CN101792602A - Halogen-free expansible flame-retardant thermoplastic resin composition - Google Patents
Halogen-free expansible flame-retardant thermoplastic resin composition Download PDFInfo
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- CN101792602A CN101792602A CN 201010122219 CN201010122219A CN101792602A CN 101792602 A CN101792602 A CN 101792602A CN 201010122219 CN201010122219 CN 201010122219 CN 201010122219 A CN201010122219 A CN 201010122219A CN 101792602 A CN101792602 A CN 101792602A
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Abstract
The invention discloses a halogen-free expansible flame-retardant thermoplastic resin composition, which is prepared by fusing and blending the following components in percentage by weight: 40 to 80 percent of thermoplastic resin, 18 to 25 percent of halogen-free expansible flame retardant, 0 to 5 percent of flame-retardant synergetic agent, 0 to 30 percent of glass fiber, 0 to 2 percent of coupling agent and 0.5 to 1 percent of antioxidant, wherein the thermoplastic resin is any one of polyamide 6, polyamide 66 and polylactic acid or glass fiber reinforced product thereof. The halogen-free expansible flame retardant in the flame-retardant thermoplastic resin composition has low additive amount and good flame retardancy, and the compound flame-retardant synergetic agent does not affect various inherent properties of the resin and can improve the flame retardancy of the material and reduce the cost of the material so as to fill the blank that the prior art has no thermoplastic resin compositions of halogen-free expansible flame-retardant polyamide, polylactic acid and the like.
Description
Technical field
The invention belongs to the fire-retardant thermoplastic resin technical field, be specifically related to a kind of efficient halogen-free expansible flame-retardant thermoplastic resin composition, comprise that halogen-free expansion type flame-proof polyamide 6 (PA6), polyamide 66 (PA66), poly(lactic acid) (PLA) and their glass strengthen product.
Background technology
Polymeric amide and poly(lactic acid) are the thermoplastic resins of two quasi-representatives.Polymeric amide is commonly called as nylon (Nylon), and English name Polyamide (PA), polyamide 6 and polyamide 66 are two most important kinds wherein.Though they become the preferred material of electric industry and automotive industry because of having favorable mechanical performance, chemical-resistant resistance, oil resistant and excellent electric insulating, but because these fields are very high to the flame retardant properties requirement of material now, and the flame retardant resistance of polymeric amide and glass enhancing product thereof is all very poor, its oxygen index has only 22～25%, refractory drips also can only reach the UL94-V2 level, thereby its application is very limited.
Poly(lactic acid) is a kind ofly to derive from renewable resources and can be degraded to carbonic acid gas fully and water " green polymer " material.Though poly(lactic acid) is also because of having favorable mechanical performance and processing characteristics, and by " green plastic " of praise for tool potentiality.But the same with polyamide resin, the inflammableness of its existence has still limited its application in fields such as aviation, electronics, packings.
In order to solve the inflammable problem of polymeric amide and polylactic resin, existing common way is to add fire retardant to improve its inflammableness in these thermoplastic resins.And additive flame retardant system commonly used at present mainly contains three kinds: (1) halogen system-Sb system fire retardant; (2) inorganic hydroxide fire retardant; (3) phosphonium flame retardant.As everyone knows, by the fire-retardant resin of halogen system-Sb system fire retardant when the burning since can discharge poisonous in a large number, be with corrosive gas, as violents in toxicity such as hydrogen halide, dioxin and the health of serious environment pollution and harm humans, even it is not burned, its recovery and processing also can throw into question for environment, Given this, with the European Union be production and the use of having promulgated a decree and forbidden this based flame retardant and corresponding flame retardant products thereof in many countries and regions of representative., thereby very big as the aluminium hydroxide of inorganic hydroxide fire retardant, magnesium hydroxide etc. to the influences such as mechanical property of material then because addition big (will reach 50～60% usually and could satisfy fire-retardant requirement) is poor with resin compatible.Though phosphonium flame retardant such as red phosphorus have good flame-retardant effect to polyamide 6 and polyamide 66, it exists poor heat stability and color can not obtain shortcomings such as light goods deeply again.In addition, polyphosphoric acid melamine salt etc. also have certain flame retardant effect to polyamide 6 and polyamide 66, but use addition big separately, and are bigger to the mechanical property influence of material.Simultaneously, also have " wick effect " because the glass of polyamide 6 and polyamide 66 strengthens product, its flame retardant resistance is poorer, thereby makes the fire-retardant difficult point that becomes in the flame retardant area of fiber glass reinforced polyamide.Fire-retardant research report for poly(lactic acid) also mainly concentrates on halogenated flame retardant, inorganic hydroxide fire retardant and phosphoric acid ester (salt) etc., there is also shortcomings such as toxicity is big, addition is big.
Summary of the invention
The objective of the invention is to strengthen the problem that product exists at existing fire-retardant polyamide 6 (PA6), polyamide 66 (PA66), poly(lactic acid) (PLA) and their glass, provide that a kind of to be added with by the triazines char-forming agent be charcoal source and source of the gas, P contained compound is that acid source is formed the fire-retardant thermoplastic resin composition of halogen-free flameproof expanding fire retardant.
Halogen-free expansible flame-retardant thermoplastic resin composition provided by the invention, said composition are by following component, make through melt blending:
Thermoplastic resin 40～80%
Halogen-free expansion fire retardant 18～25%
Fire retarding synergist 0～5%
Glass fibre 0～30%
Coupling agent 0～2%
Oxidation inhibitor 0.5～1%
Wherein said thermoplastic resin is that polyamide 6, polyamide 66, poly(lactic acid) or its glass strengthen any in the product, and each components contents is a weight percentage.
Halogen-free expansion fire retardant described in the above composition is made up of acid source, source of the gas and charcoal source, the mass ratio in acid source and source of the gas and charcoal source is 1～5: 1, acid source is phosphoric acid salt, poly-phosphate, pyrophosphate salt, phosphoric acid ester, inorganic hypophosphite, organic secondary phosphine acid salt or 9, the 10-dihydro-9-oxy is assorted-in 10-phospho hetero phenanthrene-10-oxide compound and the derivative thereof any, preferred ammonium polyphosphate or inorganic hypo-aluminum orthophosphate, wherein the molecular formula of inorganic hypo-aluminum orthophosphate is (H
2PO
2)
3Al, its mean particle size is less than 30 μ m, and maximum particle size is less than 100 μ m, and preferred average particle size is less than 20 μ m, and maximum particle size is less than 50 μ m; Source of the gas and charcoal source are triazines oligopolymer char-forming agent or branching and crosslinked triazines macromolecular carbon forming agent.Wherein used triazines oligopolymer char-forming agent is any in the following general structure:
R in the formula
1=-NH
2Or-NHCH
2CH
2OH; R
2=-NHCH
2CH
2NHCH
2CH
2NHCH
2CH
2NH-,-NHCH
2CH
2NHCH
2CH
2NHCH
2CH
2NHCH
2CH
2NH-or-NHCH
2CH
2NHCH
2CH
2Among the NH-any; m
1=0 or 1; m
2=1 or 2; R
3=(CH
2)
N1Or C
6H
4, n1=1～6; A=-NHR
4NH-or
R
4=(CH
2)
N2Or phenyl ring, n2=2～6; B represents piperazine
M=1～15, n=2～50,
Used branching and crosslinked triazine macromolecular carbon forming agent are any in the following general structure:
X, Y, Z are-NH-R in the formula
5-NH-,-NH-R
6-NH-,-NH-R
6-M-R
7-NH-,-NH-R
6-R
7-NH-,--O-R
5-O-,-O-R
6-O-,-O-R
6-M-R
7-O-,-O-R
6-R
7-O-,-S-R
5-S-,-S-R
6-S-,-S-R
6-M-R
7-S-or-S-R
6-R
7Among-the S-any, and X, Y, Z can be identical also can be inequality, wherein R
5To represent carbonatoms be 2～6 straight or branched alkyl or contain-NH-or-NH
2The straight or branched alkyl that replaces; R
6, R
7Represent the phenyl of phenyl or replacement, and R
6, R
7Can be identical, also can be inequality; It is 1～6 straight or branched alkyl that M represents carbonatoms, alkyl, sulfuryl, azo-group or sulphur atom that amido replaces.
Fire retarding synergist described in the above composition is any in polynite (MMT), organic modification montmonrillonite (OMMT), molecular sieve, wilkinite, rectorite leng, sepiolite (SEP), diatomite, metal oxide, metal-salt or the two oxyhydroxide (LDH).Wherein two oxyhydroxides are by divalent-metal ion (M
2+) and trivalent metal ion (M
3+) class that constitutes has the compound with veneer structure of hydroxyl.Divalent-metal ion is Zn in its veneer structure
2+, Mg
2+, Ni
2+, Cu
2+, Co
2+, Sn
2+, Ca
2+, Mn
2+, Fe
2+At least a Deng in the metal ion with soluble salt; Trivalent metal ion is Al in its veneer structure
3+, Fe
3+, Mn
3+, Co
3+At least a Deng in the metal ion with soluble salt.The mol ratio of divalent-metal ion and trivalent metal ion is 0.5～4: 1 in its structure.This pair oxyhydroxide both can also can prepare according to methods such as existing co-precipitation, high saturation, nucleation/crystallization isolation, non-equilibrium crystallization from buying on the market.
Glass fibre described in the above composition is any in alkali free glass fibre, E-glass fibre or the C-glass fibre.
Coupling agent described in the above composition is any in aluminate coupling agent or the silane coupling agent.Wherein aluminate coupling agent is selected from two (dioctylphosphato) isopropyl titanate, three (dodecyl benzenesulfonyl) isopropyl titanate, two (dioctyl pyrophosphoryl oxygen base) isopropyl titanate, isopropyl tri (dioctylpyrophosphato)titanate, two (dioctyl phosphite base) titanium isopropylate or compound monoalkoxytitanates; Silane coupling agent is selected from γ-Diethylenetriamine base propyl-triethoxysilicane, γ-quadrol propyl group trivinyl silane, two-(β hydroxyethyl) γ-An Bingjisanyiyangjiguiwan, vinyltriethoxysilane or γ-propyl methacrylate base Trimethoxy silane.
Oxidation inhibitor described in the above composition is by mass ratio 1～4: the composite antioxidant that 1 antioxidant 1010 and oxidation inhibitor 168 are formed.
Halogen-free expansible flame-retardant thermoplastic resin composition provided by the invention is to adopt conventional melting mixing method preparation, the concrete processing step and the condition of this method following (add-on of following material is weight percentage if no special instructions):
1, composite mixing is put into high-speed mixer with 18～25% halogen-free expansion fire retardant earlier and is mixed, and wherein the mass ratio in acid source and source of the gas and charcoal source is 1～5: 1, adds 0～2% coupling agent then and mixes, and obtains flame-retardant mixture;
2, the flame-retardant mixture after vacuum-drying will mix is under 80～100 ℃ in temperature, vacuum-drying 6-10 hour; At 80～110 ℃ of following vacuum-drying 8-10 hours, wherein poly(lactic acid) or poly(lactic acid) glass strengthened product at 80 ℃ of following vacuum-drying 8-10 hours with thermoplastic resin, and polyamide 6, polyamide 66 or its glass strengthened product 100-110 ℃ of following vacuum-drying 8-10 hour; Add glass fibre if desired, then with glass fibre at 100-110 ℃ of following vacuum-drying 8-10 hour;
3, (mass ratio of antioxidant 1010 and oxidation inhibitor 168 is 1～4 to melt blending: 1), after 0～30% glass fibre and 40～80% thermoplastic resin mix, put into the twin screw extruder melt blending and extrude with dried flame-retardant mixture, 0～5% fire retarding synergist, 0.5～1% composite antioxidant;
4, the cooling and dicing melt blended material is extruded back naturally cooling pelletizing.
The present invention has the following advantages:
1, because the fire retardant that adds in the halogen-free expansible flame-retardant thermoplastic resin composition provided by the invention is a halogen-free expansion fire retardant, thereby halogen gas release in use, particularly in combustion processes, avoided injury poisonous, that obnoxious flavour discharges pollution on the environment and human body is caused.
2, because the Heat stability is good of acid source in the halogen-free expansion fire retardant that the present invention adds, particularly the ammonium polyphosphate of high-polymerization degree or mean particle size are less than 30 μ m hypo-aluminum orthophosphates, thereby not only be used the flame retarding efficiency height with char-forming agent, and good with the thermoplastic resin consistency, processing characteristics is good.
3, because halogen-free expansible agent provided by the invention can well solve the problem of the fire-retardant difficulty of fiber glass reinforced polyamide product that causes because of " wick effect ", thereby the fiberglass reinforced fire retardant polyamide product of gained not only has the good mechanical performance, and also has good flame retardancy.
4, because halogen-free expansible flame-retardant thermoplastic resin composition provided by the invention can the compositional flame-retardant synergist, and the good nano-dispersed effect in polymkeric substance of this fire retarding synergist, thereby the mechanical property of resin is strengthened.
5, since halogen-free expansible flame-retardant thermoplastic resin provided by the invention in combustion processes, the special intercalation lift-off structure of fire retarding synergist can play good iris action in combustion processes, and but the catalyst body fire retardant forms compact carbon layer more, thereby can obtain better flame retardant effect.
Embodiment
Below by embodiment the present invention is specifically described; be necessary to be pointed out that at this following examples only are used for that the invention will be further described; can not be interpreted as limiting the scope of the invention; the person skilled in the art in this field makes some nonessential improvement and adjustment according to the invention described above content to the present invention, still belongs to protection domain of the present invention.
In addition, the percentage ratio that need to prove the used material of following each embodiment is weight percentage.As without specified otherwise, required flame-retardant mixture, resin, the glass fibre of preparation fire-proof resin composition all needs vacuum-drying before melt blending, and concrete grammar is as follows: flame-retardant mixture is under 80 ℃ in temperature, vacuum-drying 6-10 hour; Poly(lactic acid) is under 80 ℃ in temperature, vacuum-drying 8-10 hour; Polyamide 6, polyamide 66, glass fibre are under 100-110 ℃ in temperature, vacuum-drying 8-10 hour.The limiting oxygen index(LOI) LOI of resulting composition records by ASTM D2863-97 standard, and vertical combustion is to record by ASTM D3801 standard.
The used triazines char-forming agent structure of following examples is as follows:
Work as X=-NHCH
2CH
2NHCH
2CH
2NH-, and X, Y, Z are identical, this branching and crosslinked macromolecular carbon forming agent abbreviate CA1 as;
Work as X=-NHCH
2CH
2NH-, and X, Y, when Z is identical, this branching and crosslinked macromolecular carbon forming agent are CA2;
Work as X=-NHCH
2CH
2NH-, Y=-NHCH
2CH
2NHCH
2CH
2NH-, Z=-NHCH
2CH
2During NH-, this branching and crosslinked macromolecular carbon forming agent are CA3;
Work as X=-NHCH
2CH
2NHCH
2CH
2NHCH
2CH
2NH-, and X, Y, when Z is identical, this branching and crosslinked macromolecular carbon forming agent are CA4;
When the X=phenylenediamine, and X, Y, when Z is identical, this branching and crosslinked macromolecular carbon forming agent are CA5;
Work as X=-O-CH
2CH
2-O-, and X, Y, when Z is identical, this branching and crosslinked macromolecular carbon forming agent are CA6;
Embodiment 1
Earlier 24% ammonium polyphosphate and char-forming agent CA1 (mass ratio is 5: 1) are put into high-speed mixer and mix, add two (dioctyl pyrophosphoryl oxygen base) isopropyl titanate coupling agent of 1% then and continue in the high-speed mixer and mix; After the composite antioxidant of the flame-retardant mixture after the vacuum-drying, 74% polyamide 6 and 1% (antioxidant 1010 and 168 mass ratio are 1: 1) mixed, after putting into the twin screw extruder melt blending and extruding, the naturally cooling pelletizing.
The LOI of gained halogen-free expansion type flame-proof polyamide 6 composition is 29.0, and vertical combustion is the V-0 level.
Embodiment 2
Earlier 22% inorganic hypo-aluminum orthophosphate (median size is less than 20 μ m, and maximum particle diameter is less than 50 μ m) being put into high-speed mixer with char-forming agent CA1 (mass ratio is 1: 1) mixes; After the composite antioxidant of the flame-retardant mixture after the vacuum-drying, 5% organic modification montmonrillonite (OMMT), 72% polyamide 6 and 1% (antioxidant 1010 and 168 mass ratio are 4: 1) mixed, after putting into the twin screw extruder melt blending and extruding, the naturally cooling pelletizing.
The LOI of gained halogen-free expansion type flame-proof polyamide 6 composition is 30.5, and vertical combustion is the V-0 level.
Embodiment 3
Earlier 18% inorganic hypo-aluminum orthophosphate and char-forming agent CA1 (mass ratio is 1: 1) are put into high-speed mixer and mix, add γ-Diethylenetriamine base propyl-triethoxysilicane coupling agent of 2% then and continue in the high-speed mixer and mix; After the composite antioxidant of the flame-retardant mixture after the vacuum-drying, 49.5% polyamide 6 and 0.5% (antioxidant 1010 and 168 mass ratio are 1: 1) mixed, main charging opening feeding in twin screw extruder, 30% E-glass fibre feeds in the side loading mouth after the vacuum-drying, after melt blending is extruded then, the naturally cooling pelletizing.
The LOI of gained halogen-free expandable fire retardant fiber glass reinforced polyamide 6 compositions is 30.5, and vertical combustion is the V-0 level.
Embodiment 4
Earlier 24% phenyl phosphinic acid aluminium and char-forming agent CA1 (mass ratio is 3: 1) being put into high-speed mixer mixes; After the composite antioxidant of the flame-retardant mixture after the vacuum-drying, 60% polyamide 6 and 1% (antioxidant 1010 and 168 mass ratio are 1: 1) mixed, main charging opening feeding in twin screw extruder, 15% E-glass fibre feeds in the side loading mouth after the vacuum-drying, after melt blending is extruded then, the naturally cooling pelletizing.
The LOI of gained halogen-free expandable fire retardant fiber glass reinforced polyamide 6 compositions is 30.0, and vertical combustion is the V-0 level.
Embodiment 5
Earlier 25% ammonium polyphosphate and char-forming agent CA1 (mass ratio is 4: 1) being put into high-speed mixer mixes; After the composite antioxidant of the flame-retardant mixture after the vacuum-drying, 74.5% polyamide 66 and 0.5% (antioxidant 1010 and 168 mass ratio are 1: 1) mixed, after putting into the twin screw extruder melt blending and extruding, the naturally cooling pelletizing.
The LOI of gained halogen-free expansion type flame-proof polyamide 6 composition is 31.2, and vertical combustion is the V-0 level.
Embodiment 6
Earlier 20% diethyl phospho acid aluminium (median size is less than 20 μ m, and maximum particle diameter is less than 50 μ m) being put into high-speed mixer with char-forming agent CA1 (mass ratio is 1: 1) mixes; After the composite antioxidant of the flame-retardant mixture after the vacuum-drying, 1% organic modification montmonrillonite, 48% polyamide 66 and 1% (antioxidant 1010 and 168 mass ratio are 1: 1) mixed, main charging opening feeding in twin screw extruder, 30% C-glass fibre feeds in the side loading mouth after the vacuum-drying, after melt blending is extruded then, the naturally cooling pelletizing.
The LOI of gained halogen-free expandable fire retardant fiber glass reinforced polyamide 66 compositions is 32.4, and vertical combustion is the V-0 level.
Embodiment 7
Earlier 25% ammonium polyphosphate and char-forming agent CA1 (mass ratio is 2: 1) are put into high-speed mixer and mix, add 1% vinyltriethoxysilane coupling agent then and continue in the high-speed mixer and mix; After the composite antioxidant of the flame-retardant mixture after the vacuum-drying, 73% poly(lactic acid) and 1% (antioxidant 1010 and 168 mass ratio are 1: 1) mixed, after putting into the twin screw extruder melt blending and extruding, the naturally cooling pelletizing.
The LOI of gained halogen-free expansion type flame-proof poly (lactic acid) composition is 31.0, and vertical combustion is the V-0 level.
Embodiment 8
Earlier 24% ammonium polyphosphate and char-forming agent CA1 (mass ratio is 3: 1) are put into high-speed mixer and mix, add γ-propyl methacrylate base Trimethoxy silane coupling agent of 1% then and continue in the high-speed mixer and mix; After the composite antioxidant of the flame-retardant mixture after the vacuum-drying, 74.5% poly(lactic acid) and 0.5% (antioxidant 1010 and 168 mass ratio are 1: 1) mixed, after putting into the twin screw extruder melt blending and extruding, the naturally cooling pelletizing.
The LOI of gained halogen-free expansion type flame-proof poly (lactic acid) composition is 31.8, and vertical combustion is the V-0 level.
Embodiment 9
The triazines char-forming agent that present embodiment uses is CA2, and all the other kinds that add material and amount are not stated so omit because of identical with embodiment 1.
The LOI of gained halogen-free expansion type flame-proof polyamide 6 composition is 29.5, and vertical combustion is the V-0 level.
Embodiment 10
The acid source that present embodiment uses is melamine phosphate, and the triazines char-forming agent is CA2, and all the other kinds that add material and amount are not stated so omit because of identical with embodiment 4.
The LOI of gained halogen-free expandable fire retardant fiber glass reinforced polyamide 6 compositions is 29.5, and vertical combustion is the V-0 level.
Embodiment 11
The triazines char-forming agent that present embodiment uses is CA3, all the other in adding material kind with the amount because of identical with embodiment 10, do not state so omit.
The LOI of gained halogen-free expandable fire retardant fiber glass reinforced polyamide 6 compositions is 30.0, and vertical combustion is the V-0 level.
Embodiment 12
The employed acid source of present embodiment is a melamine pyrophosphate, and the triazines char-forming agent is CA4, and all the other kinds that add material and amount are not stated so omit because of identical with embodiment 5.
The LOI of gained halogen-free expandable fire retardant fiber glass reinforced polyamide 6 compositions is 30.2, and vertical combustion is the V-0 level.
Embodiment 13
The employed triazines char-forming agent of present embodiment is CA5, and all the other kinds that add material and amount are not stated so omit because of identical with embodiment 6.
The LOI of gained halogen-free expandable fire retardant fiber glass reinforced polyamide 66 compositions is 31.2, and vertical combustion is the V-0 level.
Embodiment 14
The employed acid source of present embodiment is a melamine pyrophosphate, and the triazines char-forming agent is CA5, and all the other kinds that add material and amount are not stated so omit because of identical with embodiment 7.
The LOI of gained halogen-free expansion type flame-proof poly (lactic acid) composition is 29.4, and vertical combustion is the V-0 level.
Embodiment 15
The employed triazines char-forming agent of present embodiment is CA6, and all the other add material because of identical with embodiment 14, do not state so omit.
The LOI of gained halogen-free expansion type flame-proof poly (lactic acid) composition is 30.0, and vertical combustion is the V-0 level.
Embodiment 16
Earlier 24% ammonium polyphosphate and following structure triazines oligopolymer char-forming agent (mass ratio is 3: 1) are put into high-speed mixer and mix, add γ-quadrol propyl group trivinyl silane coupling agent of 0.5% then and continue in the high-speed mixer and mix; After the composite antioxidant of the flame-retardant mixture after the vacuum-drying, 0.5% organic modification montmonrillonite (OMMT), 74.5% polyamide 6 and 0.5% (antioxidant 1010 and 168 mass ratio are 1: 1) mixed, after putting into the twin screw extruder melt blending and extruding, the naturally cooling pelletizing.
The LOI of gained halogen-free expansion type flame-proof polyamide 6 composition is 28.7, and vertical combustion is the V-0 level.
Embodiment 17
Earlier the triazines oligopolymer char-forming agent (mass ratio is 3: 1) of structure shown in 25% melamine phosphate and the embodiment 16 is put into high-speed mixer and mix, add 2% isopropyl tri (dioctylpyrophosphato)titanate coupling agent then and continue in the high-speed mixer and mix; After the composite antioxidant of the flame-retardant mixture after the vacuum-drying, 2.5% organic modification montmonrillonite (OMMT), 40% polyamide 6 and 0.5% (antioxidant 1010 and 168 mass ratio are 1: 1) mixed, main charging opening feeding in twin screw extruder, 30% alkali free glass fibre feeds in the side loading mouth after the vacuum-drying, after melt blending is extruded, the naturally cooling pelletizing.
The LOI of gained halogen-free expandable fire retardant fiber glass reinforced polyamide 6 compositions is 31.8, and vertical combustion is the V-0 level.
Embodiment 18
Earlier (median size is less than 20 μ m with 20% ethyl-methyl phospho acid aluminium, maximum particle diameter is less than 40 μ m) put into high-speed mixer with the triazines oligopolymer char-forming agent (mass ratio is 1.5: 1) of structure shown in the embodiment 16 and mix, add 1% isopropyl tri (dioctylpyrophosphato)titanate coupling agent then and continue in the high-speed mixer and mix; After the composite antioxidant of the flame-retardant mixture after the vacuum-drying, 63% polyamide 66 and 1% (antioxidant 1010 and 168 mass ratio are 1: 1) mixed, main charging opening feeding in twin screw extruder, 15% E-glass fibre feeds in the side loading mouth after the vacuum-drying, after melt blending is extruded, the naturally cooling pelletizing.
The LOI of gained halogen-free expandable fire retardant fiber glass reinforced polyamide 66 compositions is 31.2, and vertical combustion is the V-0 level.
Embodiment 19
Earlier the triazines oligopolymer char-forming agent (mass ratio is 3: 1) of structure shown in 20% ammonium polyphosphate and the embodiment 16 is put into high-speed mixer and mix, add γ-quadrol propyl group trivinyl silane coupling agent of 0.5% then and continue in the high-speed mixer and mix; After the composite antioxidant of the flame-retardant mixture after the vacuum-drying, 1% organic modification montmonrillonite (OMMT), 48% polyamide 66 and 0.5% (antioxidant 1010 and 168 mass ratio are 1: 1) mixed, main charging opening feeding in twin screw extruder, 30% E-glass fibre feeds in the side loading mouth after the vacuum-drying, after melt blending is extruded, the naturally cooling pelletizing.
The LOI of gained halogen-free expandable fire retardant fiber glass reinforced polyamide 66 compositions is 32.0, and vertical combustion is the V-0 level.
Embodiment 20
Earlier the triazines oligopolymer char-forming agent (mass ratio is 3.5: 1) of structure shown in 25% ammonium polyphosphate and the embodiment 16 is put into high-speed mixer and mix, add 0.5% vinyltriethoxysilane coupling agent then and continue in the high-speed mixer and mix; After the composite antioxidant of the flame-retardant mixture after the vacuum-drying, two oxyhydroxides (LDH) of 2%, 72% poly(lactic acid) and 0.5% (antioxidant 1010 and 168 mass ratio are 1: 1) mixed, after putting into the twin screw extruder melt blending and extruding, the naturally cooling pelletizing.
The LOI of gained halogen-free expansion type flame-proof poly (lactic acid) composition is 32.0, and vertical combustion is the V-0 level.
Embodiment 21
The structure of used triazines oligopolymer is in this enforcement:
All the other kinds that add material and amount are not stated so omit because of identical with embodiment 16.
The LOI of gained halogen-free expansion type flame-proof polyamide 6 composition is 29.5, and the vertical combustion grade is V-0.
Embodiment 22
The used triazines oligopolymer char-forming agent of present embodiment is a structure shown in the embodiment 21, and all the other kinds that add material and amount are not stated so omit because of identical with embodiment 17.
The LOI of gained halogen-free expandable fire retardant fiber glass reinforced polyamide 6 compositions is 31.5, and the vertical combustion grade is the V-0 level.
Embodiment 23
Earlier the triazines macromolecular carbon forming agent (mass ratio is 1.5: 1) of structure shown in 25% melamine pyrophosphate and the embodiment 21 is put into high-speed mixer and mix, add γ-Diethylenetriamine base propyl-triethoxysilicane coupling agent of 1% then and continue in the high-speed mixer and mix; After the composite antioxidant of the flame-retardant mixture after the vacuum-drying, 43% polyamide 6 and 1% (antioxidant 1010 and 168 mass ratio are 1: 1) mixed, main charging opening feeding in twin screw extruder, 30% alkali free glass fibre feeds in the side loading mouth after the vacuum-drying, after melt blending is extruded then, the naturally cooling pelletizing.
The LOI of gained halogen-free expandable fire retardant fiber glass reinforced polyamide 6 compositions is 32.5, and vertical combustion is the V-0 level.
Embodiment 24
Earlier (median size is less than 20 μ m with 20% inorganic hypo-aluminum orthophosphate, maximum particle diameter is less than 40 μ m) put into high-speed mixer with the triazines macromolecular carbon forming agent (mass ratio is 1: 1) of structure shown in the embodiment 21 and mix, add γ-Diethylenetriamine base propyl-triethoxysilicane coupling agent of 2% then and continue in the high-speed mixer and mix; After the composite antioxidant of the flame-retardant mixture after the vacuum-drying, 47% polyamide 6 and 1% (antioxidant 1010 and 168 mass ratio are 1: 1) mixed, main charging opening feeding in twin screw extruder, 30% E-glass fibre feeds in the side loading mouth after the vacuum-drying, after melt blending is extruded then, the naturally cooling pelletizing.
The LOI of gained halogen-free expandable fire retardant fiber glass reinforced polyamide 6 compositions is 32.0, and vertical combustion is the V-0 level.
Embodiment 25
Earlier (median size is less than 30 μ m with 18% inorganic hypo-aluminum orthophosphate, maximum particle diameter is less than 100 μ m) put into high-speed mixer with the triazines macromolecular carbon forming agent (mass ratio is 3: 1) of structure shown in the embodiment 21 and mix, add 1% isopropyl tri (dioctylpyrophosphato)titanate coupling agent then and continue in the high-speed mixer and mix; After the composite antioxidant of the flame-retardant mixture after the vacuum-drying, 2% organic modification montmonrillonite (OMMT), 48% polyamide 66 and 1% (antioxidant 1010 and 168 mass ratio are 1: 1) mixed, main charging opening feeding in twin screw extruder, 30% C-glass fibre feeds in the side loading mouth after the vacuum-drying, after melt blending is extruded then, the naturally cooling pelletizing.
The LOI of gained halogen-free expandable fire retardant fiber glass reinforced polyamide 66 compositions is 30.7, and vertical combustion is the V-0 level.
Embodiment 26
Earlier the triazines oligopolymer char-forming agent (mass ratio is 5: 1) of structure shown in 24% ammonium polyphosphate and the embodiment 21 is put into high-speed mixer and mix, add 0.5% vinyltriethoxysilane coupling agent then and continue in the high-speed mixer and mix; After flame-retardant mixture after the vacuum-drying, 2% the tired composite antioxidant that takes off stone, 73% poly(lactic acid) and 0.5% (antioxidant 1010 and 168 mass ratio are 1: 1) mixed, after putting into the twin screw extruder melt blending and extruding, the naturally cooling pelletizing.
The LOI of gained halogen-free expansion type flame-proof poly (lactic acid) composition is 31.9, and vertical combustion is the V-0 level.
Embodiment 27
Earlier the triazines oligopolymer char-forming agent (mass ratio is 2: 1) of structure shown in 19.5% ammonium polyphosphate and the embodiment 21 being put into high-speed mixer mixes, after the composite antioxidant of the flame-retardant mixture after the vacuum-drying, 80% poly(lactic acid) and 0.5% (antioxidant 1010 and 168 mass ratio are 1: 1) mixed, after putting into the twin screw extruder melt blending and extruding, the naturally cooling pelletizing.
The LOI of gained halogen-free expansion type flame-proof poly (lactic acid) composition is 28.0, and vertical combustion is the V-0 level.
Embodiment 28
The structure of the used triazines oligopolymer of present embodiment char-forming agent is:
M1=1 wherein, m2=1, R=(CH
2)
2, n=2～50, all the other kinds that add material and amount are not stated so omit because of identical with embodiment 16.
The LOI of gained halogen-free expansion type flame-proof polyamide 6 composition is 28.0, and the vertical combustion grade is the V-0 level.
Embodiment 29
The used triazines oligopolymer char-forming agent of present embodiment is a structure shown in the embodiment 28, and all the other kinds that add material and amount are not stated so omit because of identical with embodiment 17.
The LOI of gained halogen-free expandable fire retardant fiber glass reinforced polyamide 6 compositions is 29.5, and the vertical combustion grade is the V-0 level.
Embodiment 30
Earlier (median size is less than 20 μ m with 18% inorganic hypo-aluminum orthophosphate, maximum particle diameter is less than 40 μ m) put into high-speed mixer with the triazines macromolecular carbon forming agent (mass ratio is 4: 1) of structure shown in the embodiment 28 and mix, add 1% isopropyl tri (dioctylpyrophosphato)titanate coupling agent then and continue in the high-speed mixer and mix; After the composite antioxidant of the flame-retardant mixture after the vacuum-drying, 1% organic modification montmonrillonite (OMMT), 49% polyamide 66 and 1% (antioxidant 1010 and 168 mass ratio are 1: 1) mixed, main charging opening feeding in twin screw extruder, 30% alkali free glass fibre feeds in the side loading mouth after the vacuum-drying, after melt blending is extruded then, the naturally cooling pelletizing.
The LOI of gained halogen-free expandable fire retardant fiber glass reinforced polyamide 66 compositions is 31.5, and vertical combustion is the V-0 level.
Embodiment 31
The used triazines oligopolymer char-forming agent of present embodiment is a structure shown in the embodiment 28, and all the other kinds that add material and amount are not stated so omit because of identical with embodiment 27.
The LOI of gained halogen-free expansion type flame-proof poly (lactic acid) composition is 29.5, and the vertical combustion grade is the V-0 level.
Embodiment 32
The structure of the triazines oligopolymer char-forming agent that present embodiment is used is:
M1=1 wherein, m2=1, R=(CH
2)
2, n=2～50, all the other kinds that add material and amount are not stated so omit because of identical with embodiment 16.
The LOI of gained halogen-free expansion type flame-proof polyamide 6 composition is 28.0, and the vertical combustion grade is the V-0 level.
Embodiment 33
The used triazines oligopolymer char-forming agent of present embodiment is a structure shown in the embodiment 32, and all the other kinds that add material and amount are not stated so omit because of identical with embodiment 17.
The LOI of gained halogen-free expandable fire retardant fiber glass reinforced polyamide 6 compositions is 29.0, and the vertical combustion grade is the V-0 level.
Embodiment 34
Earlier the triazines oligopolymer char-forming agent (mass ratio is 4: 1) of structure shown in 25% ammonium polyphosphate and the embodiment 32 is put into high-speed mixer and mix, add γ-quadrol propyl group trivinyl silane coupling agent of 1% then and continue in the high-speed mixer and mix; After the composite antioxidant of the flame-retardant mixture after the vacuum-drying, 43% polyamide 66 and 1% (antioxidant 1010 and 168 mass ratio are 1: 1) mixed, main charging opening feeding in twin screw extruder, 30% E-glass fibre feeds in the side loading mouth after the vacuum-drying, after melt blending is extruded then, the naturally cooling pelletizing.
The LOI of gained halogen-free expandable fire retardant fiber glass reinforced polyamide 66 compositions is 31.0, and vertical combustion is the V-0 level.
Embodiment 35
The structure of the triazines oligopolymer char-forming agent that present embodiment is used is:
M1=1 wherein, m2=1, R=(CH
2)
2, m=7, X is
Y is a piperazine, n=2～50, and all the other kinds that add material and amount are not stated so omit because of identical with embodiment 16.
The LOI of gained halogen-free expansion type flame-proof polyamide 6 composition is 27.7, and the vertical combustion grade is the V-0 level.
Embodiment 36
The used triazines oligopolymer char-forming agent of present embodiment is a structure shown in the embodiment 35, and all the other kinds that add material and amount are not stated so omit because of identical with embodiment 17.
The LOI of gained halogen-free expandable fire retardant fiber glass reinforced polyamide 6 compositions is 28.5, and the vertical combustion grade is the V-0 level.
Embodiment 37
The used triazines oligopolymer char-forming agent of present embodiment is a structure shown in the embodiment 35, and all the other kinds that add material and amount are not stated so omit because of identical with embodiment 19.
The LOI of gained halogen-free expandable fire retardant fiber glass reinforced polyamide 66 compositions is 29.0, and the vertical combustion grade is the V-0 level.
Embodiment 38
The used triazines oligopolymer char-forming agent of present embodiment is a structure shown in the embodiment 35, and all the other kinds that add material and amount are not stated so omit because of identical with embodiment 26.
The LOI of gained halogen-free expansion type flame-proof poly (lactic acid) composition is 30.0, and the vertical combustion grade is the V-0 level.
Embodiment 39
The used triazines oligopolymer char-forming agent of present embodiment is a structure shown in the embodiment 35, and all the other kinds that add material and amount are not stated so omit because of identical with embodiment 27.
The LOI of gained halogen-free expansion type flame-proof poly (lactic acid) composition is 30.5, and the vertical combustion grade is the V-0 level.
Claims (9)
1. halogen-free expansible flame-retardant thermoplastic resin composition, said composition is by following component, makes through melt blending:
Thermoplastic resin 40～80%
Halogen-free expansion fire retardant 18～25%
Fire retarding synergist 0～5%
Glass fibre 0～30%
Coupling agent 0～2%
Oxidation inhibitor 0.5～1%
Wherein said thermoplastic resin is that polyamide 6, polyamide 66, poly(lactic acid) or its glass strengthen any in the product, and each components contents is a weight percentage.
2. halogen-free expansible flame-retardant thermoplastic resin composition according to claim 1, halogen-free expansion fire retardant described in the said composition is made up of acid source, source of the gas and charcoal source, the mass ratio in acid source and source of the gas and charcoal source is 1～5: 1, acid source is phosphoric acid salt, poly-phosphate, pyrophosphate salt, phosphoric acid ester, inorganic hypophosphite, organic secondary phosphine acid salt or 9, the 10-dihydro-9-oxy is assorted-and in 10-phospho hetero phenanthrene-10-oxide compound and the derivative thereof any; Source of the gas and charcoal source are any in triazines oligopolymer char-forming agent or branching and the crosslinked triazines macromolecular carbon forming agent.
3. halogen-free expansible flame-retardant thermoplastic resin composition according to claim 1, halogen-free expansion fire retardant described in the said composition is made up of acid source, source of the gas and charcoal source, the mass ratio in acid source and source of the gas and charcoal source is 1～5: 1, preferred ammonium polyphosphate of acid source or inorganic hypo-aluminum orthophosphate; Source of the gas and charcoal source are any in triazines oligopolymer char-forming agent or branching and the crosslinked triazines macromolecular carbon forming agent, and wherein the molecular formula of inorganic hypo-aluminum orthophosphate is (H
2PO
2)
3Al, its mean particle size is less than 30 μ m, and maximum particle size is less than 100 μ m.
4. halogen-free expansible flame-retardant thermoplastic resin composition according to claim 3, the mean particle size of the inorganic hypo-aluminum orthophosphate of acid source is less than 20 μ m in the said composition, and maximum particle size is less than 50 μ m.
5. according to claim 2 or 3 or 4 described halogen-free expansible flame-retardant thermoplastic resin compositions, used triazines oligopolymer char-forming agent is any in the following general structure in the said composition halogen-free expansion fire retardant:
R in the formula
1=-NH
2Or-NHCH
2CH
2OH; R
2=-NHCH
2CH
2NHCH
2CH
2NHCH
2CH
2NH-,-NHCH
2CH
2NHCH
2CH
2NHCH
2CH
2NHCH
2CH
2NH-or-NHCH
2CH
2NHCH
2CH
2Among the NH-any; m
1=0 or 1; m
2=1 or 2; R
3=(CH
2)
N1Or C
6H
4, n1=1～6; A=-NHR
4NH-or
R
4=(CH
2)
N2Or phenyl ring, n2=2～6; B represents piperazine
M=1～15, n=2～50,
Used branching and crosslinked triazine macromolecular carbon forming agent are any in the following general structure:
X, Y, Z are-NH-R in the formula
5-NH-,-NH-R
6-NH-,-NH-R
6-M-R
7-NH-,-NH-R
6-R
7-NH-,--O-R
5-O-,-O-R
6-O-,-O-R
6-M-R
7-O-,-O-R
6-R
7-O-,-S-R
5-S-,-S-R
6-S-,-S-R
6-M-R
7-S-or-S-R
6-R
7Among-the S-any, and X, Y, Z can be identical also can be inequality, wherein R
5To represent carbonatoms be 2～6 straight or branched alkyl or contain-NH-or-NH
2The straight or branched alkyl that replaces; R
6, R
7Represent the phenyl of phenyl or replacement, and R
6, R
7Can be identical, also can be inequality; It is 1～6 straight or branched alkyl that M represents carbonatoms, alkyl, sulfuryl, azo-group or sulphur atom that amido replaces.
6. according to claim 1 or 2 or 3 or 4 described halogen-free expansible flame-retardant thermoplastic resin compositions, the fire retarding synergist described in the said composition is any in polynite, organic modification montmonrillonite, molecular sieve, wilkinite, rectorite leng, sepiolite, diatomite, metal oxide, metal-salt or the two oxyhydroxide.
7. according to claim 1 or 2 or 3 or 4 described halogen-free expansible flame-retardant thermoplastic resin compositions, the glass fibre described in the said composition is any in alkali free glass fibre, E-glass fibre or the C-glass fibre.
8. according to claim 1 or 2 or 3 or 4 described halogen-free expansible flame-retardant thermoplastic resin compositions, the coupling agent described in the said composition is any in titanate coupling agent or the silane coupling agent.
9. according to claim 1 or 2 or 3 or 4 described halogen-free expansible flame-retardant thermoplastic resin compositions, the oxidation inhibitor described in the said composition is by mass ratio 1～4: the composite antioxidant that 1 antioxidant 1010 and oxidation inhibitor 168 are formed.
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| CN 201010122219 CN101792602A (en) | 2010-03-11 | 2010-03-11 | Halogen-free expansible flame-retardant thermoplastic resin composition |
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| CN 201010122219 CN101792602A (en) | 2010-03-11 | 2010-03-11 | Halogen-free expansible flame-retardant thermoplastic resin composition |
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Family
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