CN101987915B - Polymer composite containing polyalcohol and co-stabilizer - Google Patents
Polymer composite containing polyalcohol and co-stabilizer Download PDFInfo
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- CN101987915B CN101987915B CN200910160559A CN200910160559A CN101987915B CN 101987915 B CN101987915 B CN 101987915B CN 200910160559 A CN200910160559 A CN 200910160559A CN 200910160559 A CN200910160559 A CN 200910160559A CN 101987915 B CN101987915 B CN 101987915B
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Abstract
The invention relates to an application of polyalcohol with more than two hydroxide radicals and co-stabilizer in increasing long-term thermostability of polyamide composite. The co-stabilizer is selected from melamine compound, guanidine compound and hindered phenol.
Description
Invention field
The polyvalent alcohol and the co-stabilizer that the present invention relates to have more than two hydroxyls are used to improve the said composition long-term thermal stability at high temperature and the purposes of rheological behavior in daiamid composition, said co-stabilizer is selected from following material: melamine compound, guanidine compound and hindered phenol.
Background of invention
Thermostability is a kind of very crucial character to the polymkeric substance that uses in many application.When plastic components (for example, the electric or electron device part of automobile) is exposed to hot conditions following time for a long time, its mechanical property will descend owing to the thermal destruction of polymkeric substance, and this phenomenon is also referred to as thermal ageing.In order to prevent that mechanical property from descending, in polymeric matrix, add the thermal ageing property that various thermo-stabilizers improve polymkeric substance.
Polymeric amide or polyester are stablized through adding thermo-stabilizer (for example phenolic antioxidant, aromatic amine and copper, elemental copper or mixes the mantoquita that forms with potassiumiodide or Potassium Bromide) usually.Stabilization under phenolic antioxidant or aromatic amine are often used in up to 130 ℃.Be applicable to the thermostability under higher temperature with KI or KBr blended cuprous iodide, but seem that when application of temperature surpasses 170 ℃ thermostable effect is not enough.And CuI and potassium halide are very expensive, and because halid existence also possibly cause some etching problems.The develop rapidly of automotive industry and electronic industry requires polymer materials to have higher thermostability, and the prolonged application temperature of polymeric amide or polyester material need be brought up to 210 ℃, even more up to 230 ℃.It is reported that elemental iron or iron protoxide can improve the long term heat ageing performance of polymeric amide or polyester effectively.Yet the iron powder that in expressing technique, uses will not only can cause serious safety-problems and scattering problem, but also can cause the mechanical property of polyamide material to descend.
EP 1041109 disclose comprise polyamide resin, fusing point is the daiamid composition of 150 to 280 ℃ polyvalent alcohol, this daiamid composition has good flowability and physical strength and can be used for injecting welding technique.
Press for a kind of polymer compsn that excellent its physical properties of high high-temp stability while will can not affect adversely that has.
Summary of the invention
A target of the present invention provides has the purposes that in daiamid composition, is used to improve the high-temperature stability of said composition more than the polyvalent alcohol of two hydroxyls and co-stabilizer, and said co-stabilizer is selected from the group of being made up of melamine compound, guanidine compound and hindered phenol.
Detailed Description Of The Invention
In the present invention, if not explanation clearly, otherwise per-cent (%) or umber are meant weight percent (wt%) or weight part with respect to daiamid composition.
In the present invention, if explanation clearly, each component or preferred ingredients can make up each other and form the new compsn that is used for new solution.
In the present invention, except as otherwise noted, otherwise the abbreviation that numerical range " a-b " expression a makes up to any real number between the b, wherein a and b are real numbers.For example, listed the whole real numbers in " 0-5 " among numerical range " 0-5 " expression this paper, and " 0-5 " only to be the breviary of these combinations of values represent.
In the present invention, except as otherwise noted, otherwise the abbreviation that integer numerical range " a-b " expression a makes up to the arbitrary integer between the b, wherein a and b are integers.For example, integer range " 1-N " expression 1,2...N, wherein N is an integer.
In the present invention, except as otherwise noted, otherwise " their combination " represented the multicomponent mixture of each element, for example, and the multicomponent mixture of two kinds, three kinds, four kinds and as many as most probable number MPN purpose composition.
If do not spell out, then used term " a kind of " is meant " at least a " in this specification sheets.
" scope " disclosed herein is the form with the lower limit and the upper limit.Can have one or more lower limits respectively, and one or more upper limit.Given range limits through a selected lower limit and a upper limit.The concrete border that the selected lower limit and the upper limit define scope.All scopes that can limit by this way be comprising property with capable of being combined, promptly any lower limit can be combined to form a scope with any upper limit.For example, to special parameter,, should be appreciated that then 60 to 110 and 80 to 120 scope also can be predicted if listed 60 to 120 and 80 to 110 scope.In addition, if listed minimum extent value 1 and 2 and listed maximum range value 3,4 and 5, then the scope below all can be predicted: 1 to 3,1 to 4,1 to 5,2 to 3,2 to 4 and 2 to 5.
In the present invention, except as otherwise noted, otherwise " guanidine compound " expression contains the compound of following radicals:
In the present invention, except as otherwise noted, otherwise " high temperature " be meant and be equal to or higher than 170 ℃ temperature, preferably is equal to or higher than 210 ℃ temperature.
In the present invention, except as otherwise noted, otherwise " for a long time " be meant equal or be longer than 500 hours, preferably equal or be longer than 1000 hours digestion period.
In the present invention, polymkeric substance can be the polyamide thermoplastic of any routine.
In the present invention, polymeric amide is the polycondensation product of one or more dicarboxylicacid or polycarboxylic acid and one or more diamines, and/or one or more amino acid whose polycondensation products, and/or the ring-opening polymerization product of one or more cyclic lactames.Suitable cyclic lactames is hexanolactam and Ω-laurolactam.Polymeric amide can be full-cream family or half aromatics.
In polymer compsn of the present invention, full-cream polyamide is by aliphatic series and alicyclic monomer, and for example diamines, diprotic acid, lactan, amino acid and their reactive equivalent form.Suitable amino acid is the amino dodecylic acid of 11-.Suitable lactan is hexanolactam and Ω-laurolactam.
In the present invention, term " full-cream polyamide " multipolymer that also refers to form and the blend of two or more full-cream polyamides by two or more this monomers.Also can use straight chain, side chain and cyclic monomer.
The carboxylic acid monomer who comprises in the whole aliphatic polyamide includes but not limited to aliphatic dicarboxylic acid, for example hexanodioic acid (C6), pimelic acid (C7), suberic acid (C8), nonane diacid (C9), sebacic acid (C10), dodecanedioic acid (C12) and tetradecane diacid (C14).Diamines is selected from the diamines with four or more a plurality of carbon atoms, includes but not limited to tetramethylenediamine, hexanediamine, octamethylenediamine, decamethylene diamine, 2-methyl isophthalic acid, 5-pentamethylene diamine, 2-ethyl tetramethylenediamine, 2-methyl octamethylenediamine, trimethylammonium hexanediamine and their combination.
Partially aromatic polyamide is the homopolymer that formed by the monomer that contains aromatic group, multipolymer, terpolymer or high-grade polymkeric substance more.One or more aromatic carboxylic acids can be the mixtures of terephthalic acid or terephthalic acid and one or more other carboxylic acids (for example m-phthalic acid, phthalic acid, 2-methyl terephthalic acid and naphthalic acid).In addition, one or more aromatic carboxylic acids can with as above disclosed one or more aliphatic dicarboxylic acids mix.
Preferred polyamide disclosed herein is homopolymer or multipolymer, and wherein term copolymer refers to have the polymeric amide of two or more acid amides and/or diamide molecule repeating unit.Homopolymer and multipolymer are confirmed through their repeating units separately.For multipolymer disclosed herein, repeating unit is listed with the descending of the molar percentage repeating unit that exists in the multipolymer.Following abbreviation is used for confirming the monomer and the repeating unit of homopolymer and multipolymer polyamide (PA):
The HMD hexanediamine
The T terephthalic acid
The AA hexanodioic acid
The DMD decamethylene diamine
The DDA sebacic acid
The DDDA dodecanedioic acid
The I m-phthalic acid
TMD 1, the 4-tetramethylenediamine
The polymer repeat unit that 4T is formed by TMD and T
The polymer repeat unit that 6T is formed by HMD and TPA
The polymer repeat unit that DT is formed by 2-MPMD and TPA
66 polymer repeat units that form by HMD and AA
The polymer repeat unit that 10T is formed by DMD and TPA
410 polymer repeat units that form by TMD and DDA
510 by 1, the polymer repeat unit that 5-pentamethylene diamine and DDA form
610 polymer repeat units that form by HMD and DDA
612 polymer repeat units that form by HMD and DDDA
11 polymer repeat units that form by the amino undecanoic acid of 11-
12 polymer repeat units that form by 12 amino dodecanoic acid
In one embodiment, daiamid composition comprises one or more polymeric amide that is selected from following material:
(I) of the polyamide group, a melting point of less than 210 ℃, including aliphatic or semi-aromatic polyamide, selected from the following materials: poly (pentamethylene sebacamide) (PA510), poly (dodecyl pentylene diamide) (PA512), poly (ε-caprolactam / hexamethylene adipamide) (PA6/66), poly (ε-caprolactam / hexamethylene sebacamide) (PA6/610), poly (ε-caprolactam / Asia hexyl dodecane diamide) (PA6/612), poly (hexamethylene diamide tridecyl) (PA613), poly (hexamethylene diamide pentadecyl) (PA615), poly (ε-caprolactam / butylene the isophthalamide) (PA6/4T), poly (ε-caprolactam / hexamethylene terephthalamide) (PA6/6T), poly (ε-caprolactam / decamethylene terephthalamide) (PA6/10T ), poly (ε-caprolactam / dodecamethylene terephthalamide) (PA6/12T), poly (hexamethylene sebacamide / hexamethylene terephthalamide) (PA610/6T), poly (alkylene hexyl dodecane diamide / hexamethylene terephthalamide) (PA612/6T), poly (hexamethylene diamide myristic / hexamethylene terephthalamide) (PA614/6T), poly (ε-caprolactam / hexamethylene isophthalamide / hexamethylene terephthalamide) (PA6/6I/6T), poly (ε-caprolactam / hexamethylene adipamide / hexamethylene sebacamide) (PA6/66/610) , poly (ε-caprolactam / hexamethylene adipamide / hexamethylene dodecane diamide) (PA6/66/612), poly (ε-caprolactam / hexamethylene adipamide / hexamethylene sebacamide / hexamethylene Base ten dioxane diamide) (PA6/66/610/612), poly (2 - methyl pentyl adipamide / hexamethylene adipamide / hexamethylene terephthalamide) (PA? D6/66 /? / 6T), poly (2 - methyl pentyl adipamide / hexamethylene adipamide) (PA? D6/66), poly (decamethylene sebacamide) (PA1010), poly (decyl Base ten dioxane diamide) (PA1012), poly (decamethylene sebacamide / decamethylene terephthalamide) (PA1010/10T), poly (decamethylene sebacamide / sodium dodecyl sebacamide / decylene terephthalamide / dodecamethylene terephthalamide (PA1010/1210/10T/12T), poly (11 - aminoundecanoic acid amide) (PA11), poly (11 - amino ten monoalkyl amide / tetramethylene terephthalamide) (PA11/4T), poly (11 - aminoundecanoic lactam / hexamethylene terephthalamide) (PA11/6T), poly (11 - aminoundecanoic acrylamide / decamethylene terephthalamide) (PA11/10T), poly (11 - aminoundecanoic acid amide / sodium dodecyl terephthalamide) (PA11/12T), poly (12 - amino ten dioxane amide) (PA12), poly (12 - amino-acid amide dodecane / tetramethylene terephthalamide) (PA12/4T), poly (12 - amino-dodecanoic acid amide / hexamethylene terephthalamide) (PA12/6T), poly (12 - amino-dodecanoic acid amide / decamethylene terephthalamide) (PA12/10T), poly (dodecyl dodecane diamide) (PA1212) and poly ( dodecanedioic alkylene dodecyl acrylamide / dodecamethylene terephthalamide) (PA1212/12T);
(II) organizes polymeric amide; Its fusing point is at least 210 ℃, comprises the aliphatic polyamide that is selected from following material: gather (butylidene adipamide) (PA46), gather (ε-Ji Neixianan) (PA 6), gather (hexylidene adipamide/(ε-Ji Neixianan) (PA 66/6), gather (hexylidene adipamide) (PA 66), gather (hexylidene adipamide/hexylidene sebacoyl amine) (PA66/610), gather (hexylidene adipamide/hexylidene dodecyl diamide) (PA66/612), gather (hexylidene adipamide/inferior decyl sebacoyl amine) (PA66/1010), gather (hexylidene sebacoyl amine) (PA610), gather (hexylidene dodecyl diamide) (PA612), gather (hexylidene tetradecane diamide) (PA614), gather (hexylidene n-Hexadecane diamide) (PA616) and gather (butylidene adipamide/2-methyl pentylidene adipamide) (PA46/D6);
(III) organizes polymeric amide, and its fusing point is at least 210 ℃, comprises
(gg) half aromatic repeating units of 20 to 35 molar percentages, said half aromatic repeating units are derived from the monomer that is selected from one or more following materials:
V. the aromatic dicarboxylic acid and aliphatic diamine that have 8 to 20 carbon atoms with 4 to 20 carbon atoms; And
(hh) the aliphatic repeating unit of 65 to 80 molar percentages, said aliphatic repeating unit are derived from the monomer that is selected from one or more following materials:
Vi. the aliphatic dicarboxylic acid and the said aliphatic diamine that have 6-20 carbon atom with 4 to 20 carbon atoms; And
Vii. the lactan and/or the aminocarboxylic acid that have 4-20 carbon atom; And
Viii. their mixture;
(IV) organizes polymeric amide, comprises
(cc) half aromatic repeating units of 50 to 95 molar percentages, said half aromatic repeating units are derived from the monomer that is selected from one or more following materials:
(i) aromatic dicarboxylic acid that has 8 to 20 carbon atoms and aliphatic diamine with 4 to 20 carbon atoms; And
(dd) the aliphatic repeating unit of 5 to 50 molar percentages, said aliphatic repeating unit are derived from the monomer that is selected from one or more following materials:
The aliphatic dicarboxylic acid and the said aliphatic diamine that (ii) have 6 to 20 carbon atoms with 4 to 20 carbon atoms;
The lactan and/or the aminocarboxylic acid that (iii) have 4 to 20 carbon atoms; And
(iv) their mixture;
(V) organizes polymeric amide, and its fusing point is at least 260 ℃, comprises
(ee) greater than half aromatic repeating units of 95 molar percentages, said half aromatic repeating units is derived from the monomer that is selected from one or more following materials:
(i) aromatic dicarboxylic acid that has 8 to 20 carbon atoms and aliphatic diamine with 4 to 20 carbon atoms;
(ff) be less than the aliphatic repeating unit of 5 molar percentages, said aliphatic repeating unit is derived from the monomer that is selected from one or more following materials:
The aliphatic dicarboxylic acid and the said aliphatic diamine that (ii) have 6 to 20 carbon atoms with 4 to 20 carbon atoms; And
The lactan and/or the aminocarboxylic acid that (iii) have 4 to 20 carbon atoms; And
(iv) their mixture; And
(VI) organizes polymeric amide; It does not have fusing point, is selected from following material: gather (hexylidene isophthaloyl amine/hexylidene terephthalamide) (6I/6T) and gather (hexylidene isophthaloyl amine/hexylidene terephthalamide/hexylidene adipamide) (6I/6T/66).
(I) organizes polymeric amide, can have the degree that half aromatic repeating units to fusing point is lower than 210 ℃, and the partially aromatic polyamide of this group has half aromatic repeating units that is less than 40 molar percentages usually.Half aromatic repeating units be defined as derived from be selected from one or more following materials monomeric those: aromatic dicarboxylic acid with 8 to 20 carbon atoms and aliphatic diamine with 4 to 20 carbon atoms.
Preferred (III) group polymeric amide is selected from following material: gather (butylidene adipamide/butylidene terephthalamide) (PA46/4T); Gather (butylidene adipamide/hexylidene terephthalamide) (PA46/6T); Gather (butylidene adipamide/2-methyl pentylidene adipamide/inferior decyl terephthalamide) PA46/D6/10T); Gather (hexylidene adipamide/hexylidene terephthalamide) (PA66/6T); Gather (hexylidene adipamide/hexylidene isophthaloyl amine/hexylidene terephthalamide PA66/6I/6T and gather (hexylidene adipamide/2-methyl pentylidene adipamide/hexylidene terephthalamide (PA66/D6/6T); And most preferred (III) group polymeric amide is PA 66/6T.
Preferred (IV) group polymeric amide is selected from following material: gather (butylidene terephthalamide/hexylidene adipamide) (PA4T/66); Gather (butylidene terephthalamide/ε-Ji Neixianan) (PA4T/6); Gather (butylidene terephthalamide/hexylidene dodecyl diamide) (PA4T/612); Gather (butylidene terephthalamide/2-methyl pentylidene adipamide/hexylidene adipamide) (PA4T/D6/66); Gather (hexylidene terephthalamide/2-methyl pentylidene terephthalamide/hexylidene adipamide) (PA6T/DT/66); Gather (hexylidene terephthalamide/hexylidene adipamide) PA6T/66; Gather (hexylidene terephthalamide/hexylidene sebacoyl amine) (PA6T/610); Gather (hexylidene terephthalamide/hexylidene tetradecane diamide) (PA6T/614); Gather (nine methylene radical terephthalamides/nine methylene radical sebacoyl amine) (PA9T/910); Gather (nine methylene radical terephthalamides/nine methylene radical dodecyl diamide) (PA9T/912); Gather (the amino undecanoic amide of nine methylene radical terephthalamide/11-) (PA9T/11); Gather (the amino dodecyl acid amides of nine methylene radical terephthalamide/12-) (PA9T/12); Gather (the amino undecanoic amide of inferior decyl terephthalamide/11-) (PA10T/11); Gather (the amino dodecyl acid amides of inferior decyl terephthalamide/12-) (PA10T/12); Gather (inferior decyl terephthalamide/inferior decyl sebacoyl amine) (PA10T/1010); Gather (inferior decyl terephthalamide/inferior decyl dodecyl diamide) (PA10T/1012); Gather (inferior decyl terephthalamide/butylidene adipamide) (PA10T/46); Gather (inferior decyl terephthalamide/ε-Ji Neixianan) (PA10T/6); Gather (inferior decyl terephthalamide/hexylidene adipamide) (PA10T/66); Gather (inferior dodecyl terephthalamide/inferior dodecyl dodecyl diamide) (PA12T/1212); Gather (inferior dodecyl terephthalamide/ε-Ji Neixianan) (PA12T/6) and gather (inferior dodecyl terephthalamide/hexylidene adipamide) (PA12T/66); And most preferred (IV) group polymeric amide is PA6T/66.
Preferred (V) group polymeric amide is selected from following material: gather (butylidene terephthalamide/2-methyl pentylidene terephthalamide) PA4T/DT; Gather (butylidene terephthalamide/hexylidene terephthalamide) PA4T/6T; Gather (butylidene terephthalamide/inferior decyl terephthalamide) PA4T/10T; Gather (butylidene terephthalamide/inferior dodecyl terephthalamide) PA4T/12T; Gather (butylidene terephthalamide/2-methyl pentylidene terephthalamide/hexylidene terephthalamide) (PA4T/DT/6T); Gather (butylidene terephthalamide/hexylidene terephthalamide/2-methyl pentylidene terephthalamide) (PA4T/6T/DT); Gather (hexylidene terephthalamide/2-methyl pentylidene terephthalamide) (PA6T/DT); Gather (hexylidene adipamide/hexylidene isophthaloyl amine) (PA 6T/6I); Gather (hexylidene terephthalamide/inferior decyl terephthalamide) PA6T/10T; Gather (hexylidene terephthalamide/inferior dodecyl terephthalamide) (PA6T/12T); Gather (hexylidene terephthalamide/2-methyl pentylidene terephthalamide/gather (inferior decyl terephthalamide) (PA6T/DT/10T); Gather (hexylidene terephthalamide/inferior decyl terephthalamide/inferior dodecyl terephthalamide) (PA6T/10T/12T); Gather (inferior decyl terephthalamide) (PA10T); Gather (inferior decyl terephthalamide/butylidene terephthalamide) (PA10T/4T); Gather (inferior decyl terephthalamide/2-methyl pentylidene terephthalamide) (PA10T/DT); Gather (inferior decyl terephthalamide/inferior dodecyl terephthalamide) (PA10T/12T); Gather that (inferior decyl terephthalamide/2-methyl pentylidene terephthalamide/(inferior decyl terephthalamide) (PA10T/DT/12T); Gather (inferior dodecyl terephthalamide) (PA12T); Gather (inferior dodecyl terephthalamide)/butylidene terephthalamide) (PA12T/4T); Gather (inferior dodecyl terephthalamide)/hexylidene terephthalamide) PA12T/6T; Gather (inferior dodecyl terephthalamide)/inferior decyl terephthalamide) (PA12T/10T) and gather (inferior dodecyl terephthalamide)/2-methyl pentylidene terephthalamide) (PA12T/DT) and most preferred (V) group polymeric amide be PA6T/D6.
In a plurality of embodiments, polymeric amide is respectively (I) group polymeric amide, (II) group polymeric amide, (III) group polymeric amide, (IV) group polymeric amide, (V) group polymeric amide or (VI) group polymeric amide.
This polymeric amide also can be the blend of two kinds or more kinds of polymeric amide.Preferred blends comprises those that are selected from (I) group and (II) group polymeric amide, (I) group and (III) group polymeric amide, (I) group and (VI) group polymeric amide, (II) group and (VI) group polymeric amide, (II) group and (IV) group polymeric amide, (II) group and (V) group polymeric amide and (IV) group and (V) group polymeric amide.
Preferred blends comprises (II) group and (V) group polymeric amide, and especially preferred blends comprises and gathers (hexylidene adipamide) (PA 66) and gather (hexylidene terephthalamide/2-methyl pentylidene terephthalamide) (PA 6T/DT).
Preferred blends comprises (II) group and (III) group polymeric amide in addition, and special preferred blends comprise gather (ε-Ji Neixianan) (PA6) and gather (hexylidene adipamide/hexylidene terephthalamide) (PA6,6/6T).
Polyvalent alcohol can be selected from the aliphatic hydroxyl cpd that contains more than two hydroxyls, contain aliphatic series-cycloaliphatic compounds more than two hydroxyls, contain cycloaliphatic compounds, aromatic substance and sugar more than two hydroxyls.
Aliphatic chain in the polyvalent alcohol not only can comprise carbon atom but also can comprise one or more for example heteroatomss of nitrogen, oxygen and sulphur atom that are selected from.The cyclic aliphatic ring that is present in the polyvalent alcohol can be the part of monocycle or two rings or polycyclic system and can be carbocyclic ring or heterocycle.The heterocycle that is present in the polyvalent alcohol can be the part of monocycle or two rings or polycyclic system, and can comprise two or more for example heteroatomss of nitrogen, oxygen and sulphur atom that are selected from.One or more polyvalent alcohols can comprise one or more substituting groups, for example ether, carboxylic acid group, carboxylic acyloxy amido or carboxylic acid ester groups.
The examples of polyhydric alcohols that contains more than two hydroxyls includes but not limited to triol, for example glycerine, TriMethylolPropane(TMP), 2,3-two-(2 '-hydroxyethyl)-hexanaphthene-1-alcohol, hexane-1,2; 6-triol, 1,1,1-three-(methylol) ethane, 3-(2 '-hydroxyl-oxethyl)-propane-1,2-glycol, 3-(2 '-the hydroxyl propoxy-)-propane-1; 2-glycol, 2-(2 '-hydroxyl-oxethyl)-hexane-1,2-glycol, 6-(2 '-the hydroxyl propoxy-)-hexane-1,2-glycol, 1,1; 1-three-[(2 '-hydroxyl-oxethyl)-methyl]-ethane, 1,1,1-three-[(2 '-the hydroxyl propoxy-)-methyl]-propane, 1,1; 1-three-(4 '-phenylor)-ethane, 1,1,1-three-(phenylor)-propane, 1; 1,3-three-(dihydroxyl-3-aminomethyl phenyl)-propane, 1,1; 4-three-(dihydroxy phenyl)-butane, 1,1,5-three-(phenylor)-3-methylpentane, two-TriMethylolPropane(TMP), ethoxylated trimethylolpropane or propoxylation TriMethylolPropane(TMP); Polyvalent alcohol, for example tetramethylolmethane, dipentaerythritol and tripentaerythritol; And sugar, for example Schardinger dextrins, D-seminose, glucose, semi-lactosi, sucrose, fructose, wood sugar, pectinose, D-mannitol, D-Sorbitol Powder, D-or L-arabitol, Xylitol, iditol, talitol, allitol, altritol, guilitol, tetrahydroxybutane, threitol and D-gulonic acid-y-lactone or the like.
Preferred polyhydric alcohols comprises those with a pair of hydroxyl, and said hydroxyl is connected to the carbon atom that is separated each other by at least one atom separately.Special preferred polyhydric alcohols is that wherein a pair of hydroxyl is connected to those of separately the carbon atom that is separated each other by single carbon atom.
Preferably, the polyvalent alcohol that is used for according to resin combination of the present invention is tetramethylolmethane, dipentaerythritol, tripentaerythritol, two-TriMethylolPropane(TMP), D-mannitol, D-Sorbitol Powder and Xylitol.More preferably, the polyvalent alcohol that is used for according to resin combination of the present invention is dipentaerythritol and/or tetramethylolmethane.Most preferred polyvalent alcohol is a dipentaerythritol.
In a plurality of embodiments; Based on the gross weight of said daiamid composition, the content of said polyvalent alcohol in daiamid composition is the 0.25-15 weight percent, is preferably the 0.5-8 weight percent; More preferably the 1-5 weight percent most preferably is the 2-5 weight percent.
Can be used for co-stabilizer of the present invention and comprise guanidine compound.Guanidine compound refers to have the compound of one or more guanidine radicals.The example of guanidine compound includes but not limited to guanidine, Dicyanodiamide (dicyanodiamide), Guanidinium hydrochloride, guanidine sulfate, Guanidinium nitrate, phosphoguanidine, 4-amino-N-guanidine radicals benzsulfamide, N-guanidine radicals-sarcosine, 3-guanidine radicals propionic acid, N-(4-carboxyl phenyl) guanidinesalt hydrochlorate, L-l-arginine, polyhexamethylene guanidinesalt hydrochlorate, 1,3-diphenylguanidine, betanidine, guanethidine, envacar, Debrisoquine, Vatensol, guanazodine, guanabenz or their combination etc.Preferably, used guanidine compound is Dicyanodiamide, gathers (hexylidene) guanidinesalt hydrochlorate and guanidine radicals-sarcosine etc. in the polymer compsn of the present invention.More preferably, the used guanidine compound of the present invention is a Dicyanodiamide.
Another kind of co-stabilizer is the melamine compound that is selected from trimeric cyanamide, melamine cyanurate, Tripyrophosphoric acid trimeric cyanamide, melam, melem and melon.
Another kind of co-stabilizer is a hindered phenol.Hindered phenol is meant the organic cpds that contains at least one phenolic group, wherein aromatics part at least one and preferred two with have the position of phenolic hydroxyl group and be substituted as substituent carbon direct neighbor.The substituting group adjacent with hydroxyl is the alkyl that is selected from the alkyl with 1 to 10 carbon atom suitably, and will be preferably tertiary butyl groups.The molecular weight of hindered phenol is suitably at least about 260, preferably at least about 500, more preferably at least about 600.The hindered phenol that most preferably has low volatility (particularly under the processing temperature that molded said preparation adopted, having low volatility); And can further be characterized by and have at least 290 ℃; Preferably at least 300 ℃, 320 ℃, 340 ℃, and most preferably at least 350 ℃ 10% weight loss temperature (when with the scanning speed of 10 ℃/min through thermogravimetry (TGA) when measuring).
Suitable hindered phenol compound comprises for example four (methylene radical (3; 5-two-(uncle)-butyl-4-hydroxyl hydrogenated cinnamate)) methane; It can derive from CIBA SpecialtyChemicals by
1010; Tarrytown; N.Y (the Ciba ltd in New York Ta Lidun city); And N; N '-hexylidene two (3,5-two-(uncle) butyl-hydroxyl hydrocinnamamide), it also derives from CIBA Specialty Chemicals (Ciba ltd) with
1098.Other suitable hindered phenols comprise 1; 3; 5-trimethylammonium-2,4,6-three (3; 5-two-(uncle)-butyl-4-hydroxybenzyl) benzene and 1; 6-hexylidene two (3,5-two-(uncle) butyl-4-hydroxyl hydrogenated cinnamate), the two can derive from CIBA Specialty Chemicals (Ciba ltd) with
1330 and 259 respectively.Irganox 1098 is most preferred hindered phenols that are used for compsn.
In a preferred embodiment, based on the gross weight of daiamid composition, the content of said co-stabilizer is the 0.25-10 weight percent, is preferably the 0.5-8 weight percent, and more preferably the 1-5 weight percent most preferably is the 2-5 weight percent.
Above-mentioned one or more co-stabilizers also can comprise mantoquita and/or their verivate, for example, and copper halide or neutralized verdigris; Manganous salt and/or their verivate; And their combination.Preferably, mantoquita can be united use with halogenide and/or P contained compound; More preferably, mantoquita can be united use with iodide or bromide; Even more preferably, mantoquita can be united use with potassiumiodide or Potassium Bromide.In the present invention; Mantoquita and/or their verivate can also use with one or more thermo-stabilizers, and said one or more thermo-stabilizers are selected from following compound: the phenolic aldehyde inhibitor that is obstructed, hindered amine antioxidant, phosphorus inhibitor or their combination.
In the present invention, polymer compsn of the present invention can also comprise other additives that usually use this area, for example inhibitor, static inhibitor, whipping agent, lubricant, impact modifier, softening agent, tinting material and weighting agent.
In the present invention, inhibitor can be any inhibitor that usually use this area.In according to a preferred embodiment of the invention, inhibitor is selected from following material: butylation toluene (BHT), phenyl-B-naphthylamines, alkyl paraquinones, thioether, salol, sulfydryl thioether, sulfo--propionic ester, organo phosphorous compounds, dithio sulphonate, amide gp, hydrazine class, aromatic amine compound and their combination.
In the present invention, static inhibitor can be any static inhibitor that usually use this area.In according to a preferred embodiment of the invention, static inhibitor is selected from following compound: quaternary ammonium salt, ethoxylated amine, aliphatic ester and sulfonation paraffin and their combination.
In the present invention, whipping agent can be the normally used any whipping agent in this area.In according to a preferred embodiment of the invention, whipping agent is selected from following material: nitrogen, carbonic acid gas, air, butane, pentane, sherwood oil, methyl chlorofluoride, azobisformamide ABFA, the two isobutylates of azo and their combination.
In the present invention, lubricant can be the normally used any lubricant in this area.In a preferred embodiment of the invention, lubricant is selected from aliphatic ester class (for example, the direactive glyceride of lipid acid) and their combination.
In the present invention, softening agent can be the normally used any plasticizer in this area.In a preferred embodiment of the invention, softening agent is selected from following material: terephthalate, phthalic ester, aliphatic dibasic esters, SULPHOSUCCINIC ACID ESTER, clorafin and their combination.
In the present invention; Weighting agent can be any weighting agent, but is preferably selected from following material: lime carbonate, the spun glass with circle and non-circular cross sections, sheet glass, granulated glass sphere, thomel, talcum powder, mica, wollastonite, calcined clay, kaolin, zeyssatite, sal epsom, Magnesium Silicate q-agent, permanent white, titanium oxide, aluminium carbonate sodium, barium ferrite, potassium titanate and their mixture.
Spun glass with non-circular cross sections is meant the spun glass with following xsect, and said xsect has the major axis of long slant range in the vertical vertical and cross section taken in correspondence with spun glass.Non-circular cross sections has in the cross section taken in correspondence perpendicular to the minor axis of long slant range on the direction of major axis.The non-circular cross sections of fiber can have multiple shape, comprises cocoon shape (8 font), rectangle, ellipse, subtriangular, Polygons and rectangle.It should be appreciated by those skilled in the art that xsect can have other shapes.The ratio of the length of major axis and the length of minor axis is preferably between about 1.5: 1 and about 6: 1.This ratio more preferably between about 2: 1 and 5: 1, yet more preferably between about 3: 1 to about 4: 1.Suitable spun glass has disclosed in EP 0190001 and EP 0,196 194.
In an embodiment preferred according to the present invention, daiamid composition is the mixture that melt blending forms, and wherein all component of polymer are through thorough mixing, and all non-polymer compositions are well-dispersed in the polymeric matrix.Any melt-mixing method can be used for mixing component of polymer of the present invention and non-polymer composition.For example; Can be to melt mixer with component of polymer and the feeding of non-polymer composition; For example in single screw extrusion machine or twin screw extruder, stirrer, single screw rod or twin screw kneader or the Banbury mixing tank, and to add step can be disposable whole adding or progressively add in batches.When adding component of polymer and non-polymer composition with the mode that progressively adds in batches; A part that at first adds component of polymer and/or non-polymer composition; Then with the residual polymer composition that adds subsequently with non-ly aggregate into the branch fusion and mix, up to obtaining well-mixed compsn.When using the filler (for example, long glass fibres) of surplus reason shape, can use pultrusion to prepare enhancing composition.
As stated, have with the polyvalent alcohol of two or more hydroxyls and the daiamid composition of co-stabilizer and can be used for increasing molded or extruded product long-term thermal stability at high temperature by its preparation.The long-term thermal stability of goods can assess aging a plurality of cycles test duration of the thick specimen of 4mm through baking oven under a plurality of test experiments temperature.The baking oven probe temperature that is used for compsn disclosed herein is the minimum test period of minimum 170 ℃ and 500 hours.Probe temperature and test period can be higher.Behind oven ageing, test the tensile strength and the elongation at break of said specimen according to ISO 527-2/1A testing method, and compare with the not aged contrast of exsiccant when molded (DAM).With the conservation rate that tensile strength relatively is provided of DAM contrast and/or the conservation rate (retention) of elongation at break, and therefore can assess the long term high temperature aging resistance of multiple compsn.
In a plurality of embodiments of the present invention, based on the comparison of the unaged contrast of DAM, daiamid composition has at least 50%, and the stretching strength retentivity under preferred at least 60%, at least 70%, at least 80% and at least 90% 170 ℃/500 hours.
Embodiment preferred is to use the polymeric amide that is selected from (II) group polymeric amide, and wherein probe temperature is at least 210 ℃, and test period is at least 90% (comparing with not aged) at least 500 hours and stretching strength retentivity.This has remarkable and beyond thought improvement than the commercially available stable daiamid composition of copper of tradition aspect long-term thermal stability, as disclosed in the instance.
On the other hand, the present invention relates to through making resin combination of the present invention be shaped the method for article of manufacture.Examples of articles is film or laminate, trolley part or engine parts or electric component/electronic unit." shaping " is meant any forming technique, for example extrudes, injection-molded, hot-moulded, compression molding or blowing.Preferably, goods are shaped through injection-molded or blowing.
The instance of trolley part or engine parts includes but not limited to charge air cooler, rocker cover, exhaust system, gas exhaust duct and intake manifold.Expose a required anti-mechanical illustrative examples as the antagonism long term high temperature, can mention charge air cooler.Charge air cooler is the parts that improve engine combustion efficiency in the vehicle water cooler.The AT that charge air cooler reduces mover also increases the density of air after the compression in the turbo-supercharger, thereby makes more air get into cylinder and improve motor efficiency.Because the temperature of the air that when the air admission charge air cooler, gets into may be higher than 200 ℃, is by at high temperature keeping the compsn of good mechanical properties to process in a long time so require these parts.
Further illustrate the present invention below in conjunction with embodiment.Should be appreciated that following embodiment only is used for illustration purpose, is not limited to the present invention.
Material
PA66 is meant by 1; 6-hexanodioic acid and 1; The aliphatic polyamide that the 6-hexanediamine is processed; It can trade mark 6
101NC010 from E.I.DuPont de Nemours and Company; Wilmington, Delaware, USA (E.I.Du Pont Company of Wilmington City, Delaware, USA State) is purchased acquisition.
GF is meant NEG 275H short glass fiber.
The Cu stablizer is meant 7 parts of potassiumiodides and the mixture of 1 part of cuprous iodide in 0.5 part of Triple Pressed Stearic Acid ester type waxes sticker.
the 1098th can derive from Ciba Specialty Chemicals; Inc.; Tarrytown, the hindered phenol of NY (the Ciba ltd in New York Ta Lidun city).
DPE is meant dipentaerythritol.
Method
Complex method
The pill of the polymkeric substance, weighting agent, thermo-stabilizer and other additives that are suitable for listed in following table 1 and the table 2 is fed to the rear portion that the TEM35 corotation changes twin screw extruder.All embodiment and comparative example carry out with the feeding rate of 210rpm, 23kg/h and 290 ℃ cylinder temperature.Melt temperature is 300 ℃.After extruding forcing machine, compsn is made into the ball shape.The gross weight that the amount of the composition shown in table 1 and the table 2 is based on thermoplastic compounds is that unit provides with the weight percent.
Physical property
Utilize ISO 527-2 (1A type) to measure tensile modulus and elongation at break.For tensile modulus, speed is 1mm/min; For elongation at break, speed is 5mm/min.
High temperature ageing
As illustrated in table 1 and the table 2,, perhaps be oven ageing (AOA) to be treated to when molded dry (DAM) of specimen.Specimen is not applied other processing.
Table 1
The AOA=oven ageing
Data in table 1 and the table 2 show, are carrying out oven ageing under 210 ℃ after 1000 hours, and the conservation rate of tensile strength is apparently higher than the comparative example of the combination that wherein only has copper stablizer or copper stablizer and co-stabilizer.
Table 2
The AOA=oven ageing
Claims (26)
1. has the purposes that in daiamid composition, is used to increase said daiamid composition long-term thermal stability at high temperature more than the polyvalent alcohol of two hydroxyls and the co-stabilizer that is selected from melamine compound, guanidine compound and hindered phenol; Wherein, When processing the 4mm test rod by said daiamid composition; And with test rod in air atmosphere in the baking oven of at least 170 ℃ of probe temperatures aging at least 500 hours test period; And test according to ISO 527-2/1A, said test rod and not aged is compared has at least 50% stretching strength retentivity.
2. purposes according to claim 1, wherein said daiamid composition also comprises the reinforcing filler of 10 to 60 weight percents.
3. purposes according to claim 1, wherein said daiamid composition comprise one or more polymeric amide that is selected from following material:
(I) of the polyamide group, having a melting point lower than 210 ℃, containing substance selected from aliphatic or semi-aromatic polyamide: poly (pentamethylene sebacamide) (PA510), poly (pentylene twelve alkyl diamide) (PA512), poly (ε-caprolactam / hexamethylene adipamide) (PA6/66), poly (ε-caprolactam / hexamethylene sebacamide) (PA6/610), poly (ε-caprolactam / hexamethylene dodecane diamide) (PA6/612), poly (hexamethylene diamide tridecyl) (PA613), poly (hexamethylene diamide pentadecyl) (PA615), poly (ε-caprolactam / butylene terephthalamide) (PA6/4T), poly (ε-caprolactam / hexamethylene terephthalamide) (PA6/6T), poly (ε-caprolactam / decamethylene terephthalamide) (PA6 / 10T), poly (ε-caprolactam / dodecamethylene terephthalamide) (PA6/12T), poly (hexamethylene sebacamide / hexamethylene terephthalamide) (PA610/6T), poly ( hexamethylene dodecane diamide / hexamethylene terephthalamide) (PA612/6T), poly (hexamethylene diamide myristic / hexamethylene terephthalamide) (PA614/6T), poly (ε- caprolactam / hexamethylene isophthalamide / hexamethylene terephthalamide) (PA6/6I/6T), poly (ε-caprolactam / hexamethylene adipamide / hexamethylene sebacamide) (PA6/66/610 ), poly (ε-caprolactam / hexamethylene adipamide / hexamethylene dodecane diamide) (PA6/66/612), poly (ε-caprolactam / hexamethylene adipamide / hexamethylene sebacamide / hexylene dodecane diamide) (PA6/66/610/612), poly (2 - methyl pentyl adipamide / hexamethylene adipamide / hexamethylene terephthalamide) (PA? D6/66 / 6T), poly (2 - methyl pentyl adipamide / hexamethylene adipamide) (PA? D6/66), poly (decamethylene sebacamide) (PA1010), poly (decylene twelve alkyl diamide) (PA1012), poly (decamethylene sebacamide / decamethylene terephthalamide) (PA1010/10T), poly (decamethylene sebacamide / sodium dodecyl sebacamide / decamethylene terephthalamide / dodecamethylene terephthalamide (PA1010/1210/10T/12T), poly (11 - aminoundecanoic acid amide) (PA11), poly (11 - aminoundecanoic alkyl acrylamide / tetramethylene terephthalamide) (PA11/4T), poly (11 - aminoundecanoic lactam / hexamethylene terephthalamide) (PA11/6T), poly (11 - aminoundecanoic acid amide / decylene terephthalamide) (PA11/10T), poly (11 - aminoundecanoic acid amide / sodium dodecyl terephthalamide) (PA11/12T), poly (12 - aminododecanoic alkyl amide) (PA12), poly (12 - amino-dodecanoic acid amide / tetramethylene terephthalamide) (PA12/4T), poly (12 - amino-dodecanoic acid amide / hexamethylene terephthalamide) ( PA12/6T), poly (12 - amino-dodecanoic acid amide / decamethylene terephthalamide) (PA12/10T), poly (dodecyl dodecane diamide) (PA1212), and poly (alkylene dodecanedioic dodecyl acrylamide / dodecamethylene terephthalamide) (PA1212/12T);
(II) organizes polymeric amide; Its fusing point is at least 210 ℃, comprises the aliphatic polyamide that is selected from following material: gather (butylidene adipamide) (PA46), gather (ε-Ji Neixianan) (PA 6), gather (hexylidene adipamide/ε-Ji Neixianan) (PA66/6), gather (hexylidene adipamide) (PA 66), gather (hexylidene adipamide/hexylidene sebacoyl amine) (PA66/610), gather (hexylidene adipamide/hexylidene dodecyl diamide) (PA66/612), gather (hexylidene adipamide/inferior decyl sebacoyl amine) (PA66/1010), gather (hexylidene sebacoyl amine) (PA610), gather (hexylidene dodecyl diamide) (PA612), gather (hexylidene tetradecane diamide) (PA614), gather (hexylidene n-Hexadecane diamide) (PA616) with gather (butylidene adipamide/2-methyl pentylidene adipamide) (PA46/D6);
(III) organizes polymeric amide, and its fusing point is at least 210 ℃, comprises
(aa) half aromatic repeating units of 20 to 35 molar percentages, said half aromatic repeating units are derived from the monomer that is selected from one or more following materials:
I. the aromatic dicarboxylic acid and aliphatic diamine that have 8 to 20 carbon atoms with 4 to 20 carbon atoms; With
(bb) the aliphatic repeating unit of 65 to 80 molar percentages, said aliphatic repeating unit are derived from the monomer that is selected from one or more following materials:
Ii. the aliphatic dicarboxylic acid and said aliphatic diamine that have 6 to 20 carbon atoms with 4 to 20 carbon atoms; And
Iii. the lactan and/or the aminocarboxylic acid that have 4 to 20 carbon atoms; And
Iv. their mixture;
(IV) organizes polymeric amide, comprises:
(cc) half aromatic repeating units of 50 to 95 molar percentages, said half aromatic repeating units are derived from the monomer that is selected from one or more following materials:
(i) aromatic dicarboxylic acid that has 8 to 20 carbon atoms and aliphatic diamine with 4 to 20 carbon atoms; And
(dd) the aliphatic repeating unit of 5 to 50 molar percentages, said aliphatic repeating unit are derived from the monomer that is selected from one or more following materials:
The aliphatic dicarboxylic acid and the said aliphatic diamine that (ii) have 6 to 20 carbon atoms with 4 to 20 carbon atoms; And
The lactan and/or the aminocarboxylic acid that (iii) have 4 to 20 carbon atoms; And
(iv) their mixture;
(V) organizes polymeric amide, and its fusing point is at least 260 ℃, comprises:
(ee) greater than half aromatic repeating units of 95 molar percentages, said half aromatic repeating units is derived from the monomer that is selected from one or more following materials:
I. the aromatic dicarboxylic acid and aliphatic diamine that have 8 to 20 carbon atoms with 4 to 20 carbon atoms; And
(ff) less than the aliphatic repeating unit of 5 molar percentages, said aliphatic repeating unit is derived from the monomer that is selected from one or more following materials:
Ii. the aliphatic dicarboxylic acid and the said aliphatic diamine that have 6 to 20 carbon atoms with 4 to 20 carbon atoms; And
Iii. the lactan and/or the aminocarboxylic acid that have 4 to 20 carbon atoms; And
Iv. their mixture; And
(VI) organizes polymeric amide; It does not have fusing point, is selected from following material: gather (hexylidene isophthaloyl amine/hexylidene terephthalamide) (6I/6T) with gather (hexylidene isophthaloyl amine/hexylidene terephthalamide/hexylidene adipamide) (6I/6T/66).
4. purposes according to claim 3, wherein said polymeric amide are selected from (I) group polymeric amide.
5. purposes according to claim 3; Wherein said polymeric amide is selected from (II) group polymeric amide, and wherein said probe temperature is at least 210 ℃, and said test period is at least 500 hours; And compare with not aged, the conservation rate of said tensile strength is at least 90%.
6. purposes according to claim 3, wherein said polymeric amide are selected from (III) group polymeric amide.
7. purposes according to claim 3, wherein said polymeric amide are selected from (IV) group polymeric amide.
8. purposes according to claim 3, wherein said polyamide resin are selected from (V) group polymeric amide.
9. purposes according to claim 3, wherein said polyamide resin are selected from (VI) group polymeric amide.
10. purposes according to claim 3, wherein said polyamide resin comprise two or more blends that is selected from the polymeric amide of following material: (I) group and (II) group polymeric amide; (I) group and (III) polymeric amide; (I) group and (VI) group polymeric amide; (II) group and (VI) group polymeric amide; (II) group and (IV) group polymeric amide; (II) group and (V) group polymeric amide and (IV) group and (V) group polymeric amide.
11. purposes according to claim 1, the wherein said polyvalent alcohol that has more than two hydroxyls is selected from following material: tetramethylolmethane, dipentaerythritol, tripentaerythritol, two-TriMethylolPropane(TMP), D-mannitol, D-Sorbitol Powder and Xylitol.
12. purposes according to claim 1, the wherein said polyvalent alcohol that has more than two hydroxyls is dipentaerythritol and/or tetramethylolmethane.
13. purposes according to claim 1; Wherein said co-stabilizer is guanidine compound and is selected from following material: guanidine, Dicyanodiamide, Guanidinium hydrochloride, guanidine sulfate, Guanidinium nitrate, phosphoguanidine, 4-amino-N-guanidine radicals benzsulfamide, N-guanidine radicals-sarcosine, 3-guanidine radicals propionic acid, N-(4-carboxyl-phenyl) guanidinesalt hydrochlorate, L-l-arginine, gather (hexylidene guanidine) hydrochloride, 1,3-diphenylguanidine, betanidine, guanethidine, envacar, Debrisoquine, Vatensol, guanazodine, guanabenz or its combination.
14. purposes according to claim 13, wherein said guanidine compound are selected from Dicyanodiamide and gather (hexylidene guanidine) hydrochloride.
15. purposes according to claim 1, wherein said co-stabilizer are the melamine compounds that is selected from following compound: trimeric cyanamide, melamine cyanurate, Tripyrophosphoric acid trimeric cyanamide, melam, melem and melon.
16. purposes according to claim 1, wherein said co-stabilizer are the hindered phenols that is selected from following material: four (methylene radical (3,5-two-(uncle)-butyl-4-hydroxyl hydrogenated cinnamate)) methane, N; N '-hexylidene two (3,5-two-(uncle) butyl-hydroxyl hydrocinnamamide), 1,3; 5-trimethylammonium-2,4,6-three (3; 5-two-(uncle)-butyl-4-hydroxybenzyl) benzene and hexamethylene two (3,5-two-(uncle) butyl-4-hydroxyl hydrogenated cinnamate).
17. purposes according to claim 1, wherein based on the gross weight of said daiamid composition, the content of said polyvalent alcohol is the 0.25-15 weight percent.
18. purposes according to claim 1, wherein based on the gross weight of said daiamid composition, the content of said polyvalent alcohol is the 0.5-8 weight percent.
19. purposes according to claim 1, wherein based on the gross weight of said daiamid composition, the content of said polyvalent alcohol is the 1-5 weight percent.
20. purposes according to claim 1, wherein based on the gross weight of said daiamid composition, the content of said polyvalent alcohol is the 2-5 weight percent.
21. purposes according to claim 1, wherein based on the gross weight of said daiamid composition, the content of said co-stabilizer is the 0.25-10 weight percent.
22. purposes according to claim 1, wherein based on the gross weight of said daiamid composition, the content of said co-stabilizer is the 0.5-8 weight percent.
23. purposes according to claim 1, wherein based on the gross weight of said daiamid composition, the content of said co-stabilizer is the 1-5 weight percent.
24. purposes according to claim 1, wherein based on the gross weight of said daiamid composition, the content of said co-stabilizer is the 2-5 weight percent.
25. purposes according to claim 2, wherein said reinforcing filler is selected from following material: lime carbonate, the spun glass with circle and non-circular cross sections, sheet glass, granulated glass sphere, thomel, talcum powder, mica, wollastonite, calcined clay, kaolin, zeyssatite, sal epsom, Magnesium Silicate q-agent, permanent white, titanium oxide, aluminium carbonate sodium, barium ferrite, potassium titanate and their mixture.
26. purposes according to claim 1, wherein said daiamid composition also comprise one or more additives that is selected from following material: static inhibitor, whipping agent, lubricant, impact modifier, softening agent and tinting material.
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EP2924065A1 (en) | 2014-03-26 | 2015-09-30 | LANXESS Deutschland GmbH | Polyamide compositions |
FR3019822B1 (en) * | 2014-04-15 | 2017-10-20 | Arkema France | PROCESS FOR PRODUCING A THERMOPLASTIC MATERIAL BASED ON SEMI-CRYSTALLINE POLYAMIDE |
FR3032445A1 (en) * | 2015-02-05 | 2016-08-12 | Arkema France | DELAYED COMBUSTIBILITY POLYAMIDE COMPOSITION |
TW201817812A (en) * | 2016-07-29 | 2018-05-16 | 巴斯夫歐洲公司 | Polyamide blends for laser sinter powder |
CN114517012B (en) * | 2022-03-14 | 2023-06-06 | 金旸(厦门)新材料科技有限公司 | High-appearance antibacterial halogen-free flame-retardant polyamide composite material and preparation method thereof |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1646615A (en) * | 2002-04-10 | 2005-07-27 | 西巴特殊化学品控股有限公司 | Flame retardant coatings |
CN1839022A (en) * | 2003-08-19 | 2006-09-27 | 索尔维先进聚合物有限责任公司 | Impact-modified polyamide film |
CN1906246A (en) * | 2003-12-25 | 2007-01-31 | Jsr株式会社 | Thermoplastic elastomer composition, method for producing same and formed article |
-
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---|---|---|---|---|
CN1646615A (en) * | 2002-04-10 | 2005-07-27 | 西巴特殊化学品控股有限公司 | Flame retardant coatings |
CN1839022A (en) * | 2003-08-19 | 2006-09-27 | 索尔维先进聚合物有限责任公司 | Impact-modified polyamide film |
CN1906246A (en) * | 2003-12-25 | 2007-01-31 | Jsr株式会社 | Thermoplastic elastomer composition, method for producing same and formed article |
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---|---|---|---|---|
EP2924069B1 (en) | 2014-03-26 | 2017-04-26 | LANXESS Deutschland GmbH | Polyamide compositions |
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