CN101508809A - Halogen-free expansion type flame-proof polyolefin composite material - Google Patents
Halogen-free expansion type flame-proof polyolefin composite material Download PDFInfo
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- CN101508809A CN101508809A CNA2009100586248A CN200910058624A CN101508809A CN 101508809 A CN101508809 A CN 101508809A CN A2009100586248 A CNA2009100586248 A CN A2009100586248A CN 200910058624 A CN200910058624 A CN 200910058624A CN 101508809 A CN101508809 A CN 101508809A
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Abstract
The invention discloses a halogen-free intumescent flame retardant polyolefin composite material which is prepared by evenly mixing the components with the weight percentage as follows: 70 to 84 percent of polyolefin, 15 to 25 percent of halogen-free intumescent flame retardant, 0 to 5 percent of flame-retardant synergist agent, 0 to 2 percent of coupling agent and 0 to 1 percent of antioxidant. The halogen-free intumescent flame retardant polyolefin composite material of the invention is characterized in a low addition of halogen-free intumescent flame retardant as well as the compounded flame retardant synergist agent, thus not only bringing a good compatibility of the flame retardant and the polyolefin and being free from affecting the various inherent performances of the material, but also improving the flame retardance of the materials and lowering material costs. The main flame retardant contained herein can effectively promote the polyolefin to form charcoal under the catalysis of the flame retardant synergist agent and the dense carbon layer is effective in heat insulation and oxygen partition, thus impeding or delaying the combustion of internal materials. Therefore, the material has the good flame retardance.
Description
Technical field
The invention belongs to the technical field of fire retardant polyolefin composite material, be specifically related to a kind of efficient halogen-free expansion type flame-proof polyolefin composite material, comprise the halogen-free expansion type flame-proof long glass fiber reinforced polypropylene composite material.
Background technology
Polyolefine is the thermoplasticity synthetic resins of a class excellent performance, it is not only easy to process, mechanical property and electrical insulating property are good, but also have resistance to chemical attack, nontoxic, characteristics such as density is little, obtained to use widely at aspects such as industrial construction, automotive industry, household electrical appliance, electronic apparatus, packing and building materials.And fibreglass reinforced thermoplastic (is called for short the fiber glass reinforced thermoplastics, GRTP), according to document announcement, in the past few years, its market average annual growth rate is 5～6%, especially wherein long glass fibres reinforced thermoplastics(RTP) (LFRT) is developing faster, and the annual growth with 30% in the past 10 years is rising.The matrix plastic of LFRT mainly is a polypropylene.
The mid-90 in 20th century, along with rapid development of automobile industry, and the enhancing of people's environmental protection and energy saving consciousness, the automobile lightweight begins to become the development trend of new automobile.This development trend of automotive industry makes people once more attention be turned to the research and development of LFRT to come up, some world-class companies have developed a series of macrofiber reinforced thermoplastics(RTP) materials and corresponding preparation technology and equipment one after another, have the core knowledge property right of oneself respectively.At present, it is very extensive that long glass fibres strengthens the application of thermoplastic pellets in automotive field, and wherein long glass fiber reinforced polypropylene is used to the engine shield, instrument board framework, battery tray, chair framework, car front-end module, collision bumper, luggage carrier, spare tyre dish, splash pan, fan blade, engine pan, car roof lining frame of car etc.The advantage of aspects such as EATC (European thermoplastic composite alliance) thinks, the cost performance of LFRT material excellence and the environmental protection that is had thereof, density are low makes it bring into play more and more important effect in automobile is used.By 2010, automobile estimated that with LFRT will have 10% growth every year.
But, regrettably, no matter be polyolefine, or limiting oxygen index(LOI) (the Limited Oxygen Index of long glass fiber reinforced polypropylene material, LOI) all very low, not only be very easy to burning, the combustion heating amount is big, and a large amount of unsaturated gas that produces of combustion processes also will further promote burning conversely.The molten drop of combustion processes material production propagating flame very easily in addition, this just makes it can not be applied to the occasion that can have relatively high expectations to Flame Retardancy, need carry out flame-retardant modified to it.
Polyolefinic flame-retardant modified mode has a variety of, mainly is to be undertaken by adding additive flame retardant in polyolefine.Be used for the flame-retardant modified additive flame retardant of polyolefine at present and mainly contain halogen compounds and inorganic additivess such as magnesium hydroxide or aluminium hydroxide.Halogen-containing additive flame retardant, the fire retardant of particularly chloride, bromine, though be widely used and good flame retardation effect, but burning the time can discharge poisonous in a large number, be with corrosive hydrogen halide, can cause merely the Circuits System switch that can not cause and the corrosion of other metal objects, and the human respiratory tract is worked the mischief with other organ even because of the life-threatening safety of suffocating by fire institute; Volatile matter because of polymkeric substance can not get perfect combustion in addition, can make degradation production form a large amount of carbon granules, produces a large amount of smog, to the withdrawing, rescue and resume work totally unfavorablely of scene of fire personnel, becomes factor very dangerous in the fire.Abandoned at present.Therefore, the new halogen-free flame retardants of exploitation becomes a big problem of flame retardant area.
Halogen-free expansion fire retardant comes to this and arises at the historic moment, and it is to be main component with phosphorus, nitrogen, carbon-collecting source, the gentle flame-retardant system that comes from one of acid source.When being heated with its fire-retardant polymkeric substance, the surface can generate one deck and can play heat insulation, oxygen barrier, press down cigarette, and can prevent to produce certain thickness even carbonaceous foam layer, and this carbonaceous foam layer has good flame retardancy.Therefore, halogen-free expansion fire retardant is described as the revolution of flame-retarded technology.But the flame retarding efficiency of comparing expansion type flame retardant with halogen-containing fire retardant is not high, needs higher addition just can reach needed fire-retardant requirement, so not only can influence the mechanical property of material, has improved the cost value of fire retardant material simultaneously yet.As the preparation of the disclosed a kind of novel halogen-free flame-retardant polypropylene material of Chinese patent CN03138746.2, this material is traditional expansion type flame retardant ammonium polyphosphate, melamine phosphoric acid salt and the tetramethylolmethane polypropylene flame redardant that adopts addition bigger (more than 30%).The disclosed a kind of halogen-free expansion fire retardant fire retardant polyolefin that constitutes with Racemic glycidol amine epoxy resin coated ammonium polyphosphate, inorganics and triaizine compounds or derivatives thereof of Chinese patent CN1556136A, also need to add 28% or during more fire retardant, vertical combustion can reach V-0.The vertical combustion of obtained polypropylene flame redardant just reached the V-0 level when the disclosed a kind of special material for environment-friendly flame-proof polypropylene of Chinese patent CN101280086A, this material need add 35% fire retardant of being made up of ammonium polyphosphate and tetramethylolmethane, 10% zeolite, 10% nylon 6.The disclosed a kind of expanded carbon flame-proof polypropelene composition of Chinese patent CN101293984A, said composition added 25% by ammonium polyphosphate, tetramethylolmethane, polynite and zinc oxide, its LOI can reach 35.0, vertical combustion is the V-0 level.Because the disclosed matrix material of above patent documentation all exists the big problem of expansion type flame retardant addition, thereby not only the mechanical property influence to flame-proof composite material is bigger, and the raising that also can bring cost.
Summary of the invention
Flame retarding efficiency is lower when the objective of the invention is at existing halogen-free expansion fire retardant fire retardant polyolefin, addition is big, the bigger problem of physical and mechanical properties influence to material provides the halogen-free expanded flame-retardant that a kind of addition is few, flame retarding efficiency is high composite polyolefine material.
Halogen-free expansion type flame-proof polyolefin composite material provided by the invention, this matrix material are by following prescription, form through melt blending:
Polyolefine 70～84%
Halogen-free expansion fire retardant 15～25%
Fire retarding synergist 0～5%
The percentage ratio of each material is weight percentage, and described polyolefine is any in polypropylene, long glass fiber reinforced polypropylene, polyethylene or the ethylene-vinyl acetate copolymer.
Halogen-free expansion fire retardant described in this matrix material is that 1～5: 1 ammonium polyphosphate and triazines oligopolymer are formed by mass ratio, and wherein the triazines oligopolymer is a kind of compound of the new synthetic of this seminar, and its general structure is:
R in the formula
1=-NH
2Or-NHCH
2CH
2OH, R
2=-NHCH
2CH
2NHCH
2CH
2NH-,-NHCH
2CH
2NHCH
2CH
2NHCH
2CH
2NH-or-NHCH
2CH
2NHCH
2CH
2NHCH
2CH
2NHCH
2CH
2Among the NH-any one, n=2-50.
The polyolefine of this matrix material be when being long glass fiber reinforced polypropylene, and the halogen-free expansion fire retardant that it added is that 1～5: 1 ammonium polyphosphate and triazines oligopolymer are formed by mass ratio also, but but wherein the triazines oligopolymer also the utilization structure general formula be:
In any, m in the formula
1=0 or 1; m
2=1 or 2; R=(CH
2)
N1Or C
6H
4, n1=1～6; X=-NHR
1NH-or
Or
R wherein
1=(CH
2)
N2Or phenyl ring, n2=2～6; Y represent piperazine or
Or
M=1～15, n=2-50.
Fire retarding synergist described in this matrix material is any in polynite, organic modification montmonrillonite, molecular sieve, wilkinite, rectorite leng, sepiolite, diatomite, metal oxide, metal-salt or the two oxyhydroxide.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.At present two existing commercially available products of oxyhydroxide also can prepare according to methods such as existing co-precipitation, high saturation, nucleation/crystallization isolation, non-equilibrium crystallization.
Coupling agent described in this matrix material is any in aluminate coupling agent, the silane coupling agent.
Oxidation inhibitor described in this matrix material is by mass ratio 1～4: the composite antioxidant that 1 antioxidant 1010 and oxidation inhibitor 168 are formed.
Halogen-free expansion type flame-proof polyolefin composite material provided by the invention is to adopt conventional melt-mixing method preparation, the concrete technology of this method following (proportioning of following material is mass percent):
1, composite mixing will account for the ammonium polyphosphate of halogen-free anti-flaming polyolefin matrix material 15～25% and triazines oligopolymer earlier altogether and put into high-speed mixer and mix, ammonium polyphosphate and triazines oligopolymer mass ratio are 1～5: 1, add the coupling agent that accounts for halogen-free anti-flaming polyolefin matrix material 0～2% again and mix, obtain flame-retardant mixture;
2, the flame-retardant mixture after vacuum-drying will mix is under 70～100 ℃ in temperature, vacuum-drying 6-10 hour;
3, (mass ratio of antioxidant 1010 and oxidation inhibitor 168 is 1～4 to melt blending: 1) and behind 70～84% the polyolefine premix, put into the twin screw extruder melt blending and extrude with dried flame-retardant mixture, 0～5% fire retarding synergist, 0～1% oxidation inhibitor mixture;
4, the cooling and dicing melt blended material is extruded back naturally cooling pelletizing.
Prepare above-mentioned halogen-free expanded flame-retardant long glass fiber reinforced polypropylene composite material provided by the invention and can also adopt following technology (proportioning of following material is mass percent):
1, the various additive total contents of being made up of coupling agent, ammonium polyphosphate, triazines oligopolymer, fire retarding synergist by above method preparation earlier are 30～90% polypropylene flame redardant masterbatch;
2, polypropylene flame redardant masterbatch and the long glass fiber reinforced polypropylene material with preparation mixes in homogenizer, and to make the content of wherein coupling agent, ammonium polyphosphate, triazines oligopolymer and fire retarding synergist be 15～30%.
The present invention has the following advantages:
1, owing to not halogen-containing composition in the halogen-free expanded flame-retardant composite polyolefine material provided by the invention, thereby this matrix material does not in use have halogen-containing gas release, the injury of particularly having avoided obnoxious flavour to discharge pollution on the environment and human body is caused in combustion processes.
2, the addition owing to halogen-free expansion fire retardant in halogen-free expanded flame-retardant composite polyolefine material provided by the invention and the halogen-free expanded flame-retardant long glass fiber reinforced polypropylene composite material is low, when addition is 18%, the fire-retardant index oxygen index of its material not only can be up to 30.9, its UL-94 also can reach the V-0 level, the flame retarding efficiency height.
3, the addition owing to halogen-free expansion fire retardant in halogen-free expanded flame-retardant composite polyolefine material provided by the invention and the halogen-free expanded flame-retardant long glass fiber reinforced polypropylene composite material is low, thereby little to the mechanical property influence of matrix material.
4, owing to composite in halogen-free expanded flame-retardant composite polyolefine material provided by the invention and the halogen-free expanded flame-retardant long glass fiber reinforced polypropylene composite material fire retarding synergist arranged, thereby not only can make fire retardant and compatible polyolefin good, addition reduces, and can also improve Flame Retardancy and the various performances of material inherent.
5, halogen-free expanded flame-retardant composite polyolefine material provided by the invention and halogen-free expanded flame-retardant long glass fiber reinforced polypropylene composite material are in combustion processes, because main body fire retardant wherein can promote effectively that under the katalysis of fire retarding synergist the Polyolefin and long glass fiber reinforced polypropylene becomes charcoal, and compact carbon layer can play effect well heat insulation, oxygen barrier, thereby can hinder or delay the burning of material inside, make material present excellent flame-retardant performance.
6, because halogen-free expanded flame-retardant composite polyolefine material provided by the invention and halogen-free expanded flame-retardant long glass fiber reinforced polypropylene composite material contain the expansion type flame retardant that new synthetic triazines oligopolymer is formed, this fire retardant cooperates with fire retarding synergist, greatly reduces the maximum heat rate of release (see figure 1) of flame retardant polyolefine material.
Description of drawings
The graphic representation of heat release rate (the HRR)-time of flame-proof composite material and virgin pp that accompanying drawing is the flame-proof composite material that is added with fire retarding synergist, do not add fire retarding synergist.PP is a polypropylene among the figure, and IFR is an expansion type flame retardant.
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 present invention is 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 mass percent; The oxygen index LOI of gained matrix material records by ASTM D2863-97 standard, and vertical combustion is to record by ASTM D3801 standard.
Embodiment 1
To account for the ammonium polyphosphate of halogen-free anti-flaming polyolefin matrix material 24.5% and following structure triazines oligopolymer (mass ratio is 1: 1) earlier altogether and put into high-speed mixer and mix, and add 0.5% aluminate coupling agent again and in high-speed mixer, mix; Is under 90 ℃ with the flame-retardant mixture after mixing in temperature, vacuum-drying 8 hours; After the composite antioxidant of dried flame-retardant mixture, 74.45% polypropylene and 0.55% (antioxidant 1010 and 168 mass ratio are 1: 1) mixed, put into the twin screw extruder melt blending and extrude; Melt blended material is extruded back naturally cooling pelletizing.
The LOI of gained halogen-free expanded flame-retardant polypropylene matrix material is 28.9, and vertical combustion is the V-0 level.
Embodiment 2
Put into high-speed mixer and mix accounting for the ammonium polyphosphate of halogen-free anti-flaming polyolefin matrix material 25% and above structure triazines oligopolymer (mass ratio is 1.5: 1) altogether; Is under 100 ℃ with the flame-retardant mixture after mixing in temperature, vacuum-drying 10 hours; After the polypropylene of dried halogen-free expansion fire retardant and 75% mixed, put into the twin screw extruder melt blending and extrude; Melt blended material is extruded back naturally cooling pelletizing.
The LOI of gained halogen-free expanded flame-retardant polypropylene matrix material is 35.2, and vertical combustion is the V-0 level.
Embodiment 3
To account for the triazines oligopolymer (mass ratio is 2: 1) of structure shown in the ammonium polyphosphate of halogen-free anti-flaming polyolefin matrix material 24% and the embodiment 1 earlier altogether and put into high-speed mixer and mix, and add 1% γ-An Bingjisanyiyangjiguiwan coupling agent again and in high-speed mixer, mix; Is under 70 ℃ with the flame-retardant mixture after mixing in temperature, vacuum-drying 6 hours; After the composite antioxidant of dried flame-retardant mixture, 74% polypropylene and 1% (antioxidant 1010 and 168 mass ratio 4: 1) mixed, put into the twin screw extruder melt blending and extrude; Melt blended material is extruded back naturally cooling pelletizing.
The LOI of gained halogen-free expanded flame-retardant polypropylene matrix material is 33.0, and vertical combustion is the V-0 level.
Embodiment 4
To account for the triazines oligopolymer (mass ratio is 4: 1) of structure shown in the ammonium polyphosphate of halogen-free anti-flaming polyolefin matrix material 23% and the embodiment 1 earlier altogether and put into high-speed mixer and mix, and add 2% anilinomethyl trimethoxy silane coupling agent again and in high-speed mixer, mix; Is under 80 ℃ with the flame-retardant mixture after mixing in temperature, vacuum-drying 7 hours; After the composite antioxidant of dried flame-retardant mixture, 74.7% polypropylene and 0.3% (antioxidant 1010 and 168 mass ratio 2: 1) mixed, put into the twin screw extruder melt blending and extrude; Melt blended material is extruded back naturally cooling pelletizing.
The LOI of gained halogen-free expanded flame-retardant polypropylene matrix material is 32.4, and vertical combustion is the V-0 level.
Embodiment 5
To account for the triazines oligopolymer (mass ratio is 5: 1) of structure shown in the ammonium polyphosphate of halogen-free anti-flaming polyolefin matrix material 24% and the embodiment 1 earlier altogether and put into high-speed mixer and mix, and add 1% aluminate coupling agent again and in high-speed mixer, mix; Is under 80 ℃ with the flame-retardant mixture after mixing in temperature, vacuum-drying 8 hours; After the composite antioxidant of dried flame-retardant mixture, 74.7% polypropylene and 0.3% (antioxidant 1010 and 168 mass ratio 3: 1) mixed, put into the twin screw extruder melt blending and extrude; Melt blended material is extruded back naturally cooling pelletizing.
The LOI of gained halogen-free expanded flame-retardant polypropylene matrix material is 29.6, and vertical combustion is the V-0 level.
Embodiment 6
To account for the triazines oligopolymer (mass ratio is 2: 1) of structure shown in the ammonium polyphosphate of halogen-free anti-flaming polyolefin matrix material 24% and the embodiment 1 earlier altogether and put into high-speed mixer and mix, and add 0.5% aluminate coupling agent again and in high-speed mixer, mix; Is under 70 ℃ with the flame-retardant mixture after mixing in temperature, vacuum-drying 6 hours; After the composite antioxidant of dried flame-retardant mixture, 0.5% organic modification montmonrillonite, 74.7% polypropylene and 0.3% (antioxidant 1010 and 168 mass ratio 2: 1) mixed, put into the twin screw extruder melt blending and extrude; Melt blended material is extruded back naturally cooling pelletizing.
The LOI of gained halogen-free expanded flame-retardant polypropylene matrix material is 37.2, and vertical combustion is the V-0 level.
Embodiment 7
To account for the triazines oligopolymer (mass ratio is 3: 1) of structure shown in the ammonium polyphosphate of halogen-free anti-flaming polyolefin matrix material 23.5% and the embodiment 1 earlier altogether and put into high-speed mixer and mix, and add 0.5% anilinomethyl triethoxysilane coupling agent again and in high-speed mixer, mix; Is under 70 ℃ with the flame-retardant mixture after mixing in temperature, vacuum-drying 6 hours; After the composite antioxidant of dried flame-retardant mixture, 1% organic modification montmonrillonite, 74.5% polypropylene and 0.5% (antioxidant 1010 and 168 mass ratio 2: 1) mixed, put into the twin screw extruder melt blending and extrude; Melt blended material is extruded back naturally cooling pelletizing.
The LOI of gained halogen-free expanded flame-retardant polypropylene matrix material is 35.5, and vertical combustion is the V-0 level.
Embodiment 8
To account for the triazines oligopolymer (mass ratio is 2: 1) of structure shown in the ammonium polyphosphate of halogen-free anti-flaming polyolefin matrix material 23% and the embodiment 1 earlier altogether and put into high-speed mixer and mix, and add 0.5% urea propyl trimethoxy silicane coupling agent again and in high-speed mixer, mix; Is under 70 ℃ with the flame-retardant mixture after mixing in temperature, vacuum-drying 6 hours; After the composite antioxidant of dried flame-retardant mixture, 2% polynite, 74% polypropylene and 0.5% (antioxidant 1010 and 168 mass ratio 2: 1) mixed, put into the twin screw extruder melt blending and extrude; Melt blended material is extruded back naturally cooling pelletizing.
The LOI of gained halogen-free expanded flame-retardant polypropylene matrix material is 35.2, and vertical combustion is the V-0 level.
Embodiment 9
To account for the triazines oligopolymer (mass ratio is 1.5: 1) of structure shown in the ammonium polyphosphate of halogen-free anti-flaming polyolefin matrix material 23% and the embodiment 1 earlier altogether and put into high-speed mixer and mix, and add 1% aluminate coupling agent again and in high-speed mixer, mix; Is under 70 ℃ with the flame-retardant mixture after mixing in temperature, vacuum-drying 6 hours; After the composite antioxidant of dried flame-retardant mixture, 3% polynite, 72.5% polypropylene and 0.5% (antioxidant 1010 and 168 mass ratio 1: 1) mixed, put into the twin screw extruder melt blending and extrude; Melt blended material is extruded back naturally cooling pelletizing.
The LOI of gained halogen-free expanded flame-retardant polypropylene matrix material is 35.9, and vertical combustion is the V-0 level.
Embodiment 10
The structure of used triazines oligopolymer is in the present embodiment:
To account for altogether earlier halogen-free anti-flaming polyolefin matrix material 23% ammonium polyphosphate and above shown in the triazines oligopolymer (mass ratio is 5: 1) of structure put into high-speed mixer and mix, add 1% aluminate coupling agent again and in high-speed mixer, mix; Is under 70 ℃ with the flame-retardant mixture after mixing in temperature, vacuum-drying 6 hours; After the composite antioxidant of dried flame-retardant mixture, 5% organic modification polynite, 70.5% polypropylene and 0.5% (antioxidant 1010 and 168 mass ratio 3: 1) mixed, put into the twin screw extruder melt blending and extrude; Melt blended material is extruded back naturally cooling pelletizing.
The LOI of gained halogen-free expanded flame-retardant polypropylene matrix material is 30.3, and vertical combustion is the V-0 level.
Embodiment 11
The structure of used triazines oligopolymer is in the present embodiment:
Other is identical with embodiment 6, slightly.
The LOI of gained halogen-free expanded flame-retardant polypropylene matrix material is 37.8, and vertical combustion is the V-0 level.
Embodiment 12
The structure of used triazines oligopolymer is in the present embodiment:
To account for altogether earlier halogen-free anti-flaming polyolefin matrix material 21% ammonium polyphosphate and above shown in the triazines oligopolymer (mass ratio is 2: 1) of structure put into high-speed mixer and mix, add 0.5% aluminate coupling agent again and in high-speed mixer, mix; Is under 70 ℃ with the flame-retardant mixture after mixing in temperature, vacuum-drying 6 hours; After the composite antioxidant of dried flame-retardant mixture, 0.5% organic modification montmonrillonite, 77.7% polypropylene and 0.3% (antioxidant 1010 and 168 mass ratio 2: 1) mixed, put into the twin screw extruder melt blending and extrude; Melt blended material is extruded back naturally cooling pelletizing.
The LOI of gained halogen-free expanded flame-retardant polypropylene matrix material is 35, and vertical combustion is the V-0 level.
Embodiment 13
To account for the triazines oligopolymer (mass ratio is 2: 1) of structure shown in the ammonium polyphosphate of halogen-free anti-flaming polyolefin matrix material 19% and the embodiment 12 earlier altogether and put into high-speed mixer and mix, and add 0.5% aluminate coupling agent again and in high-speed mixer, mix; Is under 70 ℃ with the flame-retardant mixture after mixing in temperature, vacuum-drying 6 hours; After the composite antioxidant of dried flame-retardant mixture, 0.5% organic modification montmonrillonite, 79.7% polypropylene and 0.3% (antioxidant 1010 and 168 mass ratio 2: 1) mixed, put into the twin screw extruder melt blending and extrude; Melt blended material is extruded back naturally cooling pelletizing.
The LOI of gained halogen-free expanded flame-retardant polypropylene matrix material is 32.6, and vertical combustion is the V-0 level.
Embodiment 14
To account for the triazines oligopolymer (mass ratio is 2: 1) of structure shown in the ammonium polyphosphate of halogen-free anti-flaming polyolefin matrix material 17% and the embodiment 12 earlier altogether and put into high-speed mixer and mix, and add 0.5% aluminate coupling agent again and in high-speed mixer, mix; Is under 70 ℃ with the flame-retardant mixture after mixing in temperature, vacuum-drying 6 hours; After the composite antioxidant of dried flame-retardant mixture, 0.5% organic modification montmonrillonite, 81.7% polypropylene and 0.3% (antioxidant 1010 and 168 mass ratio 2: 1) mixed, put into the twin screw extruder melt blending and extrude; Melt blended material is extruded back naturally cooling pelletizing.
The LOI of gained halogen-free expanded flame-retardant polypropylene matrix material is 30.9, and vertical combustion is the V-0 level.
Embodiment 15
To account for the triazines oligopolymer (mass ratio is 2: 1) of structure shown in the ammonium polyphosphate of halogen-free anti-flaming polyolefin matrix material 15% and the embodiment 10 earlier altogether and put into high-speed mixer and mix, and add 0.5% aluminate coupling agent again and in high-speed mixer, mix; Is under 70 ℃ with the flame-retardant mixture after mixing in temperature, vacuum-drying 6 hours; After the composite antioxidant of dried flame-retardant mixture, 0.5% organic modification montmonrillonite, 83.7% polypropylene and 0.3% (antioxidant 1010 and 168 mass ratio 2: 1) mixed, put into the twin screw extruder melt blending and extrude; Melt blended material is extruded back naturally cooling pelletizing.
The LOI of gained halogen-free expanded flame-retardant polypropylene matrix material is 28.6, and vertical combustion is the V-0 level
Embodiment 16
To account for the triazines oligopolymer (mass ratio is 2: 1) of structure shown in the ammonium polyphosphate of halogen-free anti-flaming polyolefin matrix material 19% and the embodiment 10 earlier altogether and put into high-speed mixer and mix, and add 0.5% aluminate coupling agent again and in high-speed mixer, mix; Is under 70 ℃ with the flame-retardant mixture after mixing in temperature, vacuum-drying 6 hours; After the composite antioxidant of dried flame-retardant mixture, 1% molecular sieve, 79.2% polypropylene and 0.3% (antioxidant 1010 and 168 mass ratio 2: 1) mixed, put into the twin screw extruder melt blending and extrude; Melt blended material is extruded back naturally cooling pelletizing.
The LOI of gained halogen-free expanded flame-retardant polypropylene matrix material is 32.1, and vertical combustion is the V-0 level.
Embodiment 17
To account for total halogen-free anti-flaming polyolefin matrix material massfraction earlier and be the triazines oligopolymer (mass ratio is 2: 1) of structure shown in 19% ammonium polyphosphate and the embodiment 11 and put into high-speed mixer and mix, and add 0.5% aluminate coupling agent again and in high-speed mixer, mix; Is under 70 ℃ with the flame-retardant mixture after mixing in temperature, vacuum-drying 6 hours; After the composite antioxidant (mass ratio of antioxidant 1010 and oxidation inhibitor 168 2: 1) of dried flame-retardant mixture, 1% sepiolite, 79.2% polypropylene and 0.3% mixed, put into the twin screw extruder melt blending and extrude; Melt blended material is extruded back naturally cooling pelletizing.
The LOI of gained halogen-free expanded flame-retardant polypropylene matrix material is 31.5, and vertical combustion is the V-0 level.
Embodiment 18
To account for the triazines oligopolymer (mass ratio is 2: 1) of structure shown in the ammonium polyphosphate of halogen-free anti-flaming polyolefin matrix material 19% and the embodiment 11 earlier altogether and put into high-speed mixer and mix, and add 0.5% aluminate coupling agent again and in high-speed mixer, mix; Is under 70 ℃ with the flame-retardant mixture after mixing in temperature, vacuum-drying 6 hours; After the composite antioxidant of dried flame-retardant mixture, 1% rectorite leng, 79.2% polypropylene and 0.3% (antioxidant 1010 and 168 mass ratio 2: 1) mixed, put into the twin screw extruder melt blending and extrude; Melt blended material is extruded back naturally cooling pelletizing.
The LOI of gained halogen-free expanded flame-retardant polypropylene matrix material is 31.4, and vertical combustion is the V-0 level.
Embodiment 19
To account for the triazines oligopolymer (mass ratio is 2: 1) of structure shown in the ammonium polyphosphate of halogen-free anti-flaming polyolefin matrix material 19% and the embodiment 11 earlier altogether and put into high-speed mixer and mix, and add 0.5% aluminate coupling agent again and in high-speed mixer, mix; Is under 70 ℃ with the flame-retardant mixture after mixing in temperature, vacuum-drying 6 hours; After the composite antioxidant (mass ratio of antioxidant 1010 and oxidation inhibitor 168 2: 1) of dried flame-retardant mixture, 1% zinc borate, 79.2% polypropylene and 0.3% mixed, put into the twin screw extruder melt blending and extrude; Melt blended material is extruded back naturally cooling pelletizing.
The LOI of gained halogen-free expanded flame-retardant polypropylene matrix material is 31.3, and vertical combustion is the V-0 level.
To account for the triazines oligopolymer (mass ratio is 2: 1) of structure shown in the ammonium polyphosphate of halogen-free anti-flaming polyolefin matrix material 19% and the embodiment 11 earlier altogether and put into high-speed mixer and mix, and add 0.5% aluminate coupling agent again and in high-speed mixer, mix; Is under 70 ℃ with the flame-retardant mixture after mixing in temperature, vacuum-drying 6 hours; After the composite antioxidant of dried flame-retardant mixture, the two oxyhydroxides (mol ratio of Fe and Ni is 3:1) of 1% Fe-Ni, 79.2% polypropylene and 0.3% (antioxidant 1010 and 168 mass ratio 2: 1) mixed, put into the twin screw extruder melt blending and extrude; Melt blended material is extruded back naturally cooling pelletizing.
The LOI of gained halogen-free expanded flame-retardant polypropylene matrix material is 31.6, and vertical combustion is the V-0 level.
Embodiment 21
To account for the triazines oligopolymer (mass ratio is 2: 1) of structure shown in the ammonium polyphosphate of halogen-free anti-flaming polyolefin matrix material 19% and the embodiment 10 earlier altogether and put into high-speed mixer and mix, and add 0.5% aluminate coupling agent again and in high-speed mixer, mix; Is under 70 ℃ with the flame-retardant mixture after mixing in temperature, vacuum-drying 6 hours; After the composite antioxidant of dried flame-retardant mixture, 1% zinc oxide, 79.2% polypropylene and 0.3% (antioxidant 1010 and 168 mass ratio 2: 1) mixed, put into the twin screw extruder melt blending and extrude; Melt blended material is extruded back naturally cooling pelletizing.
The LOI of gained halogen-free expanded flame-retardant polypropylene matrix material is 31.0, and vertical combustion is the V-0 level.
Embodiment 22
Removing used polyolefine in the present embodiment is new LDPE (film grade), and other is identical with embodiment 6.
The LOI of gained halogen-free expanded flame-retardant new LDPE (film grade) matrix material is 28.6, and vertical combustion is the V-0 level.
Embodiment 23
Removing used polyolefine in the present embodiment is high density polyethylene(HDPE), and other is identical with embodiment 6.
The LOI of gained halogen-free expanded flame-retardant high-density polyethylene composite material is 28.7, and vertical combustion is the V-0 level.
Embodiment 24
Removing used polyolefine in the present embodiment is metallocene catalysed polyethylene, and other is identical with embodiment 6.
The LOI of gained halogen-free expanded flame-retardant metallocene catalysed polyethylene matrix material is 29.0, and vertical combustion is the V-0 level.
Embodiment 25
The content that removes used polyolefine in the present embodiment and be vinyl acetate is 5% vinyl acetate (EVA5), and other is identical with embodiment 6.
The LOI of gained halogen-free expanded flame-retardant EVA5 matrix material is 29.3, and vertical combustion is the V-0 level
Embodiment 26
The content that removes used polyolefine in the present embodiment and be vinyl acetate is 18% vinyl acetate (EVA18), and other is identical with embodiment 6.
The LOI of gained halogen-free expanded flame-retardant EVA18 matrix material is 31.1, and vertical combustion is the V-0 level.
Embodiment 27
The content that removes used polyolefine in the present embodiment and be vinyl acetate is 28% vinyl acetate (EVA28), and other is identical with embodiment 6.
The LOI of gained halogen-free expanded flame-retardant EVA28 matrix material is 33.1, and vertical combustion is the V-0 level.
Embodiment 28
The content that removes used polyolefine in the present embodiment and be vinyl acetate is 45% vinyl acetate (EVA45), and other is identical with embodiment 6;
The LOI of gained halogen-free expanded flame-retardant EVA45 matrix material is 35.1, and vertical combustion is the V-0 level.
Embodiment 29
Removing used polyolefine in the present embodiment is long glass fiber reinforced polypropylene (content of long glass fibres is 40%), and other is identical with embodiment 6.
The LOI of gained halogen-free expanded flame-retardant long glass fiber reinforced polypropylene material is 37.9, and vertical combustion is the V-0 level.
Embodiment 30
Removing used polyolefine in the present embodiment is long glass fiber reinforced polypropylene (content of long glass fibres is 15%), and other is identical with embodiment 6.
The LOI of gained halogen-free expanded flame-retardant long glass fiber reinforced polypropylene material is 37.0, and vertical combustion is the V-0 level.
Embodiment 31
Removing used polyolefine in the present embodiment is long glass fiber reinforced polypropylene (content of long glass fibres is 40%), and other is identical with embodiment 13;
The LOI of gained halogen-free expanded flame-retardant long glass fiber reinforced polypropylene material is 30.7, and vertical combustion is the V-0 level.
Embodiment 32
Removing used polyolefine in the present embodiment is long glass fiber reinforced polypropylene (content of long glass fibres is 15%), and other is identical with embodiment 13;
The LOI of gained halogen-free expanded flame-retardant long glass fiber reinforced polypropylene material is 30.2, and vertical combustion is the V-0 level.
Embodiment 33
The oxidation inhibitor of 30% coupling agent, ammonium polyphosphate, triazines oligopolymer, fire retarding synergist polynite (proportioning between them is identical with embodiment 6), 69% polypropylene and 1.0% is mixed, add in the twin screw extruder, continuous fusion is sheared mixing back extruding pelletization, preparation halogen-free expanded flame-retardant polypropylene masterbatch.
Get 25% long glass fiber reinforced polypropylene masterbatch (long glass fibres content is 20%) and 66.7% polypropylene flame redardant masterbatch, 8.3% polypropylene mixes through high-speed stirring, is mixed with halogen-free flame-retardant long glass fiber reinforced polypropylene composite material.
The content of the long glass fibres in the halogen-free flame-retardant long glass fiber reinforced polypropylene composite material of present embodiment preparation is 5%, and the content of expansion type flame retardant, coupling agent, fire retarding synergist and oxidation inhibitor is 20%; The LOI of gained halogen-free flame-retardant long glass fiber reinforced polypropylene composite material is 32.0, and vertical combustion is the V-0 level.
Embodiment 34
The oxidation inhibitor of 50% coupling agent, ammonium polyphosphate, triazines oligopolymer, fire retarding synergist polynite (proportioning between them is identical with embodiment 6), 49% acrylic resin and 1.0% is mixed, add in the twin screw extruder, continuous fusion is sheared mixing back extruding pelletization, preparation halogen-free expanded flame-retardant polypropylene masterbatch;
Get 25% long glass fiber reinforced polypropylene masterbatch (long glass fibres content is 20%) and 50% polypropylene flame redardant masterbatch, 25% polypropylene mixes through high-speed stirring, is mixed with halogen-free flame-retardant long glass fiber reinforced polypropylene composite material
The content of the long glass fibres in the halogen-free flame-retardant long glass fiber reinforced polypropylene composite material of present embodiment preparation is 5%, and the content of expansion type flame retardant, coupling agent, fire retarding synergist and oxidation inhibitor is 25%.The LOI of gained halogen-free flame-retardant long glass fiber reinforced polypropylene composite material is 36.2, and vertical combustion is the V-0 level.
Embodiment 35
The oxidation inhibitor of 60% coupling agent, ammonium polyphosphate, triazines oligopolymer, fire retarding synergist polynite (proportioning between them is identical with embodiment 6), 39% acrylic resin and 1.0% is mixed, add in the twin screw extruder, continuous fusion is sheared mixing back extruding pelletization, preparation halogen-free expanded flame-retardant polypropylene masterbatch;
Get 25% long glass fiber reinforced polypropylene masterbatch (long glass fibres content is 20%) and 30% polypropylene flame redardant masterbatch, 45% polypropylene mixes through high-speed stirring, is mixed with halogen-free flame-retardant long glass fiber reinforced polypropylene composite material
The content of the long glass fibres in the halogen-free flame-retardant long glass fiber reinforced polypropylene composite material of present embodiment preparation is 5%, and the content of expansion type flame retardant, coupling agent, fire retarding synergist and oxidation inhibitor is 18%.The LOI of gained halogen-free flame-retardant long glass fiber reinforced polypropylene composite material is 30.1, and vertical combustion is the V-0 level.
Embodiment 36
The oxidation inhibitor of 80% coupling agent, ammonium polyphosphate, triazines oligopolymer, fire retarding synergist polynite (proportioning between them is identical with embodiment 6), 19% acrylic resin and 1.0% is mixed, add in the twin screw extruder, continuous fusion is sheared mixing back extruding pelletization, preparation halogen-free expanded flame-retardant polypropylene masterbatch;
Get 25% long glass fiber reinforced polypropylene masterbatch (long glass fibres content is 40%) and 25% polypropylene flame redardant masterbatch, 50% polypropylene mixes through high-speed stirring, is mixed with halogen-free flame-retardant long glass fiber reinforced polypropylene composite material
The content of the long glass fibres in the halogen-free flame-retardant long glass fiber reinforced polypropylene composite material of present embodiment preparation is 10%, and the content of expansion type flame retardant, coupling agent, fire retarding synergist and oxidation inhibitor is 20%.The gained halogen-free flame-retardant long glass fiber is 32.3 at the LOI of polypropylene composite material, and vertical combustion is the V-0 level.
Embodiment 37
The oxidation inhibitor of 90% coupling agent, ammonium polyphosphate, triazines oligopolymer, fire retarding synergist polynite (proportioning between them is identical with embodiment 6), 9% acrylic resin and 1.0% is mixed, add in the twin screw extruder, continuous fusion is sheared mixing back extruding pelletization, preparation halogen-free expanded flame-retardant polypropylene masterbatch;
Get 50% long glass fiber reinforced polypropylene masterbatch (long glass fibres content is 40%) and 22.2% polypropylene flame redardant masterbatch, 27.8% polypropylene mixes through high-speed stirring, is mixed with halogen-free flame-retardant long glass fiber reinforced polypropylene composite material
The content of the long glass fibres in the halogen-free flame-retardant long glass fiber reinforced polypropylene composite material of present embodiment preparation is 20%, and the content of expansion type flame retardant, coupling agent, fire retarding synergist and oxidation inhibitor is 20%.The gained halogen-free flame-retardant long glass fiber is 32.6 at the LOI of polypropylene composite material, and vertical combustion is the V-0 level.
Embodiment 38
The oxidation inhibitor of 80% coupling agent, ammonium polyphosphate, triazines oligopolymer, fire retarding synergist polynite (proportioning between them is identical with embodiment 6), 9% acrylic resin and 1.0% is mixed, add in the twin screw extruder, continuous fusion is sheared mixing back extruding pelletization, preparation halogen-free expanded flame-retardant polypropylene masterbatch;
Get 75% long glass fiber reinforced polypropylene masterbatch (long glass fibres content is 40%) and 25% polypropylene flame redardant masterbatch, mix, be mixed with halogen-free flame-retardant long glass fiber reinforced polypropylene composite material through high-speed stirring
The content of the long glass fibres in the halogen-free flame-retardant long glass fiber reinforced polypropylene composite material of present embodiment preparation is 30%, and the content of expansion type flame retardant, coupling agent, fire retarding synergist and oxidation inhibitor is 20%.The gained halogen-free flame-retardant long glass fiber is 32.8 at the LOI of polypropylene composite material, and vertical combustion is the V-0 level.
Embodiment 39
80% coupling agent, ammonium polyphosphate, triazines oligopolymer, fire retarding synergist polynite (proportioning between them is identical with embodiment 6), 9% acrylic resin and 1.0% oxidation inhibitor mix, add in the twin screw extruder, continuous fusion is sheared mixing back extruding pelletization, preparation halogen-free expanded flame-retardant polypropylene masterbatch;
Get 67% long glass fiber reinforced polypropylene masterbatch (long glass fibres content is 60%) and 25% polypropylene flame redardant masterbatch, 8% polypropylene mixes through high-speed stirring, is mixed with halogen-free flame-retardant long glass fiber reinforced polypropylene composite material
The content of the long glass fibres in the halogen-free flame-retardant long glass fiber reinforced polypropylene composite material of present embodiment preparation is 40%, and the content of expansion type flame retardant, coupling agent, fire retarding synergist and oxidation inhibitor is 20%.The gained halogen-free flame-retardant long glass fiber is 33.3 at the LOI of polypropylene composite material, and vertical combustion is the V-0 level.
Embodiment 40
The structure of used triazines oligopolymer is in the present embodiment:
M1=0, m2=1, R=(CH
2)
2, n=2～50, other is identical with embodiment 33.
The LOI of gained halogen-free flame-retardant long glass fiber reinforced polypropylene composite material is 31.3, and vertical combustion is the V-0 level.
Embodiment 41
The content of long glass fibres is 40% in the halogen-free flame-retardant long glass fiber reinforced polypropylene composite material that present embodiment is prepared as different from Example 40, and other is identical with embodiment 40.
The LOI of gained halogen-free flame-retardant long glass fiber reinforced polypropylene composite material is 32.5, and vertical combustion is the V-0 level.
Embodiment 42
The structure of the triazines oligopolymer that present embodiment is used is:
M1=0, m2=1, R=(CH
2)
2, n=2～50, other is identical with embodiment 33.
The LOI of gained halogen-free flame-retardant long glass fiber reinforced polypropylene composite material is 31.7, and vertical combustion is the V-0 level.
Embodiment 43
The content of long glass fibres is 40% in the halogen-free flame-retardant long glass fiber reinforced polypropylene composite material that present embodiment is prepared as different from Example 42, and other is identical with embodiment 42.
The LOI of gained halogen-free flame-retardant long glass fiber reinforced polypropylene composite material is 32.8, and vertical combustion is the V-0 level.
Embodiment 44
The structure of the triazines oligopolymer that present embodiment is used is:
M1=0, m2=1, R=(CH
2)
2, m=7, X is
Y is a piperazine, n=2～50, and other is identical with embodiment 33.
The LOI of gained halogen-free flame-retardant long glass fiber reinforced polypropylene composite material is 32.1, and vertical combustion is the V-0 level.
Embodiment 45
The content of long glass fibres is 40% in the halogen-free flame-retardant long glass fiber reinforced polypropylene composite material that present embodiment is prepared as different from Example 44, and other is identical with embodiment 44.
The LOI of gained halogen-free flame-retardant long glass fiber reinforced polypropylene composite material is 33.1, and vertical combustion is the V-0 level.
Embodiment 46
Present embodiment is m=15 as different from Example 44, and other is identical with embodiment 44.
The LOI of gained halogen-free flame-retardant long glass fiber reinforced polypropylene composite material is 32.1, and vertical combustion is the V-0 level.
Embodiment 47
The content of long glass fibres is 40% in the halogen-free flame-retardant long glass fiber reinforced polypropylene composite material that present embodiment is prepared as different from Example 46, and other is identical with embodiment 46.
The LOI of gained halogen-free flame-retardant long glass fiber reinforced polypropylene composite material is 33.2, and vertical combustion is the V-0 level.
Claims (9)
1, a kind of halogen-free expansion type flame-proof polyolefin composite material, this matrix material are by following prescription, form through melt blending:
Polyolefine 70～84%
Halogen-free expansion fire retardant 15～25%
Fire retarding synergist 0～5%
Coupling agent 0～2%
Oxidation inhibitor 0～1%,
The percentage ratio of each material is weight percentage, and described polyolefine is any in polypropylene, long glass fiber reinforced polypropylene, polyethylene or the ethylene-vinyl acetate copolymer.
2, halogen-free expansion type flame-proof polyolefin composite material according to claim 1, halogen-free expansion fire retardant described in this matrix material is that 1～5: 1 ammonium polyphosphate and triazines oligopolymer are formed by mass ratio, and wherein the general structure of triazines oligopolymer is:
R in the formula
1=-NH
2Or-NHCH
2CH
2OH, R
2=-NHCH
2CH
2NHCH
2CH
2NH-,-NHCH
2CH
2NHCH
2CH
2NHCH
2CH
2NH-or-NHCH
2CH
2NHCH
2CH
2NHCH
2CH
2NHCH
2CH
2Among the NH-any one, n=2-50.
3, halogen-free expansion type flame-proof polyolefin composite material according to claim 1, the polyolefine of this matrix material is a long glass fiber reinforced polypropylene, the halogen-free expansion fire retardant that it added is that 1～5: 1 ammonium polyphosphate and triazines oligopolymer are formed by mass ratio, and wherein the general structure of triazines oligopolymer is:
Or
In any, m in the formula
1=0 or 1; m
2=1 or 2; R=(CH
2)
N1Or C
6H
4, n1=1～6; X=-NHR
1NH-or
Or
R wherein
1=(CH
2)
N2Or phenyl ring, n2=2～6; Y represent piperazine or
Or
M=1～15, n=2-50.
4, according to claim 1 or 2 or 3 described halogen-free expansion type flame-proof polyolefin composite materials, the fire retarding synergist described in this matrix material is any in polynite, organic modification montmonrillonite, molecular sieve, wilkinite, rectorite leng, sepiolite, diatomite, metal oxide, metal-salt or the two oxyhydroxide.
5, according to claim 1 or 2 or 3 described halogen-free expansion type flame-proof polyolefin composite materials, the coupling agent described in this matrix material is any in aluminate coupling agent, the silane coupling agent.
6, halogen-free expansion type flame-proof polyolefin composite material according to claim 4, the coupling agent described in this matrix material are any in aluminate coupling agent, the silane coupling agent.
7, according to claim 1 or 2 or 3 described halogen-free expansion type flame-proof polyolefin composite materials, the oxidation inhibitor described in this matrix material is by mass ratio 1～4: the composite antioxidant that 1 antioxidant 1010 and oxidation inhibitor 168 are formed.
8, halogen-free expansion type flame-proof polyolefin composite material according to claim 4, the oxidation inhibitor described in this matrix material are by mass ratio 1～4: the composite antioxidant that 1 antioxidant 1010 and oxidation inhibitor 168 are formed.
9, halogen-free expansion type flame-proof polyolefin composite material according to claim 6, the oxidation inhibitor described in this matrix material are by mass ratio 1～4: the composite antioxidant that 1 antioxidant 1010 and oxidation inhibitor 168 are formed.
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| CNA2009100586248A CN101508809A (en) | 2009-03-18 | 2009-03-18 | Halogen-free expansion type flame-proof polyolefin composite material |
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|---|---|---|---|
| CNA2009100586248A CN101508809A (en) | 2009-03-18 | 2009-03-18 | Halogen-free expansion type flame-proof polyolefin composite material |
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| CN107434878B (en) * | 2017-08-17 | 2020-07-24 | 会通新材料股份有限公司 | High glow wire, boiling-resistant and flame-retardant polypropylene composite material and preparation method thereof |
| CN108219280A (en) * | 2018-02-05 | 2018-06-29 | 厦门塑时代新材料有限公司 | A kind of halogen-free polypropylene flame redardant and preparation method thereof |
| CN109082010A (en) * | 2018-07-23 | 2018-12-25 | 武汉理工大学 | A kind of halogen-free expanded flame-retardant fibre reinforced acrylic resin composite material and preparation method |
| CN110951161A (en) * | 2019-12-17 | 2020-04-03 | 上海大学 | Flame-retardant thermoplastic polymer environment-friendly composite material and preparation method thereof |
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