CN109942882A - A kind of phosphorous inherent fire-retardant fiber element base heat-barrier material and preparation method thereof - Google Patents
A kind of phosphorous inherent fire-retardant fiber element base heat-barrier material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of phosphorous inherent fire-retardant fiber element base heat-barrier materials and preparation method thereof, preparation method is the following steps are included: step 1: in 1 wt%~10wt% concentration cellulose suspension, urea and phosphorylation modifying agent is added, under the conditions of 150 DEG C~165 DEG C, after stirring evenly sufficiently reaction, washing obtains phosphorous cellulose；Step 2: phosphorous cellulose being configured to the suspension of 0.5wt%~2wt%, adjusting its pH is 9.5~12, after sufficiently reacting under stirring condition, is obtained after washing, defibering phosphorous cellulose nano-fibrous；Step 3: by it is phosphorous it is cellulose nano-fibrous by shaped in situ method or post-processing cross-linking method, by it is phosphorous it is cellulose nano-fibrous in phosphorus-containing groups Ionization Modification after obtain needed for phosphorous inherent fire-retardant fiber element base heat-barrier material；Preparation process of the present invention is simple, raw material sources are extensive, at low cost, environmentally protective, and obtained heat-barrier material thermal coefficient and density is low, flame retardant property is good.
Description
Technical field
The present invention relates to biomass heat-barrier material technical fields, and in particular to a kind of phosphorous inherent fire-retardant fiber element base is heat-insulated
Material and preparation method thereof.
Background technique
As petroleum resources are increasingly exhausted, environmental protection is found, green, renewable resource develops new energy as substitutable resources
Source, new material have become the inexorable trend of development；Cellulose is a kind of renewable resource that nature is widely present, reserves
Greatly, materials are easy, are cheap, are one of the most abundant biomass polymers of resource on the earth；Exploitation is used based on cellulose
New function material will generate good economy and ecological benefits；But cellulosic material easily burns, and mechanical strength
Lower, which prevent its further applying in heat-insulation and heat-preservation field；That there are flame retarding efficiencies is inclined for existing cellulose flame-retarded technology
Low, the problems such as when burning is also easy to produce poison gas, preparation difficulty is larger；It is also easily led using highly filled inorganic micro-/ nano particle
The density of heat-barrier material is caused to increase, thermal coefficient raising；So needing to carry out more efficient environmental protection flame retardant to cellulosic material
It is modified.
There are commonly two ways, one kind having resistance for addition for the fire-retardant and enhancing of cellulosic material base heat-barrier material at present
The micro-/ nano particle of combustion effect；Another kind is the phosphonium flame retardant of addition response type；It is strong to add inorganic fire retardants or barrier property
In the flame-retardant system of nano particle inorganic micro-/ nano particle generally require be added to higher content could obtain it is satisfied fire-retardant
Effect；But highly filled inorganic micro-/ nano particle disperses that difficulty is big during the preparation process, and the addition of a large amount of rigid particles is held
Easily lead to the density increase of material, thermal coefficient increases；The phosphonium flame retardant of addition response type can not achieve the enhancing of material, need
In addition the modes such as crosslinking agent to be added and realize enhancing；It is avoided that using intrinsically flame retarded method because of inorganic micro-/ nano fire-retardant
The problem of pore structure caused by grain is unevenly distributed is collapsed, can keep low-density, the low heat conductivity of cellulose base heat-barrier material；It will contain
It is to realize the intrinsically flame retarded effective way of efficient halogen-free that phosphorus fire-retardant group, which introduces cellulose molecular chain,；But traditional phosphorus-containing groups
Generally there is certain gas phase fire retardation, increase the flue gas release of material in combustion, and much phosphorous gases all have
There is certain toxicity；It is the main reason for causing casualties that fire statistics, which shows that poison gas makes one to be poisoned or suffocate,.
Summary of the invention
The present invention provide it is a kind of with excellent heat-proof quality and mechanical property, it is fire-retardant efficiently, phosphorous of safety and environmental protection
Matter fire-retardant cellulose base heat-barrier material and preparation method thereof.
The technical solution adopted by the present invention is that: a kind of preparation method of phosphorous inherent fire-retardant fiber element base heat-barrier material, packet
Include following steps:
Step 1: in the cellulose suspension of 1wt%~10wt% concentration, urea and phosphorylation modifying agent is added,
Under the conditions of 150 DEG C~165 DEG C, after stirring evenly sufficiently reaction, washing obtains phosphorous cellulose；Wherein deoxyglucose in cellulose
Sugar unit, urea and phosphorylation modifier molar ratio are 0.4~1.5:4~5:1；
Step 2: the phosphorous cellulose that step 1 is obtained is configured to the suspension of 0.5wt%~2wt%, adjusts its pH and is
9.5~12, after sufficiently reacting under stirring condition, obtained after washing, defibering phosphorous cellulose nano-fibrous；
Step 3: by step 2 obtain it is phosphorous it is cellulose nano-fibrous by shaped in situ method or post-processing cross-linking method, will
It is phosphorous it is cellulose nano-fibrous in phosphorus-containing groups Ionization Modification after obtain needed for the phosphorous heat-insulated material of inherent fire-retardant fiber element base
Material.
Further, detailed process is as follows for the step 3 shaped in situ method:
The phosphorous cellulose nano-fibrous suspension for being configured to 0.5wt%~2wt% will be prepared in step 2, stir
After uniformly, 0.05mol/L aqueous metal salt or metal hydroxides aqueous solution is added dropwise, is washed after standing 6h~12h crosslinking
It washs；It is freeze-dried after freezing solidification, it is fine up to required phosphorous inherent flame retardant after finally sufficiently being dried under the conditions of 80 DEG C~100 DEG C
Tie up plain base heat-barrier material.
Further, detailed process is as follows for the post-processing cross-linking method in the step 3:
The phosphorous cellulose nano-fibrous suspension for being configured to 0.5wt%~2wt% will be prepared in step 2, stir
After uniformly, freezing solidification, freeze-drying process are then sufficiently dry under the conditions of 80 DEG C~100 DEG C；
Alcohol solution for soaking 6h~12h of saturation metal salt alcoholic solution or metal oxide is sufficiently put it into after drying,
Up to required phosphorous inherent fire-retardant fiber element base heat-barrier material after drying.
Further, the phosphorylation modifying agent is one of monoammonium phosphate and phosphoric acid dicyan ammonium.
Further, after being stirred to react in the step 2,1~2h is ultrasonically treated before washing, defibrating processing.
Further, the metal salt is one of calcium chloride, copper chloride, nickel chloride and iron chloride；Metal hydroxide
Object is calcium hydroxide.
Further, heat treatment time is 2~60min in the step 1, and the reaction time is 1~2h in step 2.
Further, the freezing is cured as handling 1~20min in liquid nitrogen bath, is freeze-dried as under the conditions of -50 DEG C
Dry for 24 hours~72h.
A kind of phosphorous inherent fire-retardant fiber element base heat-barrier material, the phosphorous inherent fire-retardant fiber element base heat-barrier material are led
Hot coefficient is 25mWm-1K-1~39mWm-1K-1。
The beneficial effects of the present invention are:
(1) the phosphorous inherent fire-retardant fiber element base heat-barrier material that the present invention obtains contains phosphonium ion with what metal-lithium ion was modified
Group is fire-retardant functional group, effectively improves the flame retarding efficiency of phosphorus-containing groups；
(2) the phosphorous inherent fire-retardant fiber element base heat-barrier material that the present invention obtains changes tradition by Ionization Modification
The fire-retardant mode of phosphorus-containing groups enhances phosphorus-containing groups condensed phase fire retardancy, reduces flue gas release, and metal ion has
Certain synergistic fire retardation, further catalysis material are decomposed to form stable layer of charcoal；Metal ion crosslinked network enhances simultaneously
The active force of cellulosic molecule interchain effectively improves the mechanical property of material；
(3) the obtained phosphorous inherent fire-retardant fiber element base heat-barrier material of the present invention is in three-dimensional porous structure, thermal coefficient and
Density is low, flame retardant property is good；
(4) preparation process of the present invention is simple, raw material sources are extensive, at low cost, environmentally protective, in answering for heat-insulation and heat-preservation field
With having a high potential.
Specific embodiment
The present invention will be further described combined with specific embodiments below.
A kind of preparation method of phosphorous inherent fire-retardant fiber element base heat-barrier material, comprising the following steps:
Step 1: to the biomass material containing cellulose, with deionized water, to obtain cellulose fibre outstanding for carrying out washing treatment repeatedly
Supernatant liquid；In the cellulose suspension of 1wt%~10wt%, urea and phosphorylation modifying agent is added, in 150 DEG C~165 DEG C items
Under part, after stirring evenly sufficiently reaction, washing obtains phosphorous cellulose；Wherein deoxyglucose sugar unit in cellulose, urea and
Phosphorylation modifier molar ratio is 0.4~1.5:4~5:1.
Phosphorylation modifying agent is one of monoammonium phosphate and phosphoric acid dicyan ammonium；Heat treatment time is 2~60min, step
The reaction time is 1~2h in rapid 2.
Step 2: the phosphorous cellulose that step 1 obtains is added in deionized water to the suspension for being configured to 0.5wt%~2wt%
Liquid, it is 9.5~12 that sodium hydroxide is added under the conditions of high-speed stirred and adjusts its pH, after continuing to stir sufficiently reaction, uses deionized water
It is obtained after washing, defibering phosphorous cellulose nano-fibrous.
After being stirred to react, 1~2h is ultrasonically treated before washing, defibrating processing；Defibering can be carried out using high pressure homogenizer
Processing or material high-speed stirred are handled.
Step 3: by step 2 obtain it is phosphorous it is cellulose nano-fibrous by shaped in situ method or post-processing cross-linking method, will
It is phosphorous it is cellulose nano-fibrous in phosphorus-containing groups Ionization Modification after obtain needed for the phosphorous heat-insulated material of inherent fire-retardant fiber element base
Material.
Wherein detailed process is as follows for shaped in situ method:
The phosphorous cellulose nano-fibrous suspension for being configured to 0.5wt%~2wt% will be prepared in step 2, high speed
After mixing evenly, 0.05mol/L aqueous metal salt or metal hydroxides aqueous solution is added dropwise, stands 6h~12h crosslinking
After be washed with deionized；It is placed in 1~20min of freezing processing in liquid nitrogen bath, carries out freezing solidification；Then by the sample after freezing
For 24 hours~72h is dried under the conditions of being placed in -50 DEG C；Finally sample is placed in vacuum drying oven sufficiently dry under the conditions of 80 DEG C~100 DEG C
Up to required phosphorous inherent fire-retardant fiber element base heat-barrier material after dry.
Post-processing cross-linking method, detailed process is as follows:
The phosphorous cellulose nano-fibrous suspension for being configured to 0.5wt%~2wt% will be prepared in step 2, high speed
After mixing evenly, it is placed in 1~20min of freezing processing in liquid nitrogen bath, carries out freezing solidification；Then the sample after freezing is placed in-
For 24 hours~72h is dried under the conditions of 50 DEG C；Sample is placed in vacuum drying oven sufficiently dry under the conditions of 80 DEG C~100 DEG C；It will dry
Sample afterwards is put into soaking at room temperature 6h~12h in the alcoholic solution of saturation metal salt alcoholic solution or metal oxide, takes out sample and is put into
Up to required phosphorous inherent fire-retardant fiber element base heat-barrier material after vacuum drying oven is dry.
Metal salt is one of calcium chloride, copper chloride, nickel chloride and iron chloride；Metal hydroxides is calcium hydroxide,
Solvent in alcoholic solution includes but is not limited to ethyl alcohol and methanol.
Stirring in text is all made of blender progress, is stirred under normal circumstances using the speed of 2000r/min or more,
So the stirring mentioned in specific embodiment is high-speed stirred；But mixing speed can also be adjusted according to specific circumstances.
Embodiment 1
Step 1: cellulose-containing raw material of wood pulp (content of cellulose about 95%) 5g is taken, after being washed repeatedly with deionized water,
The suspension that cellulose mass concentration is 1wt% is configured to deionized water；Into suspension be added 4.9g diammonium hydrogen phosphate and
8.9g urea, stirs evenly；Most of water is dried and removed under the conditions of 70 DEG C, then handles 10min under the conditions of 150 DEG C, is used
Deionized water is washed repeatedly, obtains phosphorous cellulose fibre；
Step 2: phosphorous cellulose fibre being configured to the suspension of 2wt% with deionized water, hydrogen is added under high-speed stirred
Sodium oxide molybdena adjusts pH to 9.5, reacts 1h；Continue to be ultrasonically treated 2h, deionized water washing removes excess sodium hydroxide, mechanical defibering
Handle be made phosphorus content be 0.5% it is phosphorous cellulose nano-fibrous；
Step 3: by phosphorous cellulose nano-fibrous 1wt% suspension, high-speed stirred is uniform, and 0.05mol/L is added dropwise
Calcium hydroxide aqueous solution；It is stored at room temperature 12h crosslinking, deionized water washing；It is placed in freezing processing 20min in liquid nitrogen bath, is carried out cold
Freeze solidification；Then 72h is freeze-dried under the conditions of the sample after freezing being placed in -50 DEG C；Finally sample is put into vacuum drying oven
Drying for 24 hours, finally obtains phosphorous inherent fire-retardant fiber element base heat-barrier material under the conditions of 100 DEG C.
Embodiment 2
Step 1: cellulose-containing raw material of wood pulp (content of cellulose about 95%) 5g is taken, after being washed repeatedly with deionized water,
The suspension that cellulose mass concentration is 1wt% is configured to deionized water；Into suspension be added 4.9g diammonium hydrogen phosphate and
8.9g urea, stirs evenly；Most of water is dried and removed under the conditions of 70 DEG C, then handles 60min under the conditions of 150 DEG C, is used
Deionized water is washed repeatedly, obtains phosphorous cellulose fibre；
Step 2: phosphorous cellulose fibre being configured to the suspension of 2wt% with deionized water, hydrogen is added under high-speed stirred
Sodium oxide molybdena adjusts pH to 9.5, reacts 1h；Continue to be ultrasonically treated 2h, deionized water washing removes excess sodium hydroxide, mechanical defibering
Handle be made phosphorus content be 0.7% it is phosphorous cellulose nano-fibrous；
Step 3: by phosphorous cellulose nano-fibrous 0.50wt% suspension, high-speed stirred is uniform, is added dropwise
0.05mol/L copper chloride solution；It is stored at room temperature 12h crosslinking, deionized water washing；It is placed in freezing processing 20min in liquid nitrogen bath,
Carry out freezing solidification；Then 72h is freeze-dried under the conditions of the sample after freezing being placed in -50 DEG C；Sample is finally put into vacuum
Drying for 24 hours, finally obtains phosphorous inherent fire-retardant fiber element base heat-barrier material under the conditions of 100 DEG C in baking oven.
Embodiment 3
Step 1: cellulose-containing raw material of wood pulp (content of cellulose about 95%) 5g is taken, after being washed repeatedly with deionized water,
The suspension that cellulose mass concentration is 1wt% is configured to deionized water；Into suspension be added 10.2g diammonium hydrogen phosphate and
18.6g urea, stirs evenly；Most of water is dried and removed under the conditions of 70 DEG C, then handles 30min under the conditions of 150 DEG C, is used
Deionized water is washed repeatedly, obtains phosphorous cellulose fibre；
Step 2: phosphorous cellulose fibre being configured to the suspension of 2wt% with deionized water, hydrogen is added under high-speed stirred
Sodium oxide molybdena adjusts pH to 9.5, reacts 1h；Continue to be ultrasonically treated 2h, deionized water washing removes excess sodium hydroxide, mechanical defibering
Handle be made phosphorus content be 1.7% it is phosphorous cellulose nano-fibrous；
Step 3: by phosphorous cellulose nano-fibrous 1wt% suspension, high-speed stirred is uniform, and 0.05mol/L is added dropwise
Copper chloride solution；It is stored at room temperature 12h crosslinking, deionized water washing；It is placed in freezing processing 20min in liquid nitrogen bath, is freezed
Solidification；Then 72h is freeze-dried under the conditions of the sample after freezing being placed in -50 DEG C；Finally sample is put into 80 in vacuum drying oven
DEG C~100 DEG C under the conditions of it is dry for 24 hours, finally obtain phosphorous inherent fire-retardant fiber element base heat-barrier material.
Embodiment 4
Step 1: cellulose-containing raw material of wood pulp (content of cellulose about 95%) 9g is taken, after being washed repeatedly with deionized water,
The suspension that cellulose mass concentration is 10wt% is configured to deionized water；Into suspension be added 4.3g diammonium hydrogen phosphate and
11.2g urea, stirs evenly；Most of water is dried and removed under the conditions of 70 DEG C, then handles 2min under the conditions of 165 DEG C, is used
Deionized water is washed repeatedly, obtains phosphorous cellulose fibre；
Step 2: phosphorous cellulose fibre being configured to the suspension of 2wt% with deionized water, hydrogen is added under high-speed stirred
Sodium oxide molybdena adjusts pH to 12, reacts 1h；Continue to be ultrasonically treated 2h, deionized water washing removes excess sodium hydroxide, mechanical defibering
Handle be made phosphorus content be 1.4% it is phosphorous cellulose nano-fibrous；
Step 3: by phosphorous cellulose nano-fibrous 1wt% suspension, high-speed stirred is uniform, and 0.05mol/L is added dropwise
Nickel chloride aqueous solution；It is stored at room temperature 12h crosslinking, deionized water washing；It is placed in freezing processing 20min in liquid nitrogen bath, is freezed
Solidification；Then 72h is freeze-dried under the conditions of the sample after freezing being placed in -50 DEG C；Finally sample is put into 100 in vacuum drying oven
Drying for 24 hours, finally obtains phosphorous inherent fire-retardant fiber element base heat-barrier material under the conditions of DEG C.
Embodiment 5
Step 1: cellulose-containing raw material of wood pulp (content of cellulose about 95%) 5g is taken, after being washed repeatedly with deionized water,
The suspension that cellulose mass concentration is 1wt% is configured to deionized water；Into suspension be added 10.2g diammonium hydrogen phosphate and
18.6g urea, stirs evenly；Most of water is dried and removed under the conditions of 70 DEG C, then handles 10min under the conditions of 150 DEG C, is used
Deionized water is washed repeatedly, obtains phosphorous cellulose fibre；
Step 2: phosphorous cellulose fibre being configured to the suspension of 2wt% with deionized water, hydrogen is added under high-speed stirred
Sodium oxide molybdena adjusts pH to 9.5, reacts 1h；Continue to be ultrasonically treated 2h, deionized water washing removes excess sodium hydroxide, mechanical defibering
Handle be made phosphorus content be 1.1% it is phosphorous cellulose nano-fibrous；
Step 3: by phosphorous cellulose nano-fibrous 1wt% suspension, high-speed stirred is uniform, and 0.05mol/L is added dropwise
Ferric chloride in aqueous solution；It is stored at room temperature 12h crosslinking, deionized water washing；It is placed in freezing processing 20min in liquid nitrogen bath, is freezed
Solidification；Then 72h is freeze-dried under the conditions of the sample after freezing being placed in -50 DEG C；Finally sample is put into 100 in vacuum drying oven
Drying for 24 hours, finally obtains phosphorous inherent fire-retardant fiber element base heat-barrier material under the conditions of DEG C.
Embodiment 6
Step 1: cellulose-containing raw material of wood pulp (content of cellulose about 95%) 5g is taken, after being washed repeatedly with deionized water,
The suspension that cellulose mass concentration is 1wt% is configured to deionized water；Into suspension be added 4.9g diammonium hydrogen phosphate and
8.9g urea, stirs evenly；Most of water is dried and removed under the conditions of 70 DEG C, then handles 10min under the conditions of 150 DEG C, is used
Deionized water is washed repeatedly, obtains phosphorous cellulose fibre；
Step 2: phosphorous cellulose fibre being configured to the suspension of 2wt% with deionized water, hydrogen is added under high-speed stirred
Sodium oxide molybdena adjusts pH to 9.5, reacts 1h；Continue to be ultrasonically treated 2h, deionized water washing removes excess sodium hydroxide, mechanical defibering
Handle be made phosphorus content be 0.5% it is phosphorous cellulose nano-fibrous；
Step 3: by phosphorous cellulose nano-fibrous 1wt% suspension, high-speed stirred is uniform, is placed in liquid nitrogen bath at freezing
20min is managed, freezing solidification is carried out；Then 72h is freeze-dried under the conditions of the sample after freezing being placed in -50 DEG C；Then by sample
It is put into vacuum drying oven and is further dried, the sample after drying is put into soaking at room temperature 6h in saturation calcium chloride ethanol solution, most
Taking-up sample is put into vacuum drying oven and is dried to obtain phosphorous inherent fire-retardant fiber element base heat-barrier material afterwards.
Embodiment 7
Step 1: cellulose-containing raw material of wood pulp (content of cellulose about 95%) 5g is taken, after being washed repeatedly with deionized water,
The suspension that cellulose mass concentration is 1wt% is configured to deionized water；Into suspension be added 4.9g diammonium hydrogen phosphate and
8.9g urea, stirs evenly；Most of water is dried and removed under the conditions of 70 DEG C, then handles 60min under the conditions of 150 DEG C, is used
Deionized water is washed repeatedly, obtains phosphorous cellulose fibre；
Step 2: phosphorous cellulose fibre being configured to the suspension of 2wt% with deionized water, hydrogen is added under high-speed stirred
Sodium oxide molybdena adjusts pH to 9.5, reacts 1h；Continue to be ultrasonically treated 2h, deionized water washing removes excess sodium hydroxide, mechanical defibering
Handle be made phosphorus content be 0.7% it is phosphorous cellulose nano-fibrous；
Step 3: by phosphorous cellulose nano-fibrous 1wt% suspension, high-speed stirred is uniform, is placed in liquid nitrogen bath at freezing
20min is managed, freezing solidification is carried out；Then 72h is freeze-dried under the conditions of the sample after freezing being placed in -50 DEG C；Then by sample
It is put into vacuum drying oven and is further dried, the sample after drying is put into soaking at room temperature 6h in saturation calcium chloride ethanol solution, most
Taking-up sample is put into vacuum drying oven and is dried to obtain phosphorous inherent fire-retardant fiber element base heat-barrier material afterwards.
Embodiment 8
Step 1: cellulose-containing raw material of wood pulp (content of cellulose about 95%) 5g is taken, after being washed repeatedly with deionized water,
The suspension that cellulose mass concentration is 1wt% is configured to deionized water；Into suspension be added 10.2g diammonium hydrogen phosphate and
18.6g urea, stirs evenly；Most of water is dried and removed under the conditions of 70 DEG C, then handles 30min under the conditions of 150 DEG C, is used
Deionized water is washed repeatedly, obtains phosphorous cellulose fibre；
Step 2: phosphorous cellulose fibre being configured to the suspension of 2wt% with deionized water, hydrogen is added under high-speed stirred
Sodium oxide molybdena adjusts pH to 9.5, reacts 1h；Continue to be ultrasonically treated 2h, deionized water washing removes excess sodium hydroxide, mechanical defibering
Handle be made phosphorus content be 1.7% it is phosphorous cellulose nano-fibrous；
Step 3: by the suspension of phosphorous cellulose nano-fibrous 1wt%, high-speed stirred is uniform, is placed in liquid nitrogen bath and freezes
20min is handled, freezing solidification is carried out；Then 72h is freeze-dried under the conditions of the sample after freezing being placed in -50 DEG C；Then by sample
Product are put into vacuum drying oven and are further dried, and the sample after drying is put into soaking at room temperature 6h in saturation copper chloride methanol solution,
Finally taking-up sample is put into vacuum drying oven and is dried to obtain phosphorous inherent fire-retardant fiber element base heat-barrier material.
Embodiment 9
Step 1: cellulose-containing raw material of wood pulp (content of cellulose about 95%) 9g is taken, after being washed repeatedly with deionized water,
The suspension that cellulose mass concentration is 10wt% is configured to deionized water；Into suspension be added 4.3g diammonium hydrogen phosphate and
11.2g urea, stirs evenly；Most of water is dried and removed under the conditions of 70 DEG C, then handles 2min under the conditions of 165 DEG C, is used
Deionized water is washed repeatedly, obtains phosphorous cellulose fibre；
Step 2: phosphorous cellulose fibre being configured to the suspension of 2wt% with deionized water, hydrogen is added under high-speed stirred
Sodium oxide molybdena adjusts pH to 12, reacts 1h；Continue to be ultrasonically treated 2h, deionized water washing removes excess sodium hydroxide, mechanical defibering
Handle be made phosphorus content be 1.4% it is phosphorous cellulose nano-fibrous；
Step 3: by the suspension of phosphorous cellulose nano-fibrous 1wt%, high-speed stirred is uniform, is placed in liquid nitrogen bath and freezes
20min is handled, freezing solidification is carried out；Then 72h is freeze-dried under the conditions of the sample after freezing being placed in -50 DEG C；Then by sample
Product are put into vacuum drying oven and are further dried, and the sample after drying is put into soaking at room temperature 6h in saturation nickel chloride methanol solution,
Finally taking-up sample is put into vacuum drying oven and is dried to obtain phosphorous inherent fire-retardant fiber element base heat-barrier material.
The phosphorous inherent fire-retardant fiber element base heat-barrier material being prepared in Examples 1 to 9, after tested oxygen index (OI) LOI value
21~30 are increased to from the 18~19 of pure cellulose base heat-barrier material, there is good self-extinguishment；Compression modulus is compared to pure fibre
It ties up plain base heat-barrier material and improves 1~2 times, thermal coefficient is maintained at 25mWm-1K-1~39mWm-1K-1。
P elements are a kind of efficient ignition-proof elements, and the introducing of a small amount of phosphonium flame retardant can significantly improve polymer material
Flame retardant property；Traditional organic phosphorus-containing groups generally have certain gas phase fire retardation, increase material in combustion
Flue gas release, and much phosphorous gases all have certain toxicity；Phosphorus-containing groups are ionized, and changeable phosphorus-containing groups exist
Decomposition path-ways when burning promote phosphorous fragment to move to burning surface under high temperature and are condensed to form Quadrafos；Catalytic polymer
Substrate is dehydrated the graphite-structure to form aromatisation, forms more continuous fine and close expanding layer, plays the fire-retardant work of outstanding condensed phase
With enhancing flame retarding efficiency reduces the release of poison gas；In addition certain metal ions have catalysis well to polymeric substrate
At the effect of charcoal, the addition of a small amount of metal ion tends to the anti-flammability for being obviously improved flame-retardant system；By cation be metal from
The phosphorus-containing groups of son introduce cellulose molecular chain, and the phosphorous inherent fire-retardant fiber base heat-barrier material of metal ion crosslinked is made, can
Achieve the purpose that highly effective flame-retardant and mechanical property enhancing.
The present invention uses the biomass material of cellulose, modified using phosphorylation, and by phosphate group and metal ion knot
Conjunction is prepared；The phosphorous functional group in inherent flame retardant polymer material be prepared by traditional response type phosphonium flame retardant
Usually there is apparent gas phase fire retardation, the burst size of flue gas in combustion process can be dramatically increased；Ionization changes tradition and contains
The fire-retardant mode of phosphorus group enhances phosphorus-containing groups condensed phase fire retardancy, is catalyzed fibrin substrate into charcoal, helps to show
Flue gas release when reducing material combustion is write, anti-flammability is improved.There are metal ion itself catalyst substrates to carbonize ability, and contain
Special synergistic effect between phosphonium ion group helps to further increase flame retarding efficiency and inhibits flue gas release, and enhancing layer of charcoal causes
Close property；The reversible action of metal ion and phosphorous cellulosic molecule interchain can enhance the stability of three-D pore structure, meanwhile, it is formed
Ionomer network increase the interconnection between pore structure, play mechanics enhancing effect；In addition, with addition blend
The flame resistant method of combustion is compared, and the problem of poor compatibility is with mutually separating is not present in inherent flame retardant；Phosphorous intrinsically flame retarded anti-flammability is held
Long, flame retarding efficiency is high, and the fire-retardant group amount of introducing is few and without adding other modifying agents, avoids fire retardant height addition device to hole
Structural damage helps to maintain the low-density and low thermal conductivity of material.
The phosphorous inherent fire-retardant fiber element base heat-barrier material that the present invention is prepared significantly enhances the resistance of cellulosic material
Combustion property, the characteristics of improving its mechanical property, maintain low-density and low thermal conductivity；And with other flame-retarded technology phases
Than metal-modified phosphorous ionic group flame retarding efficiency is high, and less usage amount can reach good flame retardant effect.System of the present invention
Standby simple process, raw material sources are extensive, environmentally protective, have good practical application value in heat-insulation and heat-preservation field, using latent
Power is huge.
Claims (9)
1. a kind of preparation method of phosphorous inherent fire-retardant fiber element base heat-barrier material, which comprises the following steps:
Step 1: in the cellulose suspension of 1wt%~10wt% concentration, urea and phosphorylation modifying agent is added, at 150 DEG C
Under the conditions of~165 DEG C, after stirring evenly sufficiently reaction, washing obtains phosphorous cellulose；Wherein deoxyglucose list in cellulose
Member, urea and phosphorylation modifier molar ratio are 0.4~1.5:4~5:1；
Step 2: the phosphorous cellulose that step 1 is obtained is configured to the suspension of 0.5wt%~2wt%, adjust its pH be 9.5~
12, after sufficiently reacting under stirring condition, obtained after washing, defibering phosphorous cellulose nano-fibrous；
Step 3: by step 2 obtain it is phosphorous it is cellulose nano-fibrous by shaped in situ method or post-processing cross-linking method, will be phosphorous
Phosphorous inherent fire-retardant fiber element base heat-barrier material needed for being obtained after phosphorus-containing groups Ionization Modification in cellulose nano-fibrous.
2. a kind of preparation method of phosphorous inherent fire-retardant fiber element base heat-barrier material according to claim 1, feature exist
In detailed process is as follows for the step 3 shaped in situ method:
The phosphorous cellulose nano-fibrous suspension for being configured to 0.5wt%~2wt% will be prepared in step 2, stir evenly
Afterwards, 0.05mol/L aqueous metal salt or metal hydroxides aqueous solution is added dropwise, is washed after standing 6h~12h crosslinking；It is cold
It is freeze-dried after freezing solidification, up to required phosphorous inherent fire-retardant fiber element after finally sufficiently being dried under the conditions of 80 DEG C~100 DEG C
Base heat-barrier material.
3. a kind of preparation method of phosphorous inherent fire-retardant fiber element base heat-barrier material according to claim 1, feature exist
In detailed process is as follows for the post-processing cross-linking method in the step 3:
The phosphorous cellulose nano-fibrous suspension for being configured to 0.5wt%~2wt% will be prepared in step 2, stir evenly
Afterwards, freezing solidification, freeze-drying process, it is then sufficiently dry under the conditions of 80 DEG C~100 DEG C；
Alcohol solution for soaking 6h~12h of saturation metal salt alcoholic solution or metal oxide is sufficiently put it into after drying, it is dry
Afterwards up to required phosphorous inherent fire-retardant fiber element base heat-barrier material.
4. a kind of preparation method of phosphorous inherent fire-retardant fiber element base heat-barrier material according to claim 1, feature exist
In the phosphorylation modifying agent is one of monoammonium phosphate and phosphoric acid dicyan ammonium.
5. a kind of preparation method of phosphorous inherent fire-retardant fiber element base heat-barrier material according to claim 1, feature exist
In, after being stirred to react in the step 2,1~2h of ultrasonic treatment before washing, defibrating processing.
6. a kind of preparation method of phosphorous inherent fire-retardant fiber element base heat-barrier material according to claim 2 or 3, feature
It is, the metal salt is one of calcium chloride, copper chloride, nickel chloride and iron chloride；Metal hydroxides is calcium hydroxide.
7. a kind of preparation method of phosphorous inherent fire-retardant fiber element base heat-barrier material according to claim 1, feature exist
In heat treatment time is 2~60min in the step 1, and the reaction time is 1~2h in step 2.
8. a kind of preparation method of phosphorous inherent fire-retardant fiber element base heat-barrier material according to claim 2 or 3, feature
Be, the freezing is cured as handling 1~20min in liquid nitrogen bath, be freeze-dried under the conditions of -50 DEG C it is dry for 24 hours~
72h。
9. a kind of phosphorous inherent fire-retardant fiber element base heat-barrier material that preparation method as described in claim 1 obtains, feature exist
In the thermal coefficient of the phosphorous inherent fire-retardant fiber element base heat-barrier material is 25mWm-1K-1~39mWm-1K-1。
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Application publication date: 20190628 |