CN103492488A - Flame-retardant molding materials - Google Patents
Flame-retardant molding materials Download PDFInfo
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- CN103492488A CN103492488A CN201280020075.5A CN201280020075A CN103492488A CN 103492488 A CN103492488 A CN 103492488A CN 201280020075 A CN201280020075 A CN 201280020075A CN 103492488 A CN103492488 A CN 103492488A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34922—Melamine; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K2003/026—Phosphorus
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Abstract
The invention relates to thermoplastic molding materials, containing A) 10 to 99.4 wt% of at least one thermoplastic polyamide, B) 0.5 to 20 wt% of a melam compound, C) 0.1 to 60 wt% of red phosphorus, and D) 0 to 60 wt% of further additives, wherein the total of the weight percentages of A) to D) is 100%.
Description
The present invention relates to a kind of thermoplastic composition, it comprises
A) at least one polyamide thermoplastic of 10 to 99.4 % by weight
B) % melam (melam) compound of 0.5 to 20 weight
C) red phosphorus of 0.1 to 60 % by weight
D) other additives of 0 to 60 % by weight,
A wherein) to D) weight percent add up to 100%.
The invention still further relates to the purposes of moulding compound of the present invention for the preparation of fiber, paper tinsel and moulded product, and relate to resulting moulded product.
When mixing in polymer melt by red phosphorus, owing to playing dirt and phosphine, discharge and cause the industrial safety problem.
DE-A2703052, DE-A19648503, EP-A071788, EP-A-176836 and EP-A384232 disclose the various flame retardant resistance PA thermoplastic compounds that contain red phosphorus.
Since two thousand six, the new standard of the IEC60335 about electrical equipment of promulgating is incorporated into working current by an urgent demand increased in combustion test > in the Domestic automatic electrical equipment of 0.2A.This test is applicable to all and contacted plastic components of electric conductor that have this electric current magnitude.These assemblies are manufactured by injection moulding by thermoplastics usually.This standard code assembly need be by the glow wire test (according to the GWT of IEC60695-2-11) under 750 ℃, and surpass total combustion time and within two seconds, cause considering in electrical equipment manufacture and the extra complexity of the granted middle needs of electrical equipment herein.<=2 seconds total combustion times---as considering of flame retardant resistance---by GWT glow wire test requirement under 750 ℃ (referred to as: GWT750<=2s).
Yet, while using polyamide moulding composition at present, this material need comprise halogen to meet fully reliably " GWT750<=2s " requirement.Yet halogen-containing matrix material has many defects, for example, high-density, high smoke toxicity, high smoke density and low CTI, therefore need the halogen surrogate of exploitation for these application.Obviously, also can use here and contain the polyamide moulding composition of red phosphorus as fire retardant.Regrettably, these compositions only can present not enough reproducibility level in by GWT750<=2s glow wire test, and this also greatly depends on the geometrical shape of assembly.
W02007/042446 discloses the melamine compound binding substances (particularly polyphosphoric acid melamine) of the flame retardant combinations form of PA.The flame retardant resistance of these binding substancess is not entirely satisfactory.In addition, these moulding compounds only can be marginally for painted preparation, because they have red inherent colour.
Therefore, an object of the present invention is to provide flame retardant resistance PA moulding compound, said composition has the flame retardant resistance of improvement, shows better in the glow wire test and have better tinctorial property, and meets above-mentioned standard.Be intended to greatly keep mechanical property simultaneously.
Therefore, found the flame retardant molding composition of introductory song definition.Provided such preferred moulding compound and uses thereof in dependent claims.
Moulding compound of the present invention comprises as component A) 10 to 99.4 % by weight, preferably 20 to 98 % by weight and at least one polymeric amide of being in particular 25 to 90 % by weight.
It is 90 to 350ml/g that the polymeric amide of polyamide moulding composition of the present invention has viscosity number usually, and preferably 110 to 240ml/g, according to ISO307, under 25 ℃, in 0.5 % by weight concentration solution of the sulfuric acid of 96 % by weight concentration, measures.
Hypocrystalline or amorphous resin that preferred molecular weight (weight average) is at least 5000, for example be recorded in those in US Patent specification 2071250,2071251,2130523,2130948,2241322,2312966,2512606 and 3393210.
The example of these polymeric amide is derived from the lactan with 7 to 13 ring memberses, for example polycaprolactam, poly capryllactam, nylon 12 and the polymeric amide that obtains through dicarboxylic acid and diamine reactant.
Spendable dicarboxylic acid is alkane dicarboxylic acid and the aromatic dicarboxylic acid that has 6 to 12, is in particular 6 to 10 carbon atoms.Here the acid that only can mention as an example has hexanodioic acid, nonane diacid, sebacic acid, dodecanedioic acid, terephthalic acid and/or m-phthalic acid.
Specially suitable diamines is the alkane diamines that has 6 to 12, is in particular 6 to 8 carbon atoms, and m-xylene diamine is (for example, purchased from BASF SE's
the mol ratio of MXDA and hexanodioic acid is 1:1), two (4-aminophenyl) methane, two (4-aminocyclohexyl) methane, 2,2-bis-(4-aminophenyl) propane, 2,2-bis-(4-aminocyclohexyl) propane or 1,5-diamino-2-methylpentane.
Preferred polymeric amide is polyhexamethylene adipamide, polyhexamethylene sebacamide and polycaprolactam and nylon-6/6,6 copolyamides, particularly has the polymeric amide of the hexanolactam unit of 5 to 95 % by weight ratios (for example, purchased from BASF SE's
31).
Other suitable polymeric amide can for example, be reacted and obtain through known direct polymerization with hexanediamine (PA66) by omega-amino-alkyl nitrile (aminocapronitrile (PA6)) and adiponitrile under the existence of water, and described method for example is described in DE-A10313681, EP-A1198491 and EP922065.
Also can mention for example can be by 1,4-Diaminobutane and the hexanodioic acid polymeric amide that condensation obtains at elevated temperatures (nylon-4,6).The preparation method of this kind of structure polymeric amide is recorded in for example EP-A38094, EP-A38582 and EP-A39524.
Other suitable examples have the polymeric amide that can obtain by the copolyreaction of two or more above-mentioned monomers, and with the mixture of two or more polymeric amide of any required ratio of mixture.Nylon-6 particularly preferably, 6 with the mixture, particularly nylon-6 of other polymeric amide/6,6 copolyamides.
Confirmed that particularly advantageous other polymeric amide are half aromatic copolyamides, for example PA6/6T and PA66/6T, wherein the triamine content of these polymeric amide is lower than 0.5 % by weight, especially lower than 0.3 % by weight (referring to EP-A299444).EP-A1994075 discloses other resistant to elevated temperatures polymeric amide (PA6T/6I/MXD6).
The method that is recorded in EP-A129195 and 129196 can be used for half aromatic copolyamides that preparation preferably has low triamine content.
Following list (all sidedly non-) has comprised mentioned polymeric amide A) and for other polymeric amide of the object of the invention A) and the monomer that exists:
The AB polymkeric substance:
The AA/BB polymkeric substance:
The AA/BB multipolymer:
Spendable other monomers are cyclic diamine, for example those diamines of following general formula
Wherein
R
1for hydrogen or C
1-C
4alkyl
R
2for C
1-C
4alkyl or hydrogen, and
R
3for C
1-C
4alkyl or hydrogen.
Particularly preferred diamines is two (4-aminocyclohexyl) methane, two (4-amino-3-methylcyclohexyl) methane, 2, two (4-aminocyclohexyl) propane of 2-or two (4-amino-3-methylcyclohexyl) propane of 2,2-.
Other diamines that can mention are 1,3-or Isosorbide-5-Nitrae-cyclohexanediamine or isophorone diamine,
Also can use the mixture of above-mentioned polymeric amide.
Thermoplastic composition of the present invention comprises as B component) 0.5 to 20 % by weight, preferably 0.5 to 15 % by weight and the melam compound that is in particular 6 to 15 % by weight.
Preferably be applicable to the condenses of melam compound of the present invention (B component) for preferably being obtained through thermal treatment by melamine compound (formula I),
Wherein, the radicals R in (I) and (II) is independently of each other for hydrogen or have 1 to 12 carbon atom, preferably the alkyl of 1 to 4 carbon atom.
Preferred preparation method is found in WO96/16948 or EP-A1252168.
Preferred compd B) be melam (that is, wherein all radicals R are hydrogen), it can obtain through the thermal condensation of trimeric cyanamide (the wherein all radicals R=H in (I)).
The d of melam
50grain value is particularly preferably 2.24 to 4.8 μ m, and its d
90value is particularly preferably 13 to 14.8 μ m.
Preferred fire retardant C) be element red phosphorus, the element red phosphorus of particularly being combined with glass-fiber reinforced moulding compound; It can untreated mode use.
Yet, the preparation of particularly suitable be wherein phosphorus for example, by those preparations of low-molecular-weight liquid (silicone oil, paraffin oil or phthalic ester or adipic acid ester) surface coated, or be polymerized those preparations of compound or oligomeric compound (for example resol or aminoplastics, or urethane) surface coated.
The enriched material of red phosphorus in for example polymeric amide or elastomerics be the applicable fire retardant of doing also.Specially suitable concentrated polymer is equal polyolefine and copolyolefine.Yet, if polymeric amide is not used as to thermoplastics, the content of concentrated polymer should be no more than 35 % by weight, the component A based on moulding compound of the present invention) and weighing scale B).
Preferred enriched material composition is
C
1) 30 to 90 % by weight, the preferred polymeric amide of 50 to 70 % by weight.
C
2) 10 to 70 % by weight, the preferred red phosphorus of 30 to 50 % by weight.
Polymeric amide for masterbatch can be different from A) or preferably can be equal to A) so that uncompatibility or fusing point difference can not produce any adverse influence to moulding compound.
Be distributed in the mean particle size (d of the phosphorus particle in moulding compound
50) be preferably 0.0001 to 0.5mm; Be in particular 0.001 to 0.2mm.
The component C of moulding compound of the present invention) content is 0.1 to 60 % by weight, is preferably 0.5 to 40 % by weight, and is in particular 2 to 10 % by weight, based on component A) to D) the total amount meter.
Moulding compound of the present invention can comprise as component D) 0 to 60 % by weight, particularly up to other additives and the processing aid of 50 % by weight.
Fibrous or the particulate filler D1 that can mention) be carbon fiber, glass fibre, granulated glass sphere, soft silica, Calucium Silicate powder, calcium metasilicate, magnesiumcarbonate, kaolin, chalk, flint, mica, barium sulfate and feldspar, the usage quantity of these fillers is 1 to 50 % by weight, is in particular 1 to 40 % by weight, is preferably 10 to 40 % by weight.
Preferred composition comprises:
A) 20 to 97 % by weight
B) 0.5 to 15 % by weight
C) 0.5 to 40 % by weight
D1) 1 to 40 % by weight
D2) 0 to 50 % by weight
A wherein) to D) add up to 100%.
The preferred bat wool that can mention is carbon fiber, Kevlar and potassium titanate fiber, here the glass fibre of E glass form particularly preferably.These can rove form use or use with the form of commercially available chopped glass or obscure glass.
Described bat wool can be silylated compound and carry out the consistency of surface preparation with raising and thermoplastics.
Suitable silane compound has following general formula:
(X-(CH
2)
n)
k-Si-(O-C
mH
2m+1)
4-k
Wherein:
X is
N is 2 to 10, preferred 3 to 4 integer,
M is 1 to 5, preferred 1 to 2 integer,
The integer that k is 1 to 3, preferably 1.
Preferred silane compound is TSL 8330, aminobutyl Trimethoxy silane, aminopropyltriethoxywerene werene and aminobutyl triethoxyl silane and comprises accordingly the silane as the glycidyl of substituent X.
The amount that is generally used for the silane compound of surface coated is 0.01 to 2 % by weight, preferred 0.025 to 1.0 % by weight and be in particular 0.05 to 0.5 % by weight (based on D meter).
Long glass fibres also is applicable to as component D1), the form that wherein it can rove is used.The diameter that is used as the glass fibre of rove in the present invention is 6 to 20 μ m, and preferably 10 to 18 μ m, and the transverse section of these glass fibre are circle, ellipse or polyhedron.Especially, the present invention uses the E glass fibre.Yet, can also use the glass fibre of any other type, for example A, C, D, M, S and R glass fibre and required mixture arbitrarily thereof, and with the mixture of E glass fibre.
L/D (length/diameter), than being preferably 100 to 4000, is in particular 350 to 2000, and the utmost point is in particular 350 to 700.
The needle-like mineral filler also is applicable to.
For purpose of the present invention, the needle-like mineral filler is the mineral filler with extremely ripe needle-like feature.Example is acicular wollastonite (wollastonite).The L/D that these mineral preferably have (length relative diameter) is than for 8:1 to 35:1, and preferably 8: to 11:1.This mineral filler is optionally by above-mentioned silane compound pre-treatment, but this pre-treatment is optional.
Other fillers that can mention have kaolin, calcined kaolin, wollastonite, talcum and chalk, and stratiform or acicular nanometer filler, and the amount of these fillers is preferably 0.1 to 10%.Being preferred for this purpose material is boehmite, wilkinite, montmorillonite, vermiculite, hectorite and lithium magnesium silicate.By art methods, the laminar nano filler is carried out organically-modifiedly, with this, give the excellent compatibility of they and organic binder bond.To the further raising of adding stratiform or acicular nanometer filler in nano-complex of the present invention and can obtain physical strength.
The additive D2 that other are commonly used) example is 1 to 30 % by weight, the preferred elastomer polymer of 2 to 20 % by weight amounts (also often being called as impact modifying agent, elastomerics or rubber).
Preferred composition comprises:
A) 20 to 97 % by weight
B) 0.5 to 15 % by weight
C) 0.5 to 40 % by weight
D1) 1 to 40 % by weight
D2) 1 to 30 % by weight
D3) 0 to 20 % by weight
A wherein) to D) add up to 100%.
These are very general multipolymers, they preferably consist of at least two kinds of following monomers: ethene, propylene, divinyl, iso-butylene, isoprene, chloroprene, vinyl-acetic ester have acrylate and/or the methacrylic ester of 1 to 18 carbon atom in vinylbenzene, vinyl cyanide, alkoxide component.
This base polymer is described in for example Houben-Weyl, Methoden der organischen Chemie, Vol.14/1 (Georg-Thieme-Verlag, Stuttgart, Germany, 1961), 392-406 page, and the monograph of C.B.Bucknall " Toughened Plastics " (Applied Science Publishers, London, UK, 1977) in.
The more elastomeric preferred types of this class are described below.
The elastomeric preferred type of this class is for being called those of ethylene-propylene (EPM) and ethylene-propylene-diene (EPDM) rubber.
In fact EPM rubber do not have residual double bonds usually, and every 100 carbon atoms of EPDM rubber can have 1 to 20 two key.
The example of the diene monomers for EPDM rubber that can mention has conjugated diolefine, for example isoprene and divinyl; Non-conjugated diene with 5 to 25 carbon atoms, for example Isosorbide-5-Nitrae-pentadiene, Isosorbide-5-Nitrae-hexadiene, 1,5-hexadiene, 2,5-dimethyl-1,5-hexadiene and Isosorbide-5-Nitrae-octadiene; Cyclodienes, for example cyclopentadiene, cyclohexadiene, cyclooctadiene and Dicyclopentadiene (DCPD); Also have alkenyl norbornene, for example 5-ethylidene-2-norbornene, 5-butylidene-2-norbornylene, 2-methylallyl-5-norbornylene and 2-pseudoallyl-5-norbornylene; And three cyclodieneses, for example 3-methyl three ring [5.2.1.0
2.6]-3, the 8-decadiene; And their mixture.Preferably 1,5-hexadiene, 5-ethylidene norbornene and Dicyclopentadiene (DCPD).The diene content of EPDM rubber is preferably 0.5 to 50 % by weight, is in particular 1 to 8 % by weight, the gross weight meter based on rubber.
EPM and EPDM rubber preferably can also with reactive carboxylic acid or with its derivatives graft.The example of described carboxylic acid or derivatives thereof is vinylformic acid, methacrylic acid and derivative thereof, for example (methyl) glycidyl acrylate, and maleic anhydride.
Ethene and vinylformic acid and/or methacrylic acid and/or organize preferred rubber for another with the multipolymer of these sour esters.The monomer that rubber can also comprise dicarboxylic acid (as toxilic acid and fumaric acid) or these sour derivatives (as ester and acid anhydrides) and/or comprise cycloalkyl groups.These monomers that comprise dicarboxylic acid derivatives or comprise cycloalkyl groups are preferably by adding the monomer that comprises dicarboxylic acid group and/or cycloalkyl groups and have general formula I, II, III or IV to introduce in rubber in monomer mixture,
R
1C(COOR
2)=C(COOR
3)R
4 (I)
R wherein
1to R
9for hydrogen or there is the alkyl group of 1 to 6 carbon atom, and the m integer that is 0 to 20, integer that g is 0 to 10 and the p integer that is 0 to 5.
R
1to R
9be preferably hydrogen, wherein m be 0 or 1 and g be 1.Corresponding compound is toxilic acid, fumaric acid, maleic anhydride, glycidyl allyl ether and vinyl glycidyl ether.
The preferred compound of formula I, II and IV is toxilic acid, maleic anhydride and (methyl) acrylate of comprising cycloalkyl groups, for example glycidyl acrylate and glycidyl methacrylate, and with the ester of the tertiary alcohol, for example tert-butyl acrylate.Although the latter does not have the free carboxy group, their behavior is similar to free acid, so they are called as the monomer with potential carboxyl.
Described multipolymer is advantageously by the monomer that comprises epoxy group(ing) of the ethene of 50 to 98 % by weight, 0.1 to 20 % by weight and/or methacrylic acid and/or the monomer composition that comprises anhydride group, and surplus is (methyl) acrylate.
The multipolymer particularly preferably formed by following material:
50 to 98 % by weight, the particularly ethene of 55 to 95 % by weight,
0.1 to glycidyl acrylate and/or glycidyl methacrylate, (methyl) vinylformic acid and/or the maleic anhydride of 40 % by weight, particularly 0.3 to 20 % by weight, and
N-butyl acrylate and/or the 2-Ethylhexyl Methacrylate of 1 to 45% % by weight, particularly 5 to 40 % by weight.
Other preferred (methyl) acrylate is methyl esters, ethyl ester, propyl ester, isobutyl ester and the tert-butyl ester.
Except these, spendable comonomer also has vinyl acetate and vinyl ether.
Can, by known method preparation own, preferably by the random copolymerization under high pressure and high temperature, prepare by above-mentioned ethylene copolymer.Applicable method is known.
Other preferred elastomerics is emulsion polymer, and its preparation example is as in the monograph " Emulsion Polymerization " that is described in Blackley.Spendable emulsifying agent and catalyzer are that itself is known.
In principle, can use the elastomerics of homogeneous texture or there are those elastomericss of shell structure.Described shell class formation is determined by the addition sequence of each monomer.The form of polymkeric substance also is subject to the impact of this order of addition.
The monomer for the preparation of elastomeric rubber part that only can mention as an example is acrylate, as n-butyl acrylate and 2-EHA, and corresponding methacrylic ester, divinyl and isoprene, and the mixture of these materials.These monomers can with other monomer copolymerizable such as vinylbenzene, vinyl cyanide, vinyl ether, and with other acrylate or methacrylic ester copolymerization such as methyl methacrylate, methyl acrylate, ethyl propenoate or propyl acrylate.
Elastomeric soft phase or rubber phase (second-order transition temperature is below 0 ℃) can be core, shell or middle case (for having more than for the elastomerics of two shell structures).The elastomerics had more than a shell also can have the shell be comprised of rubber phase more than.
If in this elastomer structure, except rubber phase, also comprise one or more hard components (second-order transition temperature is more than 20 ℃), they prepare by the polymerization of the vinylbenzene as principal monomer, vinyl cyanide, methacrylonitrile, alpha-methyl styrene, p-methylstyrene or acrylate or methacrylic ester (as methyl acrylate, ethyl propenoate or methyl methacrylate) usually.In addition, also can use other comonomer of relative small proportion.
Confirmed that the emulsion polymer that uses in some cases its surface to have reactive group is favourable.The example of such group is epoxy group(ing), carboxyl, potential carboxyl, amino and amide group, and the functional group that can introduce by the monomer that uses following general formula simultaneously
Wherein substituting group can be defined as follows:
R
10for hydrogen or C
1-C
4-alkyl,
R
11for hydrogen, C
1-C
8alkyl or aryl, especially phenyl,
R
12for hydrogen, C
1-C
10alkyl, C
6-C
12aryl or-OR
13,
R
13for C
1-C
8alkyl or C
6-C
12aryl, its optionally group or the group that comprises N of involved O replace,
X is chemical bond, C
1-C
10alkylidene group or C
6-C
12arylene group, or
Y is O-Z or NH-Z, and
Z is C
1-C
10alkylidene group or C
6-C
12arylene group.
The grafted monomer of describing in EP-A208187 also is suitable for introducing on surface reactive group.
Acrylate or methacrylic ester that other example that can mention is acrylamide, Methacrylamide and replacement, for example methacrylic acid (N-tertiary butyl amino) ethyl ester, vinylformic acid (N, the N-dimethylamino) ethyl ester, vinylformic acid (N, the N-dimethylamino) methyl esters and vinylformic acid (N, N-diethylamino) ethyl ester.
The particle of rubber phase can be also crosslinked.The example of cross-linking monomer is 1,3-butadiene, Vinylstyrene, Phthalic acid, diallyl ester and vinylformic acid dihydro Dicyclopentadiene (DCPD) ester, and the compound of describing in EP-A50265.
Also can use the monomer that is called grafting-connection monomer, there is the monomer of two or more polymerizable double bonds that react with different rates in polymerization.Preferably use this compounds: wherein at least one reactive group is with the rate aggregation approximately identical with other monomer, and for example significantly more slowly polymerization of another reactive group (or a plurality of reactive group).Different rates of polymerization makes in rubber to produce a certain proportion of unsaturated double-bond.If then by another grafted branches to this class rubber, at least some two keys that are present in rubber react the formation chemical bond with grafted monomer, i.e. institute's grafting there is chemical bonding at least to a certain degree with graft bases.
The example of this class grafting-connection monomer is the monomer that comprises allyl group, the allyl ester of ethylenic unsaturated carboxylic acid particularly, for example allyl acrylate, allyl methacrylate(AMA), diallyl maleate, diallyl fumarate and methylene-succinic acid diallyl, and the corresponding monoene propylated compound of these dicarboxylic acid.In addition, also has multiple other applicable grafting-connection monomer.For further details, but reference example is as US-A4148846.
The ratio of these cross-linking monomers in impact modified polymkeric substance up to 5 % by weight, preferably is no more than 3 % by weight usually, based on impact modified polymkeric substance meter.
Some preferred emulsion polymers are listed in following table.Here can at first mention the graftomer that there is core and there is at least one shell and there is following structure:
Except its structure has the graft polymerization beyond the region of objective existence more than a shell, the elastomerics that also can use homogeneous (the being monoshell) elastomerics that formed by 1,3-butadiene, isoprene and n-butyl acrylate or be formed by their multipolymer.These products also can be by prepare with cross-linking monomer or monomer with reactive group simultaneously.
The example of preferred emulsion polymer has n-butyl acrylate-(methyl) acrylic copolymer, n-butyl acrylate-glycidyl acrylate or n-butyl acrylate-glycidyl methacrylate copolymer, has the multipolymer of the comonomer of inner core or the inner core based on divinyl be comprised of n-butyl acrylate and the graftomer with the shell be comprised of above-mentioned multipolymer and ethene and supply reactive group.
Also can, by other ordinary method preparation, for example by suspension polymerization, prepare by described elastomerics.
Also preferred silicone rubber, for example be described in those rubber in DE-A3725576, EP-A235690, DE-A3800603 and EP-A319290.
Certainly, can also use the mixture of these type rubber.
Moulding compound of the present invention can comprise as component D3) 0.05 to 3 % by weight, preferably 0.1 to 1.5 % by weight, the particularly lubricant of 0.1 to 1 % by weight.
Preferably Al salt, an alkali metal salt or alkaline earth salt, or there are 10 to 44, preferably there is ester or the acid amides of the lipid acid of 12 to 44 carbon atoms.
Metal ion is preferably alkaline-earth metal and Al, is particularly preferably Ca or Mg.
Preferred metal-salt is calcium stearate and montanic acid calcium and aluminum stearate.
Can also use the mixture of the different salt of any required ratio of mixture.
Described carboxylic acid can be monobasic or binary.The example that can mention is n-nonanoic acid, palmitinic acid, lauric acid, margaric acid, dodecylic acid, docosoic, particularly preferably stearic acid, capric acid and montanic acid (mixture with lipid acid of 30 to 40 carbon atoms).
Fatty alcohol can be monobasic to quaternary.The example of alcohol is propyl carbinol, n-Octanol, stearyl alcohol, ethylene glycol, propylene glycol, neopentyl glycol, tetramethylolmethane, preferably glycerine and tetramethylolmethane.
Aliphatic amine can be monobasic to ternary.The example is stearylamine, quadrol, propylene diamine, hexanediamine, two (the amino hexyl of 6-) amine, particularly preferably quadrol and hexanediamine.Preferred ester or acid amides are corresponding distearin, Tristearoylglycerol, distearyl acid ethylene diamine ester, monopalmitin, trilaurin, Dan docosoic glyceryl ester and pentaerythritol tetrastearate.
Also can use the mixture of different esters or acid amides, or the ester mixture of being combined with any required ratio of mixture with acid amides.
Moulding compound of the present invention can comprise as component D3) 0.05 to 3 % by weight, preferably 0.1 to 1.5 % by weight and the copper stablizer that is in particular 0.1 to 1 % by weight---preferred Cu (I) halogenide, particularly with the mixture of alkali metal halide (preferably KI) with the 1:4 ratio---or sterically hindered phenol, or their mixture.
The cuprous salt used is preferably cuprous acetate, cuprous chloride, cuprous bromide, cuprous iodide.Described material comprises 5 to 500ppm, preferably 10 to 250ppm the described mantoquita based on the polymeric amide meter.
If copper exists with molecular distribution in polymeric amide, especially obtain favourable characteristic.The enriched material that this can comprise polymeric amide by adding to moulding compound, comprise cuprous salt, comprise alkali metal halide solid, the homogeneous solution form is realized.For example, enriched material commonly used is consisted of the mixture be comprised of cupric iodide or cupric bromide and potassiumiodide of the polymeric amide of 79 to 95 % by weight and 21 to 5 % by weight.Copper concentration in described solid homogeneous solution is preferably 0.3 to 3 % by weight, is in particular 0.5 to 2 % by weight, the gross weight meter based on solution, and the mol ratio of cuprous iodide and potassiumiodide is 1 to 11.5, preferably 1 to 5.
The polymeric amide that is applicable to enriched material is homopolyamide and copolyamide, particularly nylon-6 and nylon-6,6.
Suitable sterically hindered phenol D3) be in principle all compounds that there is the phenol structure and there is at least one bulky group on the phenol ring.
For example preferably use the compound with following formula
Wherein
R
1and R
2for the alkyl group of alkyl group, replacement or the triazole group of replacement, and radicals R wherein
1and R
2can be identical or different, and R
3amino group for alkyl group, alkoxy base or the replacement of alkyl group, replacement.
The antioxidant of the above-mentioned type for example is described in DE-A2702661 (US-A4360617).
Another organizes preferred sterically hindered phenol is the benzene carboxylic acid derived from replacing those, particularly derived from those of the phenylpropionic acid replaced.
Particularly preferred compound from this group is the compound with following formula
Wherein, R
4, R
5, R
7and R
8can there is substituent C for itself independently of one another
1-C
8alkyl (at least one in these groups is bulky group), and R
6also can there is the aliphatic divalent group of C-O key for thering is 1 to 10 carbon atom and its main chain.
Preferred compound corresponding to these formulas is
(purchased from BASF SE's
245)
(purchased from BASF SE's
259)
Should mention the example of following all substances as sterically hindered phenol:
2, 2 '-methylene-bis (4-methyl-6-tert-butylphenol), it is two that [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid 1, 6-hexylene glycol ester), four [3-(3, 5-di-t-butyl-4-hydroxyl-phenol) propionic acid pentaerythritol ester], distearyl-3, 5-di-tert-butyl-4-hydroxyl benzyl phosphonic acid ester, 3, 5-di-t-butyl-4-hydroxyl phenylpropionic acid-2, 6, 7-trioxa-1-phospha dicyclo [2.2.2] suffering-4-base methyl esters, 3, 5-di-t-butyl-4-hydroxyphenyl-3, 5-bis-distearyl sulfo-triamino amine, 2-(2 '-hydroxyl-3 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl)-5-chlorobenzotriazole, 2, 6-di-t-butyl-4-hydroxymethyl phenol, 1, 3, 5-trimethylammonium-2, 4, 6-tri-(3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene, 4, 4'-methylene-bis (2, the 6-DI-tert-butylphenol compounds), 3, 5-di-tert-butyl-4-hydroxyl benzyl dimethyl amine.
Confirmed that compound effective especially and that therefore preferably use is 2,2 '-methylene-bis (4-methyl-6-tert-butylphenol), two (3,5-di-tert-butyl-hydroxy phenyl) propionic acid 1,6-hexylene glycol ester (
259), four [3-(3,5-di-t-butyl-4-hydroxyl-phenol) propionic acid pentaerythritol ester] and N, the N'-hexa-methylene is two-3,5-di-t-butyl-4-hydroxyl hydrocinnamamide (
1098), and the above-mentioned product purchased from Ciba Geigy
245, it has particularly preferred suitability.
The contained D3 that can be used alone or use as mixture) amount is 0.05 to 3 % by weight, and preferably 0.1 to 1.5 % by weight, be in particular 0.1 to 1 % by weight, based on moulding compound A) to D) the gross weight meter.
In some cases, confirmed that the phenolic hydroxyl group ortho position has that to be no more than the be obstructed space hindered phenol of group of a space be particularly advantageous---particularly when colour fastness that assessment is stored for a long time in diffused light---.
Moulding compound of the present invention can preferably comprise as component D3) 0.05 to 5 % by weight, preferably 0.1 to 2 % by weight and the nigrosine (nigrosin) that is in particular 0.25 to 1.5 % by weight.
Nigrosine be generally one group relevant to indulines and take black or the grey phenazine dyes (azines) of various ways (water-soluble, oil soluble, pure dissolubility), it dyes black and leather, shoe polish, varnish, plastics for woolen dyed and wool stamp, silk, baking finish, printing ink etc. are painted, and as the microscope dyestuff.
Nigrosine industrial through oil of mirbane, aniline and anilinechloride and metallic iron and FeCl
3heating and make.
Component D3) can free alkali or the form of salt (for example hydrochloride) use.
Further details about nigrosine is found in for example electronic encyclopedia
online, Version2.8, Thieme-Verlag Stuttgart, 2006, keyword is " Nigrosin ".
Thermoplastic composition of the present invention can comprise as component D3) processing aid commonly used, caused reagent, lubricant and releasing agent, tinting material (such as dyestuff and pigment), nucleator, the softening agent etc. that decompose and caused decomposition by ultraviolet ray by heat such as stablizer, oxidation retarder, opposing.
The oxidation retarder that can mention and the example of thermo-stabilizer have living space various replacement members and composition thereof and the iron powder (being derived from pentacarbonyl iron) of hindered phenol and/or phosphorous acid ester and amine (for example TAD), quinhydrones, secondary aromatic amine (for example pentanoic), these groups, its concentration is up to 1 % by weight, the weighing scale based on thermoplastic composition.
Resorcinol, salicylate, benzotriazole and benzophenone that the UV stablizer that can mention is various replacements, the consumption based on the moulding compound meter is generally up to 2 % by weight.
The tinting material that can add is mineral dye, for example titanium dioxide, ultramarine blue, ferric oxide and carbon black, and pigment dyestuff, and as phthalocyanine, quinacridone He perylene, and dyestuff, as anthraquinone.
Spendable nucleator is sodium phenylphosphinate, aluminium, silicon-dioxide, and preferably talc.
Thermoplastic composition of the present invention can be by following known method preparation itself: by conventional mixing equipment, mixing starting ingredient in as screw extrusion press, Brabender mixing tank or Banbury mixing tank, then they are extruded; Make subsequently extrudate cooling and pulverize.Also can be by each component pre-mixing, then surplus stock adds respectively and/or with mixture.Mixing temperature is generally 230 to 320 ℃.
In another preferred method, can be by B component) and optional C) with prepolymer, mix, compounding (compound) granulation.Subsequently by the gained pellet under rare gas element lower than component A) the temperature of fusing point under solid phase is concentrated until reach required viscosity continuously or off and on.
Thermoplastic composition of the present invention is characterised in that good painted and flame retardant resistance, and good especially glow wire test's result and good mechanical property.
These materials are applicable to prepare the moulded product of fiber, paper tinsel and any type.Now provide some examples: cylinder head cover, motor car bonnet, inlet pipe, ventilation cooler head, plug-in type connector, gear, cooling air impeller and cooling water tank.
Product prepared by the polymeric amide that available mobility improves in the Electrical and Electronic field is plug, plug fitting, plug connector, thin film switch, circuit board module, micromodule, coil, the I/0 plug connector, plug for circuit card (PCB), flexible PCB (FPC) is used plug, flexible integration circuit (FFC) is used plug, high speed plug connector, the terminal connection plate, connector plug, equipment connector, the core of a cable assembly, circuit base, the circuit base assembly, three-dimensional injection moulding circuit base, circuit connection element and dynamo-electric assembly.
Possible automotive interior application is for dashboard, steering-column switch, seat-assembly, headrest, central control station, transmission case assembly and door module, and possible automobile external is applied as for door handle, outer visor assembly, windshield wiper assemblies, windscreen wiper protective sleeve, grid, roof rail, awning framework, hood, cylinder head cover, inlet pipe, windscreen wiper and outside body component.
The polymeric amide that mobility improves may be applied as the assembly of using for the manufacture of kitchen utilities in kitchen and daily field, for example frying pan, flatiron and button, and may apply in gardening and leisure field, for example, for assembly or garden facility and the door handle of irrigation system.
Embodiment
Use following component:
Component A):
Nylon-6,6, its viscosity number VN is 150ml/g, according to ISO307, under 25 ℃, in the solution that the concentration of the sulfuric acid of 96 % by weight concentration is 0.5 % by weight, measures that (material used is for from BASF SE's
a24).
B component): melam
B component) as prepared in WO96/16948.
B component/1C
The polyphosphoric acid melamine ester is (purchased from BASF SE's
200)
Component C)
Red phosphorus
Component D1)
Glass fibre
Component D2)
Positive butyl ester/the vinylformic acid of ethylene/acrylic acid/MA multipolymer
This moulding compound of preparation in ZSK40, output is 30kg/ hour and is approximately carrying out under the flat temperature curve of 290 ℃.
Carry out following test:
According to the MVR (275 ℃/5kg load) of DIN EN ISO1133.2005,
According to the Elongation test of ISO527-2, and according to but shellfish (Charpy) gap impact resistance of ISO179/1eU, according to the LOI value (limiting oxygen index) of ISO4589-2,
And glowing filament characteristic
A) according to the GWFi of DIN EN60695-2-12
B) according to the GWiT of DIN EN60695-2-13.
The sample that is 0.8mm to thickness according to UL94 carries out fire resistance mensuration.
Aging condition: 2 days, 23 ℃.
Measure total after flame time of 5 samples under the standard conditions of temperature and humidity.
Measure (burning) dropping performance of 5 samples under the temperature and humidity of standard conditions.
Provide composition and the test result of moulding compound in following table.
Table 1:
All moulding compounds comprise the lubricant (calcium stearate) that adds up to 1.54 % by weight and stablizer, and (zinc oxide, purchased from BASF's
1098).
Claims (9)
1. a thermoplastic composition, it comprises
A) at least one polyamide thermoplastic of 10 to 99.4 % by weight
B) the melam compound of 0.5 to 20 % by weight
C) red phosphorus of 0.1 to 60 % by weight
D) other additives of 0 to 60 % by weight,
A wherein) to D) weight percent add up to 100%.
2. the thermoplastic composition of claim 1, it comprises
A) 20 to 98 % by weight
B) 0.5 to 15 % by weight
C) 0.5 to 40 % by weight
D1) the fibrous or particulate filler of 1 to 40 % by weight, or their mixture
D2) other additives of 0 to 50 % by weight.
3. claim 1 or 2 thermoplastic composition, it comprises
A) 20 to 97 % by weight
B) 0.5 to 15 % by weight
C) 0.5 to 40 % by weight
D1) 1 to 40 % by weight
D2) impact modifying agent of 1 to 30 % by weight
D3) 0 to 20 other additives of % by weight.
4. the thermoplastic composition of claims 1 to 3, wherein component C) with the form of the enriched material in polymeric amide (masterbatch), use.
5. the thermoplastic composition of claim 1 to 4, the consisting of of wherein said masterbatch
C
1) polymeric amide of 30 to 90 % by weight,
C
2) red phosphorus of 10 to 70 % by weight.
6. the thermoplastic composition of claim 1 to 4, wherein B component) by the compound of following general formula, formed
Wherein, radicals R is hydrogen or the alkyl with 1 to 12 carbon atom independently of each other.
7. the thermoplastic composition of claim 1 to 6, it comprises as B component) melam (all R=hydrogen).
8. the thermoplastic composition of claim 1 to 7 is for the preparation of the purposes of fiber, paper tinsel and moulded product.
9. fiber, paper tinsel or the moulded product that can be obtained by the thermoplastic composition of claim 1 to 7.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP11164108 | 2011-04-28 | ||
| EP11164108.0 | 2011-04-28 | ||
| PCT/EP2012/057576 WO2012146624A1 (en) | 2011-04-28 | 2012-04-25 | Flame-retardant molding materials |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103492488A true CN103492488A (en) | 2014-01-01 |
Family
ID=45999852
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201280020075.5A Pending CN103492488A (en) | 2011-04-28 | 2012-04-25 | Flame-retardant molding materials |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP2702102A1 (en) |
| JP (1) | JP2014517093A (en) |
| CN (1) | CN103492488A (en) |
| BR (1) | BR112013027454A2 (en) |
| WO (1) | WO2012146624A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111138850A (en) * | 2019-12-12 | 2020-05-12 | 金发科技股份有限公司 | Polyamide composite material and preparation method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8987357B2 (en) | 2011-05-27 | 2015-03-24 | Basf Se | Thermoplastic molding composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111138850A (en) * | 2019-12-12 | 2020-05-12 | 金发科技股份有限公司 | Polyamide composite material and preparation method thereof |
| WO2021114912A1 (en) * | 2019-12-12 | 2021-06-17 | 金发科技股份有限公司 | Polyamide composite material and method for preparation thereof |
| CN111138850B (en) * | 2019-12-12 | 2021-08-13 | 金发科技股份有限公司 | Polyamide composite material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| BR112013027454A2 (en) | 2019-09-24 |
| JP2014517093A (en) | 2014-07-17 |
| WO2012146624A1 (en) | 2012-11-01 |
| EP2702102A1 (en) | 2014-03-05 |
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