * | 2003-03-26 | 2004-10-21 | Asahi Kasei Chemicals Corp | Flame-retardant polyamide resin composition |
| CN101570633A (en) * | 2008-04-30 | 2009-11-04 | 第一毛织株式会社 | Flame retardant thermoplastic resin composition and mould product produced therefrom |
| JP2009263503A (en) * | 2008-04-25 | 2009-11-12 | Asahi Kasei Chemicals Corp | Flame-retardant resin composition |
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| DE102005041966A1 (en) * | 2005-09-03 | 2007-03-08 | Clariant Produkte (Deutschland) Gmbh | Polyamide moulding material, e.g. for production of electrical switches and plugs, contains thermoplastic polyamide, phosphinate salt, synergist or phosphorus-nitrogen fire retardant, reinforcing fibres and filler |
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| JP2009263503A (en) * | 2008-04-25 | 2009-11-12 | Asahi Kasei Chemicals Corp | Flame-retardant resin composition |
| CN101570633A (en) * | 2008-04-30 | 2009-11-04 | 第一毛织株式会社 | Flame retardant thermoplastic resin composition and mould product produced therefrom |
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