CN106496951B - A kind of halogen-free flame-retardant composite material and preparation method thereof - Google Patents
A kind of halogen-free flame-retardant composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of halogen-free flame-retardant composite materials, include the component of following parts by weight：1 ~ 4 part of modified 25 ~ 40 parts of powdered rice hulls, 27 ~ 46 parts of modified bagasse, 10 ~ 20 parts of p-diethynylbenzene, 5 ~ 10 parts of triethyl borate, 80 ~ 100 parts of organic silica resin, 10 ~ 20 parts of magnesium hydroxide, 10 ~ 20 parts of aluminium hydroxide and coupling agent etc.；Preparation method is：（1）P-diethynylbenzene, triethyl borate and organic silica resin are weighed by formula, is melted；（2）Polyacetylene benzene polymer with magnesium hydroxide, aluminium hydroxide, antioxidant and coupling agent is mixed, is placed in kneading machine and melts, then by polytetrafluoroethylene (PTFE), is placed in kneading machine, is melted；（2）Granular material and lubricant are placed in vulcanizing press again, the hot pressing under 8 ~ 15MPa obtains halogen-free flame-retardant composite material.The present invention improves the flame retardant effect and mechanical property of composite material by generating organic silica resin.
Description
Technical field
The present invention relates to field of compound material, and in particular to a kind of halogen-free flame-retardant composite material and preparation method thereof.
Background technology
High molecular material is widely used in various fields, but easy firing and molten drop during its chance fire, it is therefore necessary to pass through
Fire retardant is added in improve its inflammability, there are many types for fire retardant, are divided into additive flame retardant and response type by application method
Fire retardant.
Additive flame retardant is added in polymer by mechanical mix techniques, and polymer is made to have anti-flammability, mesh
Preceding additive flame retardant mainly has organic fire-retardant and inorganic combustion inhibitor.Organic is using bromine system, machine nitrogen system of phosphorus nitrogen system as representative
Some fire retardants, inorganic mainly antimony oxide, magnesium hydroxide, magnesium hydroxide etc. flame-retardant systems.
Reactive flame retardant is then to participate in polymerisation, therefore polymer is made to contain flame-retardant composition in itself as a kind of monomer
's.
For a long time, additive flame retardant is always the first choice of the flame retardant composite material mode of production since its is simple for process,
Wherein halogenated flame retardant is important one of fire retardant kind always, discharges toxic smog when burning however, as it, easily causes
Secondary hazards bring very big difficulty to putting out a fire, escaping and resuming work.And high molecular material will reach certain flame retardant effect,
The additive amount of required magnesium hydroxide or aluminium hydroxide is larger, the processing forming of composite material can not only be made to be deteriorated, but also can lead
The mechanical property of basis material is caused to decline to a great extent.
Invention content
For above-mentioned deficiency of the prior art, the present invention provides a kind of Halogen composite material and preparation method thereof, can have
Effect solves fire retardant to the mechanical strength of composite material and the influence of impact strength.
To solve the technical issues of above-mentioned, the technical solution adopted by the present invention is：
A kind of halogen-free flame-retardant composite material includes the component of following weight：
Modified 25 ~ 40 parts of powdered rice hulls, 27 ~ 46 parts of modified bagasse, 10 ~ 20 parts of p-diethynylbenzene, triethyl borate 5 ~
10 parts, it is 80 ~ 100 parts of organic silica resin, 10 ~ 20 parts of magnesium hydroxide, 10 ~ 20 parts of aluminium hydroxide, 1 ~ 4 part of coupling agent, anti-oxidant
1 ~ 5 part of 1 ~ 5 part of agent, 5 ~ 10 parts of antiseptic, 1 ~ 5 part of lubricant and polytetrafluoroethylene (PTFE)；
The modified powdered rice hulls are prepared by the following method to obtain：
Rice husk is added in culture solution, glycine-HCI buffer solution is added in into culture solution, pH to 3.0 is adjusted, adds
Whiterot fungi reacts 36 ~ 50h at 30 ~ 35 DEG C, takes out rice husk, and drying is crushed to grain size as 50 mesh, obtains modified rice husk
The mass ratio of powder, wherein rice husk, culture solution and whiterot fungi is 1:11:5；
The modified bagasse is prepared by the following method to obtain：
Bagasse is added in culture solution, glycine-HCI buffer solution is added in into culture solution, adjusts pH to 3.0, then add
Enter whiterot fungi, 36 ~ 45h is reacted at 30 ~ 35 DEG C, take out bagasse, drying is crushed to grain size as 50 mesh, is modified
The mass ratio of bagasse, wherein bagasse, culture solution and whiterot fungi is 1:11:5；
Organic silica resin is prepared by the following method to obtain：
（One）Epoxy resin and isopropyl acetate are mixed, stirring and dissolving, and chlorosilane is slowly added in whipping process
And benzoyl peroxide, under the conditions of nitrogen atmosphere, 90 ~ 110 DEG C, 1 ~ 2h is stirred to react, obtains reactant；Wherein asphalt mixtures modified by epoxy resin
Fat, isopropyl acetate, chlorosilane and initiator weight ratio be 1 ~ 5:3~10:1~5:0.02~0.05；
（Two）By step（One）Middle gained reactant is added in absolute ethyl alcohol and is precipitated, and is filtered, is obtained sediment I, sediment I is adopted
With 50% ~ 95% 20 ~ 30h of ethanolic extraction, homopolymer is removed, sediment II is obtained, sediment II is dried in vacuo at room temperature, must have
Machine silica resin.
Further, a kind of halogen-free flame-retardant composite material includes the component of following parts by weight：Modified 36 parts of powdered rice hulls change
42 parts of bagasse of property, 14 parts of p-diethynylbenzene, 8 parts of triethyl borate, 82 parts of organic silica resin, 14 parts of magnesium hydroxide, hydrogen
1 part of 15 parts of aluminium oxide, 2 parts of coupling agent, 2 parts of antioxidant, 10 parts of antiseptic, 1 part of lubricant and polytetrafluoroethylene (PTFE).
Further, the constituent content of culture solution is：2 parts of dusty yeast, vitamin B10.4 part, it is 1.5 parts of glucose, solvable
1.5 parts of starch of property, KH2PO40.2 part and MgSO4·7H2O0.5 parts.
Further, epoxy resin and isopropyl acetate are mixed, stirring and dissolving, and chlorine is slowly added in whipping process
Silane and initiator under the conditions of nitrogen atmosphere, 110 DEG C, are stirred to react 1.6h.
Further, coupling agent is silane resin acceptor kh-550, cumyl hydroperoxide, Aluminate or ethylene-acrylic acid
Methyl esters.
Further, antiseptic is zinc oxide, copper oxide, ammonium dihydrogen phosphate or lithium carbonate.
Further, lubricant is hard cholic acid zinc, ethylene bis stearic acid amide, lead stearate, polyethylene wax, paraffin or oxygen
Change polyethylene wax.
Further, antioxidant for butylated hydroxy anisole, dibutyl hydroxy toluene, propylgallate, phytic acid or
Tert-butylhydroquinone.
The preparation method of halogen-free flame-retardant composite material, includes the following steps：
（1）P-diethynylbenzene, triethyl borate and organic silica resin are weighed by formula, is added at 120 ~ 150 DEG C
Heat fusing stirs evenly, and obtains polyacetylene benzene polymer；
（2）By step（1）The polyacetylene benzene polymer of middle gained and modified powdered rice hulls, modified bagasse, magnesium hydroxide, hydrogen
Aluminium oxide, antioxidant, antiseptic and coupling agent mixing, are placed in the open kneading machine that double roller temperature is 170 DEG C ~ 190 DEG C
Middle melting is plasticated 12 ~ 20min, obtains mixing object, then polytetrafluoroethylene (PTFE) is placed in open kneading machine, continue melting plasticate 5 ~
10min obtains sheet material；
（3）By step（2）The sheet material of middle gained is crushed as granular material, then by granular material and lubricant one
With being placed in 195 DEG C ~ 220 DEG C of vulcanizing press, it is compound to obtain halogen-free flameproof by 12 ~ 20min of hot pressing under conditions of 8 ~ 15MPa
Material.
Further, step（3）Described in treatment conditions be：In 195 DEG C of vulcanizing press, in the condition of 8MPa
Lower hot pressing 20min.
Beneficial effects of the present invention are：
（1）Silicon-containing group is imported epoxy resin point by the present invention using reaction-type flame-retarding system by graft copolymerization technology
The positions such as main chain, the side chain of son make epoxy molecule contain flame-retardant composition, form organosilicon epoxy resin, gained organosilicon
Epoxy resin except possess fire-retardant, high heat resistance, it is anti-oxidant, nonflammable the features such as in addition to, also have higher moisture-proof and strand
Flexibility, improve processing performance, mechanical performance, heat resistance of material etc., improve material draws high intensity, shock resistance
Intensity.
（2）Diacetylene-benzene, triethyl borate and organic silica resin are when being heated to 135 DEG C, melt blending, are formed
Polyacetylene benzene polymer containing siloxy and diacetylene on main chain, diacetylene can carry out thermal response and form the net containing conjugation
The cross-linked polymer of network, under the high temperature conditions, the cross-linked polymer containing conjugate network can generate charcoal-ceramic membrane, protect the charcoal under it
Layer prevents material further burning and oxidation；The presence of network structure reduces the combustibility of material, the production quantity of combustible
It is corresponding to reduce, increase charcoal production quantity, promote the flame retardant effect of polymer.
（3）The practical performance that a small amount of magnesium hydroxide and aluminium hydroxide do not interfere with composite material not only is added, may be used also
Cooperative flame retardant effect is formed with organic silica resin, promotes the flame retardant effect of material.
（4）The present invention both has good mechanical performance, has the work turned waste into wealth added with rice husk and bagasse
With reducing production cost；By whiterot fungi treated rice husk and bagasse, lignin is largely degraded, it is ensured that material
The integrality of middle cellulosic structure improves the mechanical performance of composite material entirety.
Specific embodiment
The specific embodiment of the present invention is described below, in order to facilitate understanding by those skilled in the art this hair
It is bright, it should be apparent that the present invention is not limited to the range of specific embodiment, for those skilled in the art,
As long as various change in the spirit and scope of the present invention that appended claim limits and determines, these variations are aobvious and easy
See, all are using the innovation and creation of present inventive concept in the row of protection.
Embodiment 1
A kind of halogen-free flame-retardant composite material includes the component of following parts by weight：Modified 25 parts of powdered rice hulls, modified bagasse 27
Part, 10 parts of p-diethynylbenzene, 5 parts of triethyl borate, organic 100 parts of silica resin, 20 parts of magnesium hydroxide, aluminium hydroxide 20
Part, 4 parts of silane resin acceptor kh-550,3 parts of dibutyl hydroxy toluene, 5 parts of copper oxide, 3 parts of hard cholic acid zinc and polytetrafluoroethylene (PTFE) 2
Part.
Wherein, modified powdered rice hulls are prepared by the following method to obtain：
Rice husk is added in culture solution, glycine-HCI buffer solution is added in into culture solution, pH to 3.0 is adjusted, adds
Whiterot fungi reacts 36h at 32 DEG C, takes out rice husk, and drying is crushed to grain size as 50 mesh, obtains modified powdered rice hulls, wherein
The mass ratio of rice husk, culture solution and whiterot fungi is 1:11:5；
Wherein, the modified bagasse is prepared by the following method to obtain：
Bagasse is added in culture solution, glycine-HCI buffer solution is added in into culture solution, adjusts pH to 3.0, then add
Entering whiterot fungi, 36h is reacted at 32 DEG C, take out bagasse, drying is crushed to grain size as 50 mesh, obtains modified bagasse,
Wherein the mass ratio of bagasse, culture solution and whiterot fungi is 1:11:5；
Above-mentioned culture solution includes the component of following parts by weight：2 parts of dusty yeast, vitamin B10.4 part, 1.5 parts of glucose, can
1.5 parts of soluble starch, KH2PO40.2 part and MgSO4·7H2O0.5 parts；
Wherein, organic silica resin is prepared by the following method to obtain：
（One）Epoxy resin and isopropyl acetate are mixed, stirring and dissolving, and chlorosilane is slowly added in whipping process
And benzoyl peroxide, under the conditions of nitrogen atmosphere, 100 DEG C, 1h is stirred to react, obtains reactant；Its epoxy resin, acetic acid
The weight ratio of isopropyl ester, chlorosilane and benzoyl peroxide is 1:3:1:0.02；
（Two）By step（One）The reactant of middle gained is added in absolute ethyl alcohol and is precipitated, and is filtered, is obtained sediment I, sediment I
Using 50% ethanolic extraction for 24 hours, homopolymer is removed, sediment II is obtained, sediment II is dried in vacuo 10min at room temperature, is obtained
Organic silica resin.
The preparation method of above-mentioned halogen-free flame-retardant composite material, includes the following steps：
（1）P-diethynylbenzene, triethyl borate and organic silica resin are weighed by formula, is heated at 120 DEG C molten
Melt, stir evenly, much acetylene benzene polymer；
（2）By step（1）The polyacetylene benzene polymer of middle gained and modified powdered rice hulls, modified bagasse, magnesium hydroxide, hydrogen
Aluminium oxide, silane resin acceptor kh-550, dibutyl hydroxy toluene and copper oxide mixing are placed in double roller temperature and are 190 DEG C and open
It puts and the 20min that plasticates is melted in formula kneading machine, obtain mixing object, then polytetrafluoroethylene (PTFE) is added in open kneading machine, continue to melt
Plasticate 8min, obtains sheet material；
（3）By step（2）The sheet material of middle gained is crushed as granular material, then by granular material and hard cholic acid zinc
It is placed in together in 220 DEG C of vulcanizing press, the hot pressing 12min under conditions of 10MPa obtains halogen-free flame-retardant composite material.
Embodiment 2
A kind of halogen-free flame-retardant composite material includes the component of following parts by weight：Modified 30 parts of powdered rice hulls, modified bagasse 30
Part, 15 parts of p-diethynylbenzene, 10 parts of triethyl borate, 80 parts of organic silica resin, 10 parts of magnesium hydroxide, aluminium hydroxide 10
Part, 1 part of silane resin acceptor kh-550,2 parts of dibutyl hydroxy toluene, 8 parts of copper oxide, 2 parts of hard cholic acid zinc and polytetrafluoroethylene (PTFE) 1
Part.
Wherein, modified powdered rice hulls are prepared by the following method to obtain：
Rice husk is added in culture solution, glycine-HCI buffer solution is added in into culture solution, pH to 3.0 is adjusted, adds
Whiterot fungi reacts 39h at 32 DEG C, takes out rice husk, and drying is crushed to grain size as 50 mesh, obtains modified powdered rice hulls, wherein
The mass ratio of rice husk, culture solution and whiterot fungi is 1:11:5；
Wherein, modified bagasse is prepared by the following method to obtain：
Bagasse is added in culture solution, glycine-HCI buffer solution is added in into culture solution, adjusts pH to 3.0, then add
Entering whiterot fungi, 41h is reacted at 33 DEG C, take out bagasse, drying is crushed to grain size as 50 mesh, obtains modified bagasse,
Wherein the mass ratio of bagasse, culture solution and whiterot fungi is 1:11:5；
Above-mentioned culture solution includes the component of following parts by weight：2 parts of dusty yeast, vitamin B10.4 part, 1.5 parts of glucose, can
1.5 parts of soluble starch, KH2PO40.2 part and MgSO4·7H2O0.5 parts；
Wherein, organic silica resin is prepared by the following method to obtain：
（One）Epoxy resin and isopropyl acetate are mixed, stirring and dissolving, and chlorosilane is slowly added in whipping process
And benzoyl peroxide, under the conditions of nitrogen atmosphere, 90 DEG C, 2h is stirred to react, obtains reactant；Its epoxy resin, acetic acid
The weight ratio of isopropyl ester, chlorosilane and benzoyl peroxide is 2:5:2:0.05；
（Two）By step（One）The reactant of middle gained is added in absolute ethyl alcohol and is precipitated, and is filtered, is obtained sediment I, sediment I
Using 95% ethanolic extraction 30h, homopolymer is removed, sediment II is obtained, sediment II is dried in vacuo 15min at room temperature, is obtained
Organic silica resin.
The preparation method of above-mentioned halogen-free flame-retardant composite material, includes the following steps：
（1）P-diethynylbenzene, triethyl borate and organic silica resin are weighed by formula, is heated at 130 DEG C molten
Melt, stir evenly, much acetylene benzene polymer；
（2）By step（1）The polyacetylene benzene polymer of middle gained and modified powdered rice hulls, modified bagasse, magnesium hydroxide, hydrogen
Aluminium oxide, silane resin acceptor kh-550, dibutyl hydroxy toluene and copper oxide mixing are placed in double roller temperature and are 180 DEG C and open
It puts and the 15min that plasticates is melted in formula kneading machine, obtain mixing object, then polytetrafluoroethylene (PTFE) is added in open kneading machine, continue to melt
Plasticate 10min, obtains sheet material；
（3）By step（2）The sheet material of middle gained is crushed as granular material, then by granular material and hard cholic acid zinc
It is placed in together in 210 DEG C of vulcanizing press, the hot pressing 13min under conditions of 15MPa obtains halogen-free flame-retardant composite material.
Embodiment 3
A kind of halogen-free flame-retardant composite material includes the component of following parts by weight：Modified 36 parts of powdered rice hulls, modified bagasse 42
Part, 14 parts of p-diethynylbenzene, 8 parts of triethyl borate, 82 parts of organic silica resin, 14 parts of magnesium hydroxide, 15 parts of aluminium hydroxide,
2 parts of silane resin acceptor kh-550,2 parts of dibutyl hydroxy toluene, 10 parts of copper oxide, 1 part of hard cholic acid zinc and polytetrafluoroethylene (PTFE) 1
Part.
Wherein, modified powdered rice hulls are prepared by the following method to obtain：
Rice husk is added in culture solution, glycine-HCI buffer solution is added in into culture solution, pH to 3.0 is adjusted, adds
Whiterot fungi reacts 50h at 33 DEG C, takes out rice husk, and drying is crushed to grain size as 50 mesh, obtains modified powdered rice hulls, wherein
The mass ratio of rice husk, culture solution and whiterot fungi is 1:11:5；
Wherein, modified bagasse is prepared by the following method to obtain：
Bagasse is added in culture solution, glycine-HCI buffer solution is added in into culture solution, adjusts pH to 3.0, then add
Entering whiterot fungi, 45h is reacted at 32 DEG C, take out bagasse, drying is crushed to grain size as 50 mesh, obtains modified bagasse,
Wherein the mass ratio of bagasse, culture solution and whiterot fungi is 1:11:5；
Above-mentioned culture solution includes the component of following parts by weight：2 parts of dusty yeast, vitamin B10.4 part, 1.5 parts of glucose, can
1.5 parts of soluble starch, KH2PO40.2 part and MgSO4·7H2O0.5 parts；
Wherein, organic silica resin is prepared by the following method to obtain：
（One）Epoxy resin and isopropyl acetate are mixed, stirring and dissolving, and chlorosilane is slowly added in whipping process
And benzoyl peroxide, under the conditions of nitrogen atmosphere, 110 DEG C, 1.6h is stirred to react, obtains reactant；Its epoxy resin, second
The weight ratio of isopropyl propionate, chlorosilane and benzoyl peroxide is 5:10:5:0.05；
（Two）By step（One）The reactant of middle gained is added in absolute ethyl alcohol and is precipitated, and is filtered, is obtained sediment I, sediment I
Using 80% ethanolic extraction 20h, homopolymer is removed, sediment II is obtained, sediment II is placed in and is dried in vacuo 20min at room temperature, is obtained
To organic silica resin.
The preparation method of above-mentioned halogen-free flame-retardant composite material, includes the following steps：
（1）P-diethynylbenzene, triethyl borate and organic silica resin are weighed by formula, is heated at 135 DEG C molten
Melt, stir evenly, much acetylene benzene polymer；
（2）By step（1）The polyacetylene benzene polymer of middle gained and magnesium hydroxide, aluminium hydroxide, silane coupling agent KH-
550th, dibutyl hydroxy toluene and copper oxide mixing are placed in the open kneading machine that double roller temperature is 170 DEG C to melt and plasticate
17min obtains mixing object, then polytetrafluoroethylene (PTFE) is added in open kneading machine, continues to melt the 7min that plasticates, obtains sheet material；
（3）By step（2）The sheet material of middle gained is crushed as granular material, then by granular material and hard cholic acid zinc
It is placed in together in 195 DEG C of vulcanizing press, the hot pressing 20min under conditions of 8MPa obtains halogen-free flame-retardant composite material.
Embodiment 4
A kind of halogen-free flame-retardant composite material includes the component of following parts by weight：Modified 40 parts of powdered rice hulls, modified bagasse 46
Part, 16 parts of p-diethynylbenzene, 5 parts of triethyl borate, 93 parts of organic silica resin, 17 parts of magnesium hydroxide, 14 parts of aluminium hydroxide,
2 parts of 3 parts of silane resin acceptor kh-550,3 parts of dibutyl hydroxy toluene, 6 parts of copper oxide, 2 parts of hard cholic acid zinc and polytetrafluoroethylene (PTFE).
Wherein, modified powdered rice hulls are prepared by the following method to obtain：
Rice husk is added in culture solution, glycine-HCI buffer solution is added in into culture solution, pH to 3.0 is adjusted, adds
Whiterot fungi reacts 43h at 32 DEG C, takes out rice husk, and drying is crushed to grain size as 50 mesh, obtains modified powdered rice hulls, wherein
The mass ratio of rice husk, culture solution and whiterot fungi is 1:11:5；
Wherein, modified bagasse is prepared by the following method to obtain：
Bagasse is added in culture solution, glycine-HCI buffer solution is added in into culture solution, adjusts pH to 3.0, then add
Entering whiterot fungi, 39h is reacted at 32 DEG C, take out bagasse, drying is crushed to grain size as 50 mesh, obtains modified bagasse,
Wherein the mass ratio of bagasse, culture solution and whiterot fungi is 1:11:5；
Above-mentioned culture solution includes the component of following parts by weight：2 parts of dusty yeast, vitamin B10.4 part, 1.5 parts of glucose, can
1.5 parts of soluble starch, KH2PO40.2 part and MgSO4·7H2O0.5 parts；
Wherein, organic silica resin is prepared by the following method to obtain：
（One）Epoxy resin and isopropyl acetate are mixed, stirring and dissolving, and chlorosilane is slowly added in whipping process
And benzoyl peroxide, under the conditions of nitrogen atmosphere, 105 DEG C, 1.4h is stirred to react, obtains reactant；Its epoxy resin, second
The weight ratio of isopropyl propionate, chlorosilane and benzoyl peroxide is 3:8:3:0.04；
（Two）By step（One）The reactant of middle gained, which is poured into absolute ethyl alcohol, to be precipitated, and filtering obtains sediment I, sediment I
Using 90% ethanolic extraction 22h, homopolymer is removed, sediment II is obtained, sediment II is placed in and is dried in vacuo 20min at room temperature, is obtained
To organic silica resin.
The preparation method of above-mentioned halogen-free flame-retardant composite material, includes the following steps：
（1）P-diethynylbenzene, triethyl borate and organic silica resin are weighed by formula, is heated at 150 DEG C molten
Melt, stir evenly, much acetylene benzene polymer；
（2）By step（1）The polyacetylene benzene polymer of middle gained and modified powdered rice hulls, modified bagasse, magnesium hydroxide, hydrogen
Aluminium oxide, silane resin acceptor kh-550, dibutyl hydroxy toluene and copper oxide mixing are placed in double roller temperature and are 185 DEG C and open
It puts and the 12min that plasticates is melted in formula kneading machine, obtain mixing object, then polytetrafluoroethylene (PTFE) is added in open kneading machine, continue to melt
Plasticate 8min, obtains sheet material；
（3）By step（2）The sheet material of middle gained is crushed as granular material, then by granular material and hard cholic acid zinc
It is placed in together in 206 DEG C of vulcanizing press, the hot pressing 13min under conditions of 12MPa obtains halogen-free flame-retardant composite material.
Embodiment 5
A kind of halogen-free flame-retardant composite material includes the component of following parts by weight：Modified 37 parts of powdered rice hulls, modified bagasse 42
Part, 11 parts of p-diethynylbenzene, 10 parts of triethyl borate, 85 parts of organic silica resin, 12 parts of magnesium hydroxide, aluminium hydroxide 12
Part, 2 parts of silane resin acceptor kh-550,2 parts of dibutyl hydroxy toluene, 7 parts of copper oxide, 2 parts of hard cholic acid zinc and polytetrafluoroethylene (PTFE) 3
Part.
Wherein, modified powdered rice hulls are prepared by the following method to obtain：
Rice husk is added in culture solution, glycine-HCI buffer solution is added in into culture solution, pH to 3.0 is adjusted, adds
Whiterot fungi reacts 48h at 33 DEG C, takes out rice husk, and drying is crushed to grain size as 50 mesh, obtains modified powdered rice hulls, wherein
The mass ratio of rice husk, culture solution and whiterot fungi is 1:11:5；
Wherein, modified bagasse is prepared by the following method to obtain：
Bagasse is added in culture solution, glycine-HCI buffer solution is added in into culture solution, adjusts pH to 3.0, then add
Entering whiterot fungi, 38h is reacted at 33 DEG C, take out bagasse, drying is crushed to grain size as 50 mesh, obtains modified bagasse,
Wherein the mass ratio of bagasse, culture solution and whiterot fungi is 1:11:5；
The constituent content of above-mentioned culture solution is：2 parts of dusty yeast, vitamin B10.4 part, 1.5 parts of glucose, soluble starch
1.5 parts, KH2PO40.2 part and MgSO4·7H2O0.5 parts；
Wherein, organic silica resin is prepared by the following method to obtain：
（One）Epoxy resin and isopropyl acetate are added in into stirring and dissolving in beaker, and chlorine is slowly added in whipping process
Silane and benzoyl peroxide under the conditions of nitrogen atmosphere, 100 DEG C, are stirred to react 1h, obtain reactant；Its epoxy resin,
The weight ratio of isopropyl acetate, chlorosilane and benzoyl peroxide is 1:4:1:0.05；
（Two）By step（One）The reactant of middle gained, which is poured into absolute ethyl alcohol, to be precipitated, and filtering obtains sediment I, sediment I
Using 50% ethanolic extraction for 24 hours, homopolymer is removed, sediment II is obtained, sediment II is placed in and is dried in vacuo 18min at room temperature, is obtained
To organic silica resin.
The preparation method of above-mentioned halogen-free flame-retardant composite material, includes the following steps：
（1）P-diethynylbenzene, triethyl borate and organic silica resin are weighed by formula, is heated at 145 DEG C molten
Melt, stir evenly, much acetylene benzene polymer；
（2）By step（1）The polyacetylene benzene polymer of middle gained and modified powdered rice hulls, modified bagasse, magnesium hydroxide, hydrogen
Aluminium oxide, silane resin acceptor kh-550, dibutyl hydroxy toluene and copper oxide mixing are placed in double roller temperature and are 180 DEG C and open
It puts and the 15min that plasticates is melted in formula kneading machine, obtain mixing object, then polytetrafluoroethylene (PTFE) is added in open kneading machine, continue to melt
Plasticate 9min, obtains sheet material；
（3）By step（2）The sheet material of middle gained is crushed as granular material, then by granular material and hard cholic acid zinc
It is placed in together in 210 DEG C of vulcanizing press, the hot pressing 15min under conditions of 10MPa obtains halogen-free flame-retardant composite material.
Comparative example 1
The bittern-free flame-proof material ingredient and content compared with Example 3, lack polytetrafluoroethylene (PTFE), magnesium hydroxide and hydrogen-oxygen
Change aluminium, remaining ingredient and content are same as Example 3, and preparation method is also same as Example 3.
Comparative example 2
Compared with Example 3, magnesium hydroxide and aluminium hydroxide content are 50 parts for the bittern-free flame-proof material point and content,
Remaining ingredient and content are same as Example 3, and preparation method is also same as Example 3.
Experimental example
1st, under equal conditions, burn comparative example 1, comparative example 2 and the product obtained by embodiment 3 respectively, and comparative example 1 is more
Easy firing, and 2 plank good flame retardation effect of embodiment 3 and comparative example, are not easy to be burned, even if burned, emit flue gas it is small and
It is micro- slight, therefore 3 plank flame retardant effect of embodiment is more preferably, it is more environmentally friendly.
2nd, under equal conditions, the composite material of comparative example 1, comparative example 2 and embodiment 3 is struck using iron hammer
It hits, checks the damage situations of the composite material of comparative example and embodiment 3.
When being impacted, comparative example 1 is suitable with 3 extent of damage of embodiment, and comparative example 2 is compared to comparative example 1 with implementing
Example 3 be damaged it is even more serious, show a small amount of aluminium hydroxide and magnesium hydroxide do not interfere with not only composite material shock resistance it is strong
Degree can also promote the flame retardant effect of composite material.
Claims (10)
1. a kind of halogen-free flame-retardant composite material, it is characterised in that：Include the component of following parts by weight：
Modified 25~40 parts of powdered rice hulls, 27~46 parts of modified bagasse, 10~20 parts of p-diethynylbenzene, triethyl borate 5~
10 parts, it is 80~100 parts of organic silica resin, 10~20 parts of magnesium hydroxide, 10~20 parts of aluminium hydroxide, 1~4 part of coupling agent, anti-
1~5 part of 1~5 part of oxidant, 5~10 parts of antiseptic, 1~5 part of lubricant and polytetrafluoroethylene (PTFE)；
The modified powdered rice hulls are prepared by the following method to obtain：
Rice husk is added in culture solution, glycine-HCI buffer solution is added in into culture solution, pH to 3.0 is adjusted, adds white rot
Bacterium reacts 36~50h at 30~35 DEG C, takes out rice husk, and drying is crushed to grain size as 50 mesh, obtains modified powdered rice hulls,
Wherein the mass ratio of rice husk, culture solution and whiterot fungi is 1:11:5；
The modified bagasse is prepared by the following method to obtain：
Bagasse is added in culture solution, glycine-HCI buffer solution is added in into culture solution, pH to 3.0 is adjusted, adds white
Rotten bacterium reacts 36~45h at 30~35 DEG C, takes out bagasse, and drying is crushed to grain size as 50 mesh, obtains modified sweet
The mass ratio of bagasse, wherein bagasse, culture solution and whiterot fungi is 1:11:5；
Organic silica resin is prepared by the following method to obtain：
(1) epoxy resin and isopropyl acetate are mixed, stirring and dissolving, and be slowly added in whipping process chlorosilane and
Benzoyl peroxide under the conditions of nitrogen atmosphere, 90~110 DEG C, is stirred to react 1~2h, obtains reactant；Its epoxy resin,
The weight ratio of isopropyl acetate, chlorosilane and initiator is 1~5:3~10:1~5:0.02~0.05；
(2) gained reactant in step (1) is added in absolute ethyl alcohol and precipitated, filtered, obtain sediment I, sediment I uses
50%~95% 20~30h of ethanolic extraction removes homopolymer, obtains sediment II, sediment II is dried in vacuo at room temperature, is obtained
Organic silica resin.
2. halogen-free flame-retardant composite material according to claim 1, it is characterised in that：Include the component of following parts by weight：Change
36 parts of powdered rice hulls of property, 42 parts of modified bagasse, 14 parts of p-diethynylbenzene, 8 parts of triethyl borate, 82 parts of organic silica resin,
14 parts of magnesium hydroxide, 15 parts of aluminium hydroxide, 2 parts of coupling agent, 2 parts of antioxidant, 10 parts of antiseptic, 1 part of lubricant and poly- four
1 part of vinyl fluoride.
3. halogen-free flame-retardant composite material according to claim 1, it is characterised in that：The culture solution includes following parts by weight
Component：2 parts of dusty yeast, vitamin B10.4 part, 1.5 parts of glucose, 1.5 parts of soluble starch, KH2PO40.2 part and
MgSO4·7H2O0.5 parts.
4. halogen-free flame-retardant composite material according to claim 1, it is characterised in that：Epoxy resin and isopropyl acetate are mixed
It closes, stirring and dissolving, and chlorosilane and initiator is slowly added in whipping process, under the conditions of nitrogen atmosphere, 110 DEG C, stir
Mix reaction 1.6h.
5. halogen-free flame-retardant composite material according to claim 1 or 2, it is characterised in that：The coupling agent is silane coupled
Agent KH-550 or Aluminate.
6. halogen-free flame-retardant composite material according to claim 1 or 2, it is characterised in that：The antiseptic is zinc oxide, oxygen
Change copper, ammonium dihydrogen phosphate or lithium carbonate.
7. halogen-free flame-retardant composite material according to claim 1 or 2, it is characterised in that：The lubricant is stearic acid
Zinc, ethylene bis stearic acid amide, lead stearate, polyethylene wax, paraffin or oxidized polyethylene wax.
8. halogen-free flame-retardant composite material according to claim 1 or 2, it is characterised in that：The antioxidant is butyl hydroxyl
Base anisole, dibutyl hydroxy toluene, propylgallate, phytic acid or tert-butylhydroquinone.
9. the preparation method of claim 1~8 any one of them halogen-free flame-retardant composite material, it is characterised in that：Including following
Step：
(1) p-diethynylbenzene, triethyl borate and organic silica resin are weighed by formula, is heated at 120~150 DEG C molten
Melt, stir evenly, much acetylene benzene polymer；
(2) by the polyacetylene benzene polymer of gained in step (1) and modified powdered rice hulls, modified bagasse, magnesium hydroxide, hydroxide
Aluminium, antioxidant, antiseptic and coupling agent mixing, are placed in the open kneading machine that double roller temperature is 170 DEG C~190 DEG C and melt
Melt the 12~20min that plasticates, obtain mixing object, then polytetrafluoroethylene (PTFE) is placed in open kneading machine, continue melting plasticate 5~
10min obtains sheet material；
(3) it is granular material, then granular material is put together with lubricant to crush the sheet material of gained in step (2)
In 195 DEG C~220 DEG C of vulcanizing press, 12~20min of hot pressing under conditions of 8~15MPa obtains halogen-free flameproof composite wood
Material.
10. the preparation method of halogen-free flame-retardant composite material according to claim 9, it is characterised in that：Described in step (3)
Treatment conditions be：In 195 DEG C of vulcanizing press, the hot pressing 20min under conditions of 8MPa.
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| 碳材料表面特性及形貌对阻燃环氧树脂燃烧和热解行为的影响;王芳，等.;《高分子学报》;20170731(第7期);第860-870页 * |
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