CN109161149A - A kind of flame resistant heat insulation material and preparation method thereof - Google Patents
A kind of flame resistant heat insulation material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of flame resistant heat insulation material, composition and its parts by weight are as follows: 15~18 parts by weight of phosphorus hybrid oligomer, 82~85 parts by weight of styrene, 12~15 parts by weight of silane-modified bamboo powder, 18~22 parts by weight of stearic acid modified bamboo powder.The invention also discloses a kind of preparation methods of flame resistant heat insulation material, including alkali process, silane treatment, stearic acid are handled, synthesis phosphorus hybrid oligomer, prepare composite material.Have the beneficial effect that the flame resistant heat insulation material in the method for the present invention has excellent anti-flaming thermal-insulation performance, bamboo powder and the compatibility of resin matrix and mechanical engagement degree are preferable, the compactness extent of composite material and the uniformity are preferable, improve the mechanical strength of material, preparation method can greatly improve the component homogeneity and structural stability of flame resistant heat insulation material, and composite material is made to have stronger self-extinguishment and thermal insulation.
Description
Technical field
The present invention relates to special material fields, more particularly, to a kind of flame resistant heat insulation material and preparation method thereof.
Technical background
With the development of economy, demand of the whole world to the energy increasingly increases, in the total energy consumption being increasing, building energy consumption
Account for about the 11~25% of total energy consumption, therefore, Building Energy-saving causes the attention of more and more countries.It was verified that building
The most directly effective method of energy conservation is using heat preserving and insulating material.Currently used heat-barrier material mainly has: foam glass, polyphenyl
Vinylic foam, nano-pore heat-barrier material, glue powder polyphenyl granule insulating material, thermal insulation mortar, air entrained concrete, foam stone
Cotton, composite silicate thermal insulation material etc..But it generally has the disadvantages that firstly, damping performance is poor, and oxidizable and rotten
Erosion, service life is short, gradually loses waterproof, heat insulation function within general 2 to three years.Secondly, this material stretches and vertically and horizontally tension
It is easily rupturable under intensity is lower and foreign matter contact or weight, and surface smoothness is poor, and sunray reflectivity is lower；Heat-insulated,
Thermal insulation property is relatively poor.Again, the centre of this material is without air barrier, the convection current easy to form of interior outside energy, conduction,
To influence heat-insulated efficiency；Finally, being easy burning, poor fire.
Summary of the invention
The purpose of the present invention is to provide a kind of flame resistant heat insulation material and preparation method thereof, flame resistant heat insulation material has excellent
Anti-flaming thermal-insulation performance, the compatibility and mechanical engagement degree of bamboo powder and resin matrix are preferable, the compactness extent of composite material and
Evenness is preferable, improves the mechanical strength of material, preparation method can greatly improve the component homogeneity of flame resistant heat insulation material with
Structural stability makes composite material have stronger self-extinguishment and thermal insulation.
The present invention in background technique aiming at the problem that mentioning, the technical solution taken are as follows:
A kind of flame resistant heat insulation material, composition and its parts by weight are as follows: 15~18 parts by weight of phosphorus hybrid oligomer, styrene 82~85
Parts by weight, 12~15 parts by weight of silane-modified bamboo powder, 18~22 parts by weight of stearic acid modified bamboo powder；In phosphorus hybrid oligomer and benzene
Silane-modified bamboo powder and stearic acid modified bamboo powder are added in material after ethylene prepolymerization, styrene materials product can not only be improved
Mechanical property and structural strength, can also be effectively improved its consistency and mechanical property, at the same its corrosion-resistant antioxidation with
Anti-flaming thermal-insulation performance can also be greatly improved, it is made to can be applied to a variety of extreme environments, be a kind of efficient, safety fire-retardant
Heat-barrier material.
A kind of preparation method of flame resistant heat insulation material, comprising: alkali process, silane treatment, stearic acid processing, synthesis phospha
Oligomer prepares composite material, specifically includes the following steps:
Alkali process: bamboo powder is added in the NaOH solution that 10~12 times of concentration are 10.5~11.0wt%, is also contained in NaOH solution
There is the sparteine of 0.52~0.55wt ‰, stir lower 4~6h of soak at room temperature, filter and washes product to neutrality, drying to perseverance
It is alkali process bamboo powder after weight；On the one hand, alkali process can dissolve the amorphous components such as bamboo fibre hemicellulose, lignin, make
Fiber surface becomes coarse to improve the bonding force between resin, and lye can also weaken the work of the hydrogen bond inside cellulosic molecule
With increased fiber element intermolecular distance improves the accessibility of fiber, so that modifying agent is easier to penetrate into fibrous inner structure
It goes；On the other hand, under the action of lye, sparteine can enter bamboo powder cellulose inner space, further improve bamboo powder
The roughness on surface and inside, significantly improves the polarity of bamboo powder, and further increase the mechanical engagement degree of bamboo powder and resin matrix,
The compactness extent and the uniformity for enhancing composite material, improve the mechanical strength of material；
Silane treatment: alkali process bamboo powder is added to 10~12 times of 90 containing 0.5~0.6wt% vinyltrimethoxysilane
In~85wt% ethanol solution, stirring makes it be uniformly dispersed, and with salt acid for adjusting pH value to 4.3~4.4, then at 65~72 DEG C
It is stirred to react 4~8h, neutrality is washed with distilled water to after cooling, silane-modified bamboo powder is obtained after drying to constant weight；Use ethylene
Base trimethoxy silane is twice-modified to alkali-treated bamboo powder progress, can significantly improve the compatibility of composite material, composite wood
The mechanical strength of material is also improved significantly with impact strength, and after alkali process, silane can effectively enter bamboo powder fiber
Crystal region and noncrystalline domain, with hydroxyl occur substitution reaction, form flexible boundary layer, thus effectively transmit load, dispersion
Stress improves mechanical property；Vinyltrimethoxysilane issues unboiled water solution in acidic environment, and the Si-OH for hydrolyzing generation occurs
Polycondensation reaction, polycondensation generate Si-O-Si, and silicon oxygen chain and cellulosic molecule occur overlapping and winding, not only increase bamboo powder and tree
The compatibility of aliphatic radical material also improves the consistency and mechanical property of composite material, improves its corrosion-resistant antioxidation；
Stearic acid processing: 0.8~1 parts by weight stearic acid and 0.015~0.018 parts by weight 3- bromcamphor -8- sulfonic acid ammonium salt are taken
It is added in 220~250 parts by weight distilled water, stirring is warming up to 68~75 DEG C, and 50~55 parts by weight alkali are added after being completely dissolved
Bamboo powder is handled, constant temperature is stirred to react 30~45min；Product is washed repeatedly with distilled water and removes unreacted modifying agent, and drying is extremely
Constant weight obtains stearic acid modified bamboo powder；Stearic acid not only can with the hydroxyl in powder occur chemical bond and, can also pass through
The powder surface that is mutually wrapped in of long chain hydrocarbon groups forms monolayer cladding, to reduce powder surface polarity；Meanwhile stearic acid
Cooperative gain effect occurs with micro 3- bromcamphor -8- sulfonic acid ammonium salt, cooperative gain effect can greatly increase fibre
The crystallization rate for tieing up plain molecule, improves the accounting of cellulose ii structure, is conducive to the structural stability and component that improve fiber
The impact fracture surface structure of uniform level, manufactured composite material is finer and close, and interface compatibility obtains obviously between bamboo powder and resin
Improve, bamboo powder is uniformly dispersed in resin matrix resin, plays good toughening effect；
It synthesizes phosphorus hybrid oligomer: first leading to 8~10min of nitrogen in a reservoir, 22~23 parts by weight dichloro-phenyl phosphates, 23 are added
~23.4 parts by weight triethylamines, 0.044~0.045 parts by weight alchlor, 0.0014~0.0015 parts by weight (R)-Alpha-Methyl
Benzylamine and 100~140 weight parts Methylene chlorides, are stirred to react 30~45min in ice-water bath, and 6.5~6.8 weight are slowly added dropwise
Part ethylene glycol, drips and is warming up to 25~27 DEG C of 1~1.5h of heat preservation, be warming up to 43~45 DEG C of 4~6h of back flow reaction, be cooled to 25
~27 DEG C and 0.2~0.21 parts by weight anhydrous methanol of dropwise addition, are warming up to 43~45 DEG C of 6~8h of back flow reaction, take advantage of after reaction
Heat filtering is washed with distilled water to filtrate neutrality, and vacuum distillation removes solvent after anhydrous sodium sulfate is dry, is sunk again with anhydrous ether
It forms sediment twice, filter cake is put into vacuum oven and is dried to obtain light red brown thick liquid, as product phosphorus hybrid oligomer after filtering；
With this gradually synthetic method prepare phosphorus hybrid oligomer yield it is higher, up to 80% or more, while introducing in the reaction system
(R)-Alpha-Methyl benzylamine has the function of reducing the phospha fluidized polymer degree of polymerization, stablizes polymerization system, polymerization reaction can be made in phase
To completing under conditions of mild, and the molecular weight distribution of product phosphorus hybrid oligomer can be effectively controlled, control its molecular weight between
Between 1650~1750, the component homogeneity and structural stability of phosphorus hybrid oligomer are substantially increased, by phosphorus hybrid oligomer
The thermal stability and flame retardant property that composite material is effectively improved after introducing PS material, make composite material have stronger self-extinguishment
Property and thermal insulation, optimize the anti-flaming thermal-insulation performance of composite material, expand its application range；
It prepares composite material: taking 15~18 parts by weight phosphorus hybrid oligomers and 82~85 parts by weight of styrene in reactor, lead to
Enter nitrogen, add the azodiisobutyronitrile of 0.5~0.8wt% of styrene quality, stir and be warming up to 68~70 DEG C of pre-polymerizations 25~
30min stops stirring；The silane-modified bamboo powder of 12~15 parts by weight and the stearic acid modified bamboo powder of 18~22 parts by weight is added, stirring is equal
Discharging is cast in mold after even, sets casting mold in baking oven, is warming up to 80~85 DEG C of 12~16h of curing, and cooling demoulding obtains
To flame resistant heat insulation material；Modified bamboo powder is added in the material after phosphorus hybrid oligomer and styrene prepolymerization, can not only improve
The mechanical property and structural strength of styrene materials product can also be effectively improved its consistency and mechanical property, while its corrosion resistant
Erosion antioxidation can also be greatly improved with anti-flaming thermal-insulation performance, it is made to can be applied to a variety of extreme environments；Composite wood
In hot oxygen environment, the phosphonate moiety in phosphorus hybrid oligomer decomposes material first, and decomposition product promotes matrix can be lower
At a temperature of start to decompose, generate PO, P, with gas phase in H and OH generate HPO interrupt or inhibit combustion process, together
Phosphate is thermally generated metaphosphoric acid, and is covered in polymer surfaces, promotes matrix heat-insulated at layer of charcoal, oxygen barrier, the protection charcoal of formation
Layer can inhibit heat and oxygen is further melted and reacted to polymer, make flame self-extinguish, be a kind of efficient, safety fire-retardant
Heat-barrier material.
Compared with the prior art, the advantages of the present invention are as follows:
1) when carrying out alkali process to bamboo powder, under lye effect, sparteine can enter inside bamboo powder cellulose, improve bamboo powder table
The roughness in face and inside, significantly improves the polarity of bamboo powder, and further increase the mechanical engagement degree of bamboo powder and resin matrix, increases
The compactness extent and the uniformity of strong composite material, improve the mechanical strength of material；
2) cooperative gain effect when carrying out stearic acid processing to bamboo powder, between stearic acid and 3- bromcamphor -8- sulfonic acid ammonium salt
The crystallization rate that cellulosic molecule can be greatly increased improves the accounting of cellulose ii structure, is conducive to improve fiber
Structural stability and component uniform level, between bamboo powder and resin interface compatibility be improved significantly, bamboo powder is in resin matrix tree
It is uniformly dispersed in rouge, plays good toughening effect；
3) introducing (R)-Alpha-Methyl benzylamine in the reaction system has the reduction phospha fluidized polymer degree of polymerization, stablizes polymerization system
Effect, can be such that polymerization reaction completes under relatively mild conditions, and the molecular weight of product phosphorus hybrid oligomer can be effectively controlled
Distribution, controls its molecular weight between 1650~1750, substantially increases the component homogeneity and structure of phosphorus hybrid oligomer
Stability；
4) silane-modified bamboo powder and stearic acid modified bamboo powder is added in the material after phosphorus hybrid oligomer and styrene prepolymerization,
The mechanical property and structural strength that styrene materials product can not only be improved, can also be effectively improved its consistency and mechanical property,
Its corrosion-resistant antioxidation can also be greatly improved with anti-flaming thermal-insulation performance simultaneously, it is made to can be applied to a variety of extreme rings
Border is a kind of flame resistant heat insulation material efficiently, safe.
Specific embodiment
The present invention program is described further below by embodiment:
Embodiment 1:
A kind of flame resistant heat insulation material, composition and its parts by weight are as follows: 15 parts by weight of phosphorus hybrid oligomer, 885 parts by weight of styrene,
Silane-modified 12 parts by weight of bamboo powder, 18 parts by weight of stearic acid modified bamboo powder；After phosphorus hybrid oligomer and styrene prepolymerization
Silane-modified bamboo powder and stearic acid modified bamboo powder are added in material, the mechanical property and knot of styrene materials product can not only be improved
Structure intensity can also be effectively improved its consistency and mechanical property, while its corrosion-resistant antioxidation and anti-flaming thermal-insulation performance
It can be greatly improved, it is made to can be applied to a variety of extreme environments, be a kind of flame resistant heat insulation material efficiently, safe.
A kind of preparation method of flame resistant heat insulation material, comprising the following steps:
S1: bamboo powder being added in the NaOH solution that 10 times of concentration are 10.5wt%, is stirred lower soak at room temperature 4h, is filtered and wash
Product is alkali process bamboo powder after drying to constant weight to neutrality；
S2: alkali process bamboo powder is added in 10 times of 90wt% ethanol solutions containing 0.5wt% vinyltrimethoxysilane, is stirred
Mixing makes it be uniformly dispersed, and with salt acid for adjusting pH value to 4.3, and 4h is then stirred to react at 65 DEG C, is washed with distilled water after cooling
To neutrality, silane-modified bamboo powder is obtained after drying to constant weight；
S3: 0.8 parts by weight stearic acid and 0.015 parts by weight 3- bromcamphor -8- sulfonic acid ammonium salt is taken to be added to the distillation of 220 parts by weight
In water, stirring is warming up to 68 DEG C, 50 parts by weight alkali process bamboo powders is added after being completely dissolved, constant temperature is stirred to react 30min；
S4: first leading to nitrogen 8min in a reservoir, and 22 parts by weight dichloro-phenyl phosphates, 23 parts by weight triethylamines, 0.044 weight are added
Part alchlor, 0.0014 parts by weight (R)-Alpha-Methyl benzylamine and 100 weight parts Methylene chlorides, are stirred to react in ice-water bath
6.5 parts by weight ethylene glycol are slowly added dropwise in 30min, drip and are warming up to 25 DEG C of heat preservation 1h, are warming up to 43 DEG C of back flow reaction 4h, drop
Temperature is to 25 DEG C and 0.2 parts by weight anhydrous methanol is added dropwise, and is warming up to 43 DEG C of back flow reaction 6h, filters while hot after reaction, with steaming
Distilled water is washed to filtrate neutrality, and vacuum distillation removes solvent after anhydrous sodium sulfate is dry, twice with anhydrous ether reprecipitation, filtering
Filter cake is put into vacuum oven and is dried to obtain light red brown thick liquid, as product phosphorus hybrid oligomer afterwards；
S5: it takes 15 parts by weight phosphorus hybrid oligomers and 82 parts by weight of styrene in reactor, is passed through nitrogen, adds styrene
The azodiisobutyronitrile of quality 0.5% stirs and is warming up to 68 DEG C of pre-polymerization 25min, stops stirring；It is silane-modified that 12 parts by weight are added
Bamboo powder and the stearic acid modified bamboo powder of 18 parts by weight, discharging is cast in mold after mixing evenly, sets casting mold in baking oven, is risen
Temperature to 80 DEG C of curing 12h, cooling demoulding obtains flame resistant heat insulation material；Material after phosphorus hybrid oligomer and styrene prepolymerization
Modified bamboo powder is added in material, the mechanical property and structural strength of styrene materials product can not only be improved, can also be effectively improved it
Consistency and mechanical property, while its corrosion-resistant antioxidation can also be greatly improved with anti-flaming thermal-insulation performance, make it
It can be applied to a variety of extreme environments；In hot oxygen environment, the phosphonate moiety in phosphorus hybrid oligomer decomposes composite material first,
Decomposition product promotes matrix that can start to decompose at a lower temperature, and the H and OH generated in PO, P, with gas phase is produced
Raw HPO interrupts or inhibits combustion process, is thermally generated metaphosphoric acid with phosphate, and be covered in polymer surfaces, promote matrix at
Layer of charcoal is heat-insulated, oxygen barrier, and the protection layer of charcoal of formation can inhibit heat and oxygen is further melted and reacted to polymer, makes flame voluntarily
Extinguish, is a kind of flame resistant heat insulation material efficiently, safe.
Embodiment 2:
A kind of preparation method of flame resistant heat insulation material, specifically includes the following steps:
S1: bamboo powder being added in the NaOH solution that 12 times of concentration are 11.0wt%, the gold in NaOH solution also containing 0.55wt ‰
Sparrow spends alkali, stirs lower soak at room temperature 6h, filters and washes product to neutrality, is alkali process bamboo powder after drying to constant weight；
S2: alkali process bamboo powder is added in 12 times of 85wt% ethanol solutions containing 0.6wt% vinyltrimethoxysilane, is stirred
Mixing makes it be uniformly dispersed, and with salt acid for adjusting pH value to 4.4, and 8h is then stirred to react at 72 DEG C, is washed with distilled water after cooling
To neutrality, silane-modified bamboo powder is obtained after drying to constant weight；
S3: 1 parts by weight stearic acid and 0.018 parts by weight 3- bromcamphor -8- sulfonic acid ammonium salt is taken to be added to 250 parts by weight distilled water
In, stirring is warming up to 75 DEG C, 55 parts by weight alkali process bamboo powders is added after being completely dissolved, constant temperature is stirred to react 45min；Product steams
Distilled water is washed repeatedly removes unreacted modifying agent, and drying to constant weight obtains stearic acid modified bamboo powder；
S4: first leading to nitrogen 10min in a reservoir, and 23 parts by weight dichloro-phenyl phosphates, 23.4 parts by weight triethylamines, 0.045 are added
Parts by weight alchlor and 140 weight parts Methylene chlorides, are stirred to react 45min in ice-water bath, and 6.8 parts by weight second are slowly added dropwise
Glycol drips and is warming up to 27 DEG C of heat preservation 1.5h, is warming up to 45 DEG C of back flow reaction 6h, is cooled to 27 DEG C and 0.21 parts by weight are added dropwise
Anhydrous methanol is warming up to 45 DEG C of back flow reaction 8h, filters while hot after reaction, is washed with distilled water to filtrate neutrality, anhydrous
Vacuum distillation removes solvent after sodium sulphate is dry, and twice with anhydrous ether reprecipitation, it is dry to be put into vacuum oven for filter cake after filtering
It is dry to obtain light red brown thick liquid, as product phosphorus hybrid oligomer；
S5: it takes 18 parts by weight phosphorus hybrid oligomers and 85 parts by weight of styrene in reactor, is passed through nitrogen, adds styrene
The azodiisobutyronitrile of quality 0.8% stirs and is warming up to 70 DEG C of pre-polymerization 30min, stops stirring；It is silane-modified that 15 parts by weight are added
Bamboo powder and the stearic acid modified bamboo powder of 22 parts by weight, discharging is cast in mold after mixing evenly, sets casting mold in baking oven, is risen
Temperature to 85 DEG C of curing 16h, cooling demoulding obtains flame resistant heat insulation material；Material after phosphorus hybrid oligomer and styrene prepolymerization
Modified bamboo powder is added in material, the mechanical property and structural strength of styrene materials product can not only be improved, can also be effectively improved it
Consistency and mechanical property, while its corrosion-resistant antioxidation can also be greatly improved with anti-flaming thermal-insulation performance, make it
It can be applied to a variety of extreme environments；In hot oxygen environment, the phosphonate moiety in phosphorus hybrid oligomer decomposes composite material first,
Decomposition product promotes matrix that can start to decompose at a lower temperature, and the H and OH generated in PO, P, with gas phase is produced
Raw HPO interrupts or inhibits combustion process, is thermally generated metaphosphoric acid with phosphate, and be covered in polymer surfaces, promote matrix at
Layer of charcoal is heat-insulated, oxygen barrier, and the protection layer of charcoal of formation can inhibit heat and oxygen is further melted and reacted to polymer, makes flame voluntarily
Extinguish, is a kind of flame resistant heat insulation material efficiently, safe.
Embodiment 3:
A kind of flame resistant heat insulation material, composition and its parts by weight are as follows: 16 parts by weight of phosphorus hybrid oligomer, 84 parts by weight of styrene,
Silane-modified 14 parts by weight of bamboo powder, 21 parts by weight of stearic acid modified bamboo powder；After phosphorus hybrid oligomer and styrene prepolymerization
Silane-modified bamboo powder and stearic acid modified bamboo powder are added in material, the mechanical property and knot of styrene materials product can not only be improved
Structure intensity can also be effectively improved its consistency and mechanical property, while its corrosion-resistant antioxidation and anti-flaming thermal-insulation performance
It can be greatly improved, it is made to can be applied to a variety of extreme environments, be a kind of flame resistant heat insulation material efficiently, safe.
A kind of preparation method of flame resistant heat insulation material, comprising: alkali process, silane treatment, stearic acid processing, synthesis phospha
Oligomer prepares composite material, specifically includes the following steps:
Alkali process: bamboo powder is added in the NaOH solution that 10 times of concentration are 11wt%, also containing 0.54wt's ‰ in NaOH solution
Sparteine stirs lower soak at room temperature 5h, filters and washes product to neutrality, is alkali process bamboo powder after drying to constant weight；One
Aspect, alkali process can dissolve the amorphous components such as bamboo fibre hemicellulose, lignin, and fiber surface is made to become coarse to mention
Bonding force between high and resin, lye can also weaken the hydrogen bond action inside cellulosic molecule, increased fiber element intermolecular distance,
The accessibility for improving fiber, so that modifying agent is easier to penetrate into fibrous inner structure；On the other hand, in the effect of lye
Under, sparteine can enter bamboo powder cellulose inner space, further improve the roughness on bamboo powder surface and inside, significantly mention
The polarity of high bamboo powder, and further increase the mechanical engagement degree of bamboo powder and resin matrix, enhance the compactness extent of composite material with
The uniformity improves the mechanical strength of material；
Silane treatment: it is molten that alkali process bamboo powder is added to 12 times of 90wt% ethyl alcohol containing 0.55wt% vinyltrimethoxysilane
In liquid, stirring makes it be uniformly dispersed, and uses salt acid for adjusting pH value to 4.4, is then stirred to react 5h at 70 DEG C, it is cooling after with distilling
Water washing obtains silane-modified bamboo powder to neutrality after drying to constant weight；With vinyltrimethoxysilane to alkali-treated
Bamboo powder progress is twice-modified, can significantly improve the compatibility of composite material, and the mechanical strength and impact strength of composite material also obtain
To significantly improving, after alkali process, silane can effectively enter crystal region and the noncrystalline domain of bamboo powder fiber, send out with hydroxyl
Raw substitution reaction, forms flexible boundary layer, to effectively transmit load, dispersive stress improves mechanical property；Vinyl front three
Oxysilane issues unboiled water solution in acidic environment, and polycondensation reaction occurs for the Si-OH for hydrolyzing generation, and polycondensation generates Si-O-Si, silicon oxygen
Overlapping and winding occurs for chain and cellulosic molecule, not only increases the compatibility of bamboo powder and resin base material, also raising composite wood
The consistency and mechanical property of material improve its corrosion-resistant antioxidation；
Stearic acid processing: 1 parts by weight stearic acid and 0.016 parts by weight 3- bromcamphor -8- sulfonic acid ammonium salt is taken to be added to 240 weight
In part distilled water, stirring is warming up to 70 DEG C, 54 parts by weight alkali process bamboo powders is added after being completely dissolved, constant temperature is stirred to react 35min；
Product is washed repeatedly with distilled water and removes unreacted modifying agent, and drying to constant weight obtains stearic acid modified bamboo powder；Stearic acid
Not only can with the hydroxyl in powder occur chemical bond and, can also be formed by the powder surface that is mutually wrapped in of long chain hydrocarbon groups
Monolayer cladding, to reduce powder surface polarity；Meanwhile stearic acid and micro 3- bromcamphor -8- sulfonic acid ammonium salt are sent out
Raw cooperative gain effect, the cooperative gain act on the crystallization rate that can greatly increase cellulosic molecule, improve cellulose II
The accounting of type structure, is conducive to the structural stability and component uniform level that improve fiber, and the impact of manufactured composite material is disconnected
Face structure is finer and close, between bamboo powder and resin interface compatibility be improved significantly, bamboo powder is dispersed in resin matrix resin
It is even, play good toughening effect；
It synthesizes phosphorus hybrid oligomer: first leading to nitrogen 8min in a reservoir, 22 parts by weight dichloro-phenyl phosphates, 23 parts by weight three are added
Ethamine, 0.044 parts by weight alchlor, 0.0015 parts by weight (R)-Alpha-Methyl benzylamine and 120 weight parts Methylene chlorides, in ice water
It is stirred to react 40min in bath, 6.6 parts by weight ethylene glycol are slowly added dropwise, drips and is warming up to 26 DEG C of heat preservation 1h, is warming up to 44 DEG C and returns
Stream reaction 5h is cooled to 26 DEG C and 0.2 parts by weight anhydrous methanol is added dropwise, is warming up to 44 DEG C of back flow reaction 7h, takes advantage of after reaction
Heat filtering is washed with distilled water to filtrate neutrality, and vacuum distillation removes solvent after anhydrous sodium sulfate is dry, is sunk again with anhydrous ether
It forms sediment twice, filter cake is put into vacuum oven and is dried to obtain light red brown thick liquid, as product phosphorus hybrid oligomer after filtering；
With this gradually synthetic method prepare phosphorus hybrid oligomer yield it is higher, up to 80% or more, while introducing in the reaction system
(R)-Alpha-Methyl benzylamine has the function of reducing the phospha fluidized polymer degree of polymerization, stablizes polymerization system, polymerization reaction can be made in phase
To completing under conditions of mild, and the molecular weight distribution of product phosphorus hybrid oligomer can be effectively controlled, control its molecular weight between
Between 1650~1750, the component homogeneity and structural stability of phosphorus hybrid oligomer are substantially increased, by phosphorus hybrid oligomer
The thermal stability and flame retardant property that composite material is effectively improved after introducing PS material, make composite material have stronger self-extinguishment
Property and thermal insulation, optimize the anti-flaming thermal-insulation performance of composite material, expand its application range；
It prepares composite material: taking 16 parts by weight phosphorus hybrid oligomers and 84 parts by weight of styrene in reactor, be passed through nitrogen, then
The azodiisobutyronitrile of styrene quality 0.6% is added, stirs and is warming up to 70 DEG C of pre-polymerization 30min, stop stirring；14 weight are added
The silane-modified bamboo powder of part and the stearic acid modified bamboo powder of 21 parts by weight, discharging is cast in mold after mixing evenly, sets casting mold
In baking oven, 80 DEG C of curing 15h are warming up to, cooling demoulding obtains flame resistant heat insulation material；It is pre- in phosphorus hybrid oligomer and styrene
Modified bamboo powder is added in material after polymerization, the mechanical property and structural strength of styrene materials product can not only be improved, may be used also
It is effectively improved its consistency and mechanical property, while its corrosion-resistant antioxidation and anti-flaming thermal-insulation performance can also obtain significantly
It improves, it is made to can be applied to a variety of extreme environments；Phosphonate moiety of the composite material in hot oxygen environment, in phosphorus hybrid oligomer
It decomposes first, decomposition product promotes matrix that can start to decompose at a lower temperature, generates in PO, P, with gas phase
H and OH generates HPO and interrupts or inhibit combustion process, is thermally generated metaphosphoric acid with phosphate, and be covered in polymer surfaces,
Promote matrix heat-insulated at layer of charcoal, oxygen barrier, the protection layer of charcoal of formation can inhibit heat and oxygen is further melted and reacted to polymer,
Make flame self-extinguish, is a kind of flame resistant heat insulation material efficiently, safe.
Routine operation in operation of the present invention step is well known to those skilled in the art, herein without repeating.
Technical solution of the present invention is described in detail in embodiment described above, it should be understood that the above is only
For specific embodiments of the present invention, it is not intended to restrict the invention, all any modifications made in spirit of the invention,
Supplement or similar fashion substitution etc., should all be included in the protection scope of the present invention.
Claims (9)
1. a kind of flame resistant heat insulation material, it is characterised in that: the composition and its parts by weight of the flame resistant heat insulation material are as follows: phosphaization is low
15~18 parts by weight of polymers, 82~85 parts by weight of styrene, 12~15 parts by weight of silane-modified bamboo powder, stearic acid modified bamboo powder 18
~22 parts by weight.
2. a kind of preparation method of flame resistant heat insulation material, comprising: alkali process, silane treatment, stearic acid processing, synthesis phosphaization are low
Polymers prepares composite material, it is characterised in that: the alkali treatment are as follows: bamboo powder is added to 10~12 times and contains broom top
In the NaOH solution of alkali, lower soak at room temperature is stirred, filter and washes product to neutrality, is alkali process bamboo after drying to constant weight
Powder.
3. a kind of preparation method of flame resistant heat insulation material according to claim 2, it is characterised in that: the alkali treatment
In, the concentration of NaOH solution is 10.5~11.0wt%, and the content of sparteine is 0.52~0.55wt ‰.
4. a kind of preparation method of flame resistant heat insulation material according to claim 2, it is characterised in that: the silane treatment step
Suddenly are as follows: alkali process bamboo powder is added to 10~12 times of 90~85wt% second containing 0.5~0.6wt% vinyltrimethoxysilane
In alcoholic solution, stirring makes it be uniformly dispersed, and adjusts pH value to 4.3~4.4, is then stirred to react, is washed with distilled water after cooling
To neutrality, silane-modified bamboo powder is obtained after drying to constant weight.
5. a kind of preparation method of flame resistant heat insulation material according to claim 2, it is characterised in that: the stearic acid processing
Step are as follows: take stearic acid and 3- bromcamphor -8- sulfonic acid ammonium salt to be added in distilled water, stirring heating is added after being completely dissolved
Alkali process bamboo powder, constant temperature are stirred to react；Product is washed repeatedly with distilled water and removes unreacted modifying agent, is dried to constant weight to obtain the final product
To stearic acid modified bamboo powder.
6. a kind of preparation method of flame resistant heat insulation material according to claim 5, it is characterised in that: the stearic acid processing
In step, the parts by weight of each reactant are as follows: 0.8~1 parts by weight of stearic acid, 3- bromcamphor -8- sulfonic acid ammonium salt 0.015~
0.018 parts by weight, 220~250 parts by weight of distilled water, 50~55 parts by weight of alkali process bamboo powder.
7. a kind of preparation method of flame resistant heat insulation material according to claim 2, it is characterised in that: the synthesis phospha
Oligomer step are as follows: first lead to nitrogen in a reservoir, dichloro-phenyl phosphate, triethylamine, alchlor, (R)-Alpha-Methyl benzylamine is added
It with methylene chloride, is stirred to react in ice-water bath, ethylene glycol is slowly added dropwise, dripped and be warming up to 25~27 DEG C of 1~1.5h of heat preservation,
43~45 DEG C of 4~6h of back flow reaction are warming up to, be cooled to 25~27 DEG C and anhydrous methanol is added dropwise, it is anti-to be warming up to 43~45 DEG C of reflux
Answer 6~8h, filter while hot after reaction, it is washed, dry, go solvent, precipitating, filtering after, filter cake is put into vacuum oven
It is dried to obtain light red brown thick liquid, as product phosphorus hybrid oligomer.
8. a kind of preparation method of flame resistant heat insulation material according to claim 7, it is characterised in that: the synthesis phospha
In oligomer step, the parts by weight of each reactant are as follows: 22~23 parts by weight of dichloro-phenyl phosphate, 23~23.4 weight of triethylamine
Part, 0.044~0.045 parts by weight of alchlor, 0.0014~0.0015 parts by weight of (R)-Alpha-Methyl benzylamine, methylene chloride 100
~140 parts by weight, 6.5~6.8 parts by weight of ethylene glycol, 0.2~0.21 parts by weight of anhydrous methanol.
9. a kind of preparation method of flame resistant heat insulation material according to claim 2, it is characterised in that: described to prepare composite wood
Expect step are as follows: the phosphorus hybrid oligomer and styrene for taking formula ratio are passed through nitrogen, add styrene quality in reactor
The azodiisobutyronitrile of 0.5~0.8wt%, is stirred and the pre-polymerization that heats up, and stops stirring；Be added silane-modified bamboo powder with it is stearic acid modified
Bamboo powder, discharging is cast in mold after mixing evenly, is set casting mold and is cured in baking oven, and cooling demoulding obtains anti-flaming thermal-insulation
Material.
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