CN102276899B - Magnesium hydroxide flame-retardant composite material and preparation method thereof - Google Patents
Magnesium hydroxide flame-retardant composite material and preparation method thereof Download PDFInfo
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- CN102276899B CN102276899B CN 201110200646 CN201110200646A CN102276899B CN 102276899 B CN102276899 B CN 102276899B CN 201110200646 CN201110200646 CN 201110200646 CN 201110200646 A CN201110200646 A CN 201110200646A CN 102276899 B CN102276899 B CN 102276899B
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Abstract
The invention discloses a magnesium hydroxide flame-retardant composite material and a preparation method thereof. The flame-retardant material comprises the following components in parts by weight: 20-100 parts of high polymer, 40-80 parts of magnesium hydroxide and 5-20 parts of toughening agent, wherein the high polymer is one or more of polyethylene, polyvinyl chloride, polypropylene, polystyrene, polyamide, polyformaldehyde, rubber or nylon; and the toughening agent is one or more of dioctyl phthalate, poly(ethylene-octene) elastomer, tricresyl phosphate, styrene-butadiene-styrene block copolymer, hydrogenated styrene-butadiene-styrene block copolymer or styrene-isoprene-styrene block copolymer. Practice proves that the magnesium hydroxide flame-retardant composite material has the advantages of strong shock resistance, high tensile strength and high oxygen index. The preparation method of the composite material is simple in operation, has low cost and high production efficiency,and can be widely used in the field of engineering plastics.
Description
Technical field
The invention belongs to the inorganic anti-flaming material technical field, specifically refer to a kind of magnesium hydroxide composite flame retardant material and preparation method thereof.
Background technology
At present, the fire retardant that adopts on the market mostly is Halogen or phosphorous compound greatly, and this class material has cheap, the characteristics of actual good flame retardation effect, but when burning, can give out obnoxious flavour, thus personal damage and environmental pollution caused.Because the hazardness of halogen compounds is progressively by cognitive and draw attention, the environmental protection development trend will be impelled increasing human consumer to use halogen, low toxicity, press down the inorganic combustion inhibitor of cigarette.Study and use more novel inorganic fire retardant at home and abroad, mainly be magnesium hydroxide and aluminium hydroxide and antimony peroxide etc., because aluminium hydroxide can be finished dehydration reaction in 245～320 ℃ of scopes, absorb latent heat and reduce temperature, therefore its effective use range is lower, is applicable to resin such as polyethylene (PE), polyvinyl chloride (PVC), Resins, epoxy, unsaturated polyester, acrylic resin and AB S resin etc. that processing temperature is lower.And magnesium hydroxide has that decomposition temperature is higher, thermal stability good, the nontoxic characteristics such as cigarette that press down, be fit to be prepared into the inorganic combustion inhibitor of polymkeric substance, especially sheet or fibrous magnesium hydroxide also have multiple functions such as obstruct, antiacid and filling, and extremely people pay attention in recent years.Compare with the most salable aluminium hydroxide, magnesium hydroxide polymer inorganic fire retardant in the fire retardancy of thermostability, deacidification ability, suitable polymkeric substance, press down aspect such as cigarette ability and be much better than aluminium hydroxide, be a kind of worth inorganic combustion inhibitor of exploitation energetically, and it have the trend of further replacement aluminium hydroxide.
Before the present invention, application number is that the Chinese patent of 200610039374.X discloses a kind of thermoplastic resin/magnesium hydroxide high-performance refractory composites and production method thereof.Thermoplastic resin/magnesium hydroxide high-performance refractory composites is mainly formed by thermoplastic resin with through the magnesium hydroxide of calcination process, also can comprise oxidation inhibitor, lubricant in addition, and typical thermoplastic resin is nylon.The matrix material of this inventive method preparation has higher mechanical property and good flame retardant property, but this invention only is confined to thermoplastic resin nylon flame-proof composite material and preparation method thereof, can not be suitable for other matrixes.
Application number a kind of magnesium hydrate halogen-free flame resistance polyethylene composite material that has been 02124390.5 Chinese state patent disclosure is made up of following component and content thereof in weight part: polyethylene 100; Magnesium hydroxide 30～330; Elastomerics 50～120; Coupling agent 0.3～5.0; Interface modifier 0.2～6.0; Dispersion agent 0.2～5.0; Synergistic agent 0.1～2.0; Oxidation inhibitor 0.1～2.0; Described magnesium hydroxide is natural crystal powder or synthetic magnesium hydroxide, and its granularity is generally 11 μ m～100 μ m; Described elastomerics is ethylene-propylene rubber(EPR), terpolymer EP rubber, ethylene-octene copolymer, ethene-vinyl acetate vinegar multipolymer etc.Matrix material of the present invention has high tenacity and high-intensity magnesium hydroxide flame retardant composite polyethylene material simultaneously: vertical combustion FV-0 level, tensile strength 18.0MPa, shock strength 423.5J/m, elongation at break 120.8%.But this patented method is only applicable to prepare the polyethylene composite flame-proof material, can not be suitable for other matrixes, and need the adding elastomerics to improve composite property, and cost is higher.
Summary of the invention
An object of the present invention is to provide the magnesium hydroxide composite flame retardant material that a kind of shock resistance is strong, tensile strength is high, oxygen index is high.
For achieving the above object, magnesium hydroxide composite flame retardant material of the present invention, it comprises the component of following weight part: 20～100 parts of superpolymer, 40～80 parts of magnesium hydroxides, 5～20 parts of toughner, wherein, described superpolymer is one or more in polyethylene, polyvinyl chloride, polypropylene, polystyrene, polymeric amide, polyoxymethylene, rubber or the nylon; Described toughner is one or more in dioctyl phthalate (DOP), polyethylene octene elastomerics, phosphoric acid trimethylbenzene phenolic ester, styrene-butadiene-styrene block copolymer, hydrogenated styrene-butadiene-styrene block copolymers or the styrene isoprene styrene block copolymer (SIS).
Further, described magnesium hydroxide composite flame retardant material comprises the component of following weight part: 5～30 parts of polyethylene, 10～50 parts of polystyrene, 5～20 parts of polypropylene, 60～70 parts of magnesium hydroxides, 1～5 part of dioctyl phthalate (DOP), 2～10 parts on polyethylene octene elastomerics, 2～5 parts of phosphoric acid trimethylbenzene phenolic esters.
Further again, also contain weight part in the described magnesium hydroxide composite flame retardant material and be 1～10 part fire retarding synergist, described fire retarding synergist is one or more in aluminium hydroxide, trimeric cyanamide, ammonium polyphosphate, tetramethylolmethane, weisspiessglanz, organic silicide, red phosphorus, zinc oxide, zinc borate, silicon-dioxide or the graphite.
Another object of the present invention is exactly the preparation method that a kind of magnesium hydroxide composite flame retardant material will be provided, and this preparation method's technology is simple, with low cost, be easy to promote.
For achieving the above object, the preparation method of magnesium hydroxide composite flame retardant material of the present invention may further comprise the steps:
1) superpolymer, magnesium hydroxide, toughner are mixed by described weight ratio after, join in the forcing machine blend and extrude;
2) with carrying out granulation after the described extruded material cooling, obtain composite material granular;
3) with gained particle constant temperature drying 18～30h, obtain magnesium hydroxide composite flame retardant material.
Further, in the described step 3), the control bake out temperature is 60～100 ℃.
It is as follows that each composition of magnesium hydroxide composite flame retardant material of the present invention arranges principle:
When superpolymer reaches 25% when above as the magnesium hydroxide loading level in the fire retardant material of matrix, matrix material can be made fire retardant material and use, and good smoke elimination performance is arranged, and can not cause secondary pollution.Along with the magnesium hydroxide loading level increases, the carbon residue amount increases, and the flame retardant properties of material is improved, and when the charge of filling out magnesium hydroxide reached 80%, matrix material can be made nonflammable material and use.But, can influence the mechanical property of matrix material when loading level is excessive.Because, ordinary hydrogen magnesium oxide is the very strong mineral compound of a kind of polarity, possess hydrophilic property, not good enough with the avidity of oil loving polymer molecule, crystal grain trends towards secondary aggregation, agglomeration takes place, simultaneously, the interface of magnesium hydroxide and polymkeric substance produces the space, and both consistencies are also poor, cause magnesium hydroxide to be reunited therein, and the mechanical property of polymer materials also can reduce.If adopt tensio-active agent that magnesium hydroxide is carried out surface modification, particularly adopt the flake magnesium hydroxide after the modification to do fire retardant, can effectively improve flame retardant resistance and the smoke elimination performance of composite flame-proof material, and the flame-proof composite material that can obtain to have better mechanical property.
Toughner is to have the auxiliary agent that reduces matrix material fragility and improve the matrix material shock resistance.Contain on the molecular chain of toughner can with matrix resin reactive activity group, it can form network structure, increase a part of flexible chain, in composite flame-proof material, add toughner and can effectively reduce matrix material fragility and improve the matrix material shock resistance, improve the mechanical property of composite flame-proof material.
In order further to improve the performance of composite flame-proof material, can in raw material, add one or more fire retarding synergists, be used for optimizing composite flame-proof material prevention, delay or stop the ability of propagation of flame.After in fire retardant material, having added two or more fire retardants, this two or more fire retardant acting in conjunction effects adding and better effects if than one-component.In the magnesium hydroxide flame retardant polymkeric substance, add a small amount of fire retarding synergist, can significantly improve the flame retardant effect of composite flame-retardant agent when can effectively reduce the magnesium hydroxide loading level, the mechanical property of material is also played tangible improvement effect.
Beneficial effect of the present invention is: by adopting superpolymer as matrix, to wherein filling magnesium hydroxide as fire retardant, and add a certain amount of toughner and reduce matrix material fragility and improve the matrix material shock resistance, thereby the shock resistance that realizes magnesium hydroxide composite flame retardant material of the present invention is strong, tensile strength, excellent properties that oxygen index is high, and preparation method of the present invention is simple to operate, cost is low, production efficiency is high, can be widely used in the engineering plastics field.
Embodiment
Below in conjunction with specific examples magnesium hydroxide composite flame retardant material of the present invention is described in further detail:
Embodiment 1:
A kind of magnesium hydroxide composite flame retardant material comprises following parts by weight of component: 70 parts of polypropylenes, 40 parts of modified magnesium hydroxides, 15 parts on polyethylene octene elastomerics.
Embodiment 2
A kind of magnesium hydroxide composite flame retardant material comprises following parts by weight of component: 100 parts of polyvinyl chloride, 45 parts of magnesium hydroxides, 10 parts of dioctyl phthalate (DOP)s, 10 parts of phosphoric acid trimethylbenzene phenolic esters, 1 part in zinc oxide.
Embodiment 3
A kind of magnesium hydroxide composite flame retardant material comprises following parts by weight of component: 40 parts of 60 parts of polypropylene, crystal formation modified magnesium hydroxides in the form of sheets, 10 parts of dioctyl phthalate (DOP)s, 10 parts on polyethylene octene elastomerics, 1 part in zinc oxide, 2 parts of zinc borates.
Embodiment 4
A kind of magnesium hydroxide composite flame retardant material comprises following parts by weight of component: 20 parts of polyethylene, 50 parts of polystyrene, 20 parts of polypropylene, 70 parts of magnesium hydroxides, 5 parts of dioctyl phthalate (DOP)s, 5 parts of phosphoric acid trimethylbenzene phenolic esters, 10 parts on polyethylene octene elastomerics.
Embodiment 5
A kind of magnesium hydroxide composite flame retardant material comprises following parts by weight of component: 30 parts of polyethylene, 10 parts of polystyrene, 20 parts of polypropylene, 60 parts of magnesium hydroxides, 1 part of dioctyl phthalate (DOP), 2 parts of phosphoric acid trimethylbenzene phenolic esters, 2 parts on polyethylene octene elastomerics, 10 parts in aluminium hydroxide.
Embodiment 6
A kind of magnesium hydroxide composite flame retardant material comprises following parts by weight of component: 60 parts of polypropylene, 43.6 parts of magnesium hydroxides, 20 parts on polyethylene octene elastomerics, 4.8 parts of ammonium polyphosphates, 1.6 parts of tetramethylolmethanes.
Embodiment 7
A kind of magnesium hydroxide composite flame retardant material comprises following parts by weight of component: 60 parts of nylon, 20 parts of rubber, 80 parts of magnesium hydroxides, 5 parts of dioctyl phthalate (DOP)s, 10 parts of styrene isoprene styrene block copolymer (SIS), 5 parts of weisspiessglanzs.
Embodiment 8
A kind of magnesium hydroxide composite flame retardant material comprises following parts by weight of component: 55 parts of polymeric amide, 25 parts of polyvinyl chloride, 60 parts of crystal formation magnesium hydroxides in the form of sheets, 20 parts of styrene isoprene styrene block copolymer (SIS), 2 parts of organic silicides, 3 parts in zinc oxide.
Its preparation method of above-described embodiment is:
1) each component is even by described mixed, join in the forcing machine blend and extrude;
2) described extruded material is put into the tablets press granulation after the water-bath cooling, obtain composite material granular;
3) with the particle constant temperature drying 18～30h under 60～100 ℃ of conditions that obtains, obtain magnesium hydroxide composite flame retardant material.
Mechanical property and flame retardant properties to gained embodiment product detect, and the gained detected result sees Table 1.
Table 1: the mechanical property of embodiment product and flame retardant resistance data sheet.
Claims (2)
1. magnesium hydroxide composite flame retardant material, it is characterized in that: it comprises the component of following weight part:
5 ~ 30 parts of polyethylene, 10 ~ 50 parts of polystyrene, 5 ~ 20 parts of polypropylene, 60 ~ 70 parts of magnesium hydroxides, 1 ~ 5 part of dioctyl phthalate (DOP), 2 ~ 10 parts on polyethylene octene elastomerics, 2 ~ 5 parts of phosphoric acid trimethylbenzene phenolic esters; It also contains and comprises that weight part is 1 ~ 10 part fire retarding synergist, wherein, described fire retarding synergist is one or more in aluminium hydroxide, trimeric cyanamide, ammonium polyphosphate, tetramethylolmethane, weisspiessglanz, organic silicide, zinc oxide, zinc borate, silicon-dioxide or the graphite, its preparation method may further comprise the steps:
1) above-mentioned each components in weight portion is mixed after, join in the forcing machine blend and extrude;
2) with carrying out granulation after the described extruded material cooling, obtain composite material granular;
3) with the particle constant temperature drying 18 ~ 30h of gained, obtain magnesium hydroxide composite flame retardant material.
2. according to the described magnesium hydroxide composite flame retardant material of claim 1, it is characterized in that: in the described step 3) of its preparation method, the control bake out temperature is 60 ~ 100 ℃.
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| CN1209405C (en) * | 2002-06-21 | 2005-07-06 | 中国科学院化学研究所 | Magnetsium hydroxide halogen-free polythene flame redardant composite material |
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