CN107573630A - A kind of chitosan tetramethylene sulfuric acid phosphine fire retardant and its preparation method and application - Google Patents
A kind of chitosan tetramethylene sulfuric acid phosphine fire retardant and its preparation method and application Download PDFInfo
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Abstract
The invention provides a kind of preparation method of chitosan tetramethylene sulfuric acid phosphine fire retardant, following preparation process is included：Tetrakis hydroxymetyl phosphonium sulfuric and chitosan are subjected to Electrostatic Absorption in water, obtain tetrakis hydroxymetyl phosphonium sulfuric/chitosan complexes；Tetrakis hydroxymetyl phosphonium sulfuric/the chitosan complexes are carried out into dehydration covalence graft to react to obtain chitosan tetramethylene sulfuric acid phosphine fire retardant.The chitosan tetramethylene sulfuric acid phosphine fire retardant that method provided by the invention is prepared is free of halogen, has antibacterial action, and non-toxic degradable, green；Flame retardant molecule amount is high, it is linear to keep, non-volatility, water-fastness, resistance to migration, compatibility is good, stability is high, good flame retardation effect.
Description
Technical field
The present invention relates to halogen-free flame retardants technical field, more particularly to a kind of chitosan tetramethylene sulfuric acid phosphine fire retardant and
Its preparation method and application.
Background technology
Polyacrylonitrile belongs to inflammable high polymer material, and larger cyanide of toxicity etc. is released when burning.Work in the world
The fire-retardant polyacrylonitrile material of industry, fire resistance, but halogen flame retardant are mainly improved by VCM modification by copolymerization
Agent smoke amount during fire-retardant is huge, can produce a large amount of pernicious gases, is not environment-friendly products.
Expansion type flame retardant is typically the unimolecule or molecule composite flame-retardant agent based on phosphorus, nitrogen, carbon, wherein carbon member
Element is charing source；Phosphorus is acid source, plays catalytic action；Nitrogen is source of the gas, plays expansion.Expansion type flame retardant is to general high
Molecular material has good flame-retarding characteristic, because being free of halogen, is referred to as Green Flammability agent.But compared with halogen flame,
Traditional expanding fire retardant also has many shortcomings, for example, flame retarding efficiency is low, heat endurance is low, low water resistance, these problems are serious
Influence expanding fire retardant application.
Tetrakis hydroxymetyl phosphonium sulfuric is often used as environment-friendly type bactericide, and completely harmless thing can be degraded rapidly to after use
Matter.Tetrakis hydroxymetyl phosphonium sulfuric can use as the permanent sex flame retardant of polyester-cotton fabric, and can be with urea, thiocarbamide, melamine etc.
Amine substance prepares fire retardant, but these flame retardant molecule amounts are small, and poor compatibility, degradability are poor.
The content of the invention
In view of this, it is an object of the invention to provide a kind of chitosan tetramethylene sulfuric acid phosphine fire retardant and its preparation side
Method, the flame retardant molecule amount of the invention being prepared is high, compatibility is good, non-toxic degradable, and good flame retardation effect.
In order to realize foregoing invention purpose, the present invention provides following technical scheme：
A kind of preparation method of chitosan tetramethylene sulfuric acid phosphine fire retardant, includes following preparation process：
Tetrakis hydroxymetyl phosphonium sulfuric and chitosan are subjected to Electrostatic Absorption in water, obtain tetrakis hydroxymetyl phosphonium sulfuric/chitosan
Compound；
Tetrakis hydroxymetyl phosphonium sulfuric/the chitosan complexes are carried out into dehydration covalence graft to react to obtain the methylene of chitosan four
Base sulfuric acid phosphine fire retardant.
Preferably, the mass ratio of the tetrakis hydroxymetyl phosphonium sulfuric and chitosan is 1：1~5：1, the chitosan and water
Mass ratio is 1:0.5~1:1.
Preferably, the viscosity average molecular weigh of the chitosan is 30,000~150,000；The deacetylation of the chitosan is not less than
80%.
Preferably, the temperature of the Electrostatic Absorption is 80~95 DEG C.
Preferably, the time of the Electrostatic Absorption is 1.5~3h.
Preferably, the dehydration covalence graft reaction temperature is 140~180 DEG C.
Preferably, the time of the dehydration covalence graft reaction is 2~4h.
Present invention also offers the chitosan tetramethylene sulfuric acid phosphine fire retardant by described preparation method preparation.
Present invention also offers chitosan tetramethylene sulfuric acid phosphine fire retardant described in such scheme is fire-retardant as polyacrylonitrile
The application of agent.
Advantageous effects：
The invention provides a kind of preparation method of chitosan tetramethylene sulfuric acid phosphine fire retardant.The preparation method of the present invention
Using chitosan and tetrakis hydroxymetyl phosphonium sulfuric as raw material, chitosan has linear macromolecule structure, thus and tetrakis hydroxymetyl phosphonium sulfuric
The fire retardant of gained also has macromolecular structure after polymerization；The macromolecular structure of fire retardant make its with it is polyacrylonitrile blended after,
It is not easy to overflow, it is lasting with good water-fast persistence, usability；And the easy film forming of chitosan, has well with polyacrylonitrile
Interface compatibility, prepared fire retardant surface is uniform, non-blooming；Chitosan has antibacterial functions, thus is improving polypropylene
Can endowing antibacterial energy while nitrile anti-flaming function；Containing more ignition-proof elements such as C, S, P, N in flame retardant molecule, because element sulphur has
There are a catalytic performance and anti-dropping function, more common expansion type flame retardant is more efficient.The preparation method of the present invention is simple, without using
Organic solvent, reaction product need not carry out washing purifying, and raw material is cheap and easy to get, without halogen, without metal, because of chitosan and four
Methylol sulfuric acid phosphorus is degradable, therefore prepared chitosan tetramethylene sulfuric acid phosphine is also degradable, green.
Present invention also offers fire retardant prepared by preparation method described in such scheme.Fire retardant prepared by the present invention is free of
Halogen, there is antibacterial action, and non-toxic degradable, it is green；Flame retardant molecule amount is high, it is linear to keep, non-volatility, water-fast
Wash, it is resistance to migration, compatibility is good, stability is high, good flame retardation effect.Embodiment result shows to be prepared into by technical scheme
To fire retardant charring rate it is high, expansion multiple is high, flame retardant rating can reach B1 grades.
Brief description of the drawings
Fig. 1 is the IR Characterization collection of illustrative plates of gained chitosan tetramethylene sulfuric acid phosphine solid powder in the embodiment of the present invention 1；
Fig. 2 is the polyacrylonitrile flame-retardant compounds film obtained in embodiment 6；
Fig. 3 is the polyacrylonitrile system after the cohesion obtained in comparative example 3.
Embodiment
The invention provides a kind of preparation method of chitosan tetramethylene sulfuric acid phosphine fire retardant, and step is prepared comprising following
Suddenly：
Tetrakis hydroxymetyl phosphonium sulfuric and chitosan are subjected to Electrostatic Absorption in water, obtain tetrakis hydroxymetyl phosphonium sulfuric/chitosan
Compound；
Tetrakis hydroxymetyl phosphonium sulfuric/the chitosan complexes are carried out into dehydration covalence graft to react to obtain the methylene of chitosan four
Base sulfuric acid phosphine fire retardant.
Tetrakis hydroxymetyl phosphonium sulfuric and chitosan are carried out Electrostatic Absorption by the present invention in water, obtain tetrakis hydroxymetyl phosphonium sulfuric/
Chitosan complexes.In the present invention, the mass ratio of the tetrakis hydroxymetyl phosphonium sulfuric and chitosan is preferably 1：1~5：1, it is more excellent
Elect 2 as：1~4：1；The mass ratio of the chitosan and water is preferably 1:0.5~1:1, more preferably 1：1.In the present invention, institute
The viscosity average molecular weigh for stating chitosan is preferably 30,000~150,000, more preferably 50,000~120,000, most preferably 80,000~100,000；It is described
The deacetylation of chitosan is preferably to spend >=80%, more preferably >=90%.In the present invention, the temperature of the Electrostatic Absorption is excellent
Elect 80~95 DEG C, more preferably 85~90 DEG C as；The Electrostatic Absorption time is preferably 1.5~3h, more preferably 2~2.5h.
In the present invention, the Electrostatic Absorption is preferably carried out under agitation, and the stir speed (S.S.) is preferably 200~400r/min,
More preferably 250~350r/min.
In a particular embodiment of the present invention, after preferably tetrakis hydroxymetyl phosphonium sulfuric, chitosan and water being mixed at normal temperatures
Stirring and dissolving, Electrostatic Absorption temperature is then warming up to again；The Electrostatic Absorption time of the present invention is from when being warming up to Electrostatic Absorption temperature
Start to calculate.Many basic amine groups are dispersed with chitosan molecule chain, can be with sulfate ion Electrostatic Absorption into salt；And hydroxyl
Base, N- acetylaminos provide P, O in lone electron and tetrahydroxy sulfuric acid phosphorus etc. and produce intermolecular force, are inhaled so as to complete electrostatic
Attached effect.
After obtaining tetrakis hydroxymetyl phosphonium sulfuric/chitosan complexes, the present invention is multiple by the tetrakis hydroxymetyl phosphonium sulfuric/chitosan
Compound carries out being dehydrated covalence graft reaction, obtains chitosan tetramethylene sulfuric acid phosphine fire retardant.In the present invention, the dehydration is common
Valency graft reaction temperature is preferably 140~180 DEG C, more preferably 150~170 DEG C；The dehydration covalence graft reaction time is excellent
Elect 2~4h, more preferably 2.5~3.5h as.The device that the present invention is used dehydration covalence graft reaction does not have particular/special requirement, energy
Enough reach temperature needed for dehydration covalence graft reaction, in specific embodiment of the present invention, described dehydration covalence graft
Reaction preferably stands and carried out in an oven.
In a particular embodiment of the present invention, dehydration is directly warming up to preferably by Electrostatic Absorption products therefrom system covalently to connect
Branch reaction temperature carries out being dehydrated covalence graft reaction, without carrying out any post processing to Electrostatic Absorption product system.
It is dehydrated after the completion of covalence graft reaction, the present invention will preferably obtain chitosan dehydration covalence graft reaction product system
Dry, obtain chitosan tetramethylene sulfuric acid phosphine fire retardant.In the present invention, the drying temperature is preferably 60~90 DEG C, more
Preferably 70~80 DEG C；The drying time is preferably 10~15h, more preferably 12~14h.The present invention will preferably be dehydrated covalent
Graft reaction product system is cooled to drying temperature, is then dried, and the present invention is to the specific method of the cooling without spy
It is different to limit, cooled using this area conventional warm-down method, such as natural cooling.The present invention is to specific drying means without spy
It is different to limit, using drying means well known to those skilled in the art, such as it is dried in drying box.
Present invention also offers the chitosan tetramethylene sulfuric acid phosphine resistance that the preparation method described in such scheme is prepared
Fire agent.In the dehydration covalence graft course of reaction of the present invention, on the hydroxyl and chitosan on the tetrakis hydroxymetyl phosphonium sulfuric
Covalence graft reaction occurs for amino dehydration, and the corresponding water for sloughing a molecule, primary amine all participates in or subparticipation is converted into secondary amine,
Tetrakis hydroxymetyl phosphonium sulfuric is grafted in chitosan molecule chain.The methylene of chitosan four when primary amine all participates in being converted into secondary amine
Base sulfuric acid phosphine fire retardant has structure shown in Formulas I：
In the present invention, the n values are preferably 50~250, more preferably 100~200, most preferably 150~180.
Fire retardant provided by the invention has the linear macromolecule structure of similar chitosan, for the fire-retardant of polyacrylonitrile
When, by fire retardant described in above-mentioned technical proposal with it is polyacrylonitrile blended after, be not easy to overflow, there is good water-fast persistence, make
It is lasting with property；And the easy film forming of chitosan, there is a good interface compatibility with polyacrylonitrile, prepared fire retardant surface is equal
It is even, it is non-blooming；Chitosan has antibacterial functions, thus can endowing antibacterial energy while polyacrylonitrile anti-flaming function is improved；
It is relatively common swollen because element sulphur has catalytic performance and anti-dropping function containing more ignition-proof elements such as C, S, P, N in flame retardant molecule
Swollen type fire retardant is more efficient.
Present invention also offers application of the chitosan tetramethylene sulfuric acid phosphine fire retardant as polyacrylonitrile fire retardant.
The present invention is not particularly limited to application of the chitosan tetramethylene sulfuric acid phosphine fire retardant in polyacrylonitrile material, using ability
The application process of fire retardant known to field technique personnel, it specifically will such as use blending method, chitosan tetramethylene sulfuric acid
Phosphine fire retardant is directly made an addition in polyacrylonitrile matrix, and fire-retardant polyacrylonitrile material is then made.In the specific implementation of the present invention
In example, the addition of the chitosan tetramethylene sulfuric acid phosphine fire retardant is preferably the 2%~20% of polyacrylonitrile quality, more excellent
Elect 5%~15% as.
Chitosan tetramethylene sulfuric acid phosphine fire retardant provided by the invention and preparation method thereof is entered with reference to embodiment
Row detailed description, but they can not be interpreted as limiting the scope of the present invention.
Embodiment 1
Under normal temperature, chitosan 10g is weighed, is 5 by the mass ratio of tetrakis hydroxymetyl phosphonium sulfuric and chitosan：1, water and chitosan
Mass ratio be 1：1 ratio weighs tetrakis hydroxymetyl phosphonium sulfuric, chitosan (viscosity average molecular weigh is 150,000) and water, is added to reaction
In kettle, stir to chitosan and be completely dissolved, be warming up to 90 DEG C, insulated and stirred 2h, discharging, stand reaction in an oven afterwards, instead
Answer condition：150 DEG C, it is incubated 2h.80 DEG C are cooled to afterwards, are dried 12h, are obtained chitosan tetramethylene sulfuric acid phosphine solid powder
40.61g。
Embodiment 2
Under normal temperature, chitosan 10g is weighed, is 4 by the mass ratio of tetrakis hydroxymetyl phosphonium sulfuric and chitosan：1, water and chitosan
Mass ratio be 1：1 ratio weighs tetrakis hydroxymetyl phosphonium sulfuric, chitosan (viscosity average molecular weigh is 30,000) and water, is added to reaction
In kettle, stir to chitosan and be completely dissolved, be warming up to 80 DEG C, insulated and stirred 3h, discharging, stand react in an oven afterwards, 140
DEG C, it is incubated 4h.60 DEG C are cooled to afterwards, are dried 12h, are obtained chitosan tetramethylene sulfuric acid phosphine solid powder 34.31g.
Embodiment 3
Under normal temperature, chitosan 10g is weighed, is 3 by the mass ratio of tetrakis hydroxymetyl phosphonium sulfuric and chitosan：1, water and chitosan
Mass ratio be 1：1 ratio weighs tetrakis hydroxymetyl phosphonium sulfuric, chitosan (viscosity average molecular weigh is 100,000) and water, is added to reaction
In kettle, stir to chitosan and be completely dissolved, be warming up to 95 DEG C, insulated and stirred 1.5h, discharging, stand reaction in an oven afterwards,
180 DEG C, it is incubated 2h.90 DEG C are cooled to afterwards, are dried 12h, are obtained chitosan tetramethylene sulfuric acid phosphine solid powder 29.03g.
Embodiment 4
Under normal temperature, chitosan 10g is weighed, is 2 by the mass ratio of tetrakis hydroxymetyl phosphonium sulfuric and chitosan：1, water and chitosan
Mass ratio be 0.8：1 ratio weighs tetrakis hydroxymetyl phosphonium sulfuric, chitosan (viscosity average molecular weigh is 130,000) and water, is added to anti-
Answer in kettle, stir to chitosan and be completely dissolved, be warming up to 85 DEG C, insulated and stirred 2.5h, discharging, stand in an oven afterwards anti-
Should, 150 DEG C, it is incubated 3.5h.70 DEG C are cooled to afterwards, are dried 15h, are obtained chitosan tetramethylene sulfuric acid phosphine solid powder
22.94g。
Its IR Characterization collection of illustrative plates is as shown in Figure 1：3220.3cm-1It is hydroxyl-OH and NH to locate wide absworption peak2Stretching vibration
Peak.1646.8cm-1It is primary amine NH in-plane bending vibration absworption peak, illustrates that amino does not participate in reaction completely in chitosan.
1421.8cm-1It is S=O stretching vibration absworption peaks, 1298.3cm-1It is secondary amine C-N stretching vibration absworption peaks, illustrates in chitosan
Amino has dehydration covalence graft reaction with the hydroxyl in tetrakis hydroxymetyl phosphonium sulfuric.1106.7cm-1For C-O stretching vibration absworption peaks.
1044.1cm-1For C-O stretching vibration absworption peaks.924.9cm-1For NH out-of-plane bending vibration absworption peaks.
Embodiment 5
Under normal temperature, chitosan 10g is weighed, is 1 by the mass ratio of tetrakis hydroxymetyl phosphonium sulfuric and chitosan：1, water and chitosan
Mass ratio be 0.5：1 ratio weighs tetrakis hydroxymetyl phosphonium sulfuric, chitosan (viscosity average molecular weigh is 80,000) and water, is added to anti-
Answer in kettle, stir to chitosan and be completely dissolved, be warming up to 90 DEG C, insulated and stirred 2h, discharging, stand reaction in an oven afterwards,
170 DEG C, it is incubated 2.5h.80 DEG C are cooled to afterwards, are dried 14h, are obtained chitosan tetramethylene sulfuric acid phosphine solid powder 15.64g.
The chitosan tetramethylene sulfuric acid phosphine solid powder 0.5g described in embodiment 1~5 is weighed respectively, is put into crucible,
It is placed in Muffle furnace and is warming up to 500 DEG C, be incubated 60min, observes degrees of expansion and carbon yield is calculated according to following formula：
The yield of the chitosan tetramethylene sulfuric acid phosphine of embodiment 1~5, charring rate and expansion multiple are as shown in table 1.
Yield, carbon yield and the expansion multiple of the chitosan tetramethylene sulfuric acid phosphine of table 1
| Embodiment | Yield (%) | Carbon yield (%) | Expansion multiple |
| 1 | 85.49 | 29.0 | 14 |
| 2 | 85.76 | 43.8 | 15 |
| 3 | 89.32 | 35.2 | 12 |
| 4 | 91.76 | 31.1 | 10 |
| 5 | 89.37 | 30.6 | 10 |
The calculation formula of wherein yield is：Yield=chitosan tetramethyl sulfuric acid phosphorus/(chitosan+tetra methylol sulfuric acid
Phosphorus) * 100%, wherein tetrakis hydroxymetyl phosphonium sulfuric is with actual solid content Mass Calculation.
Data in table 1 can be seen that fire retardant carbon yield height prepared by the present invention, and expansion multiple is high, fire-retardant effect
Fruit is good.
Embodiment 6
DMF is added in reactor, by polyacrylonitrile：N, N-dimethylformamide=1:10 ratio
Polyacrylonitrile is added portionwise in reactor to mix with DMF and dissolved, the solution temperature is 50 DEG C.Poly- third
After alkene nitrile is completely dissolved, the chitosan tetramethylene sulfuric acid phosphine solid powder being prepared, the chitosan are added in embodiment 1
Tetramethylene sulfuric acid phosphine solid powder is the 2% of polyacrylonitrile quality, is sufficiently stirred and disperses to obtain translucent stabilising system slurries.
Above-mentioned slurries are applied on inclined glass, slowly rinsed from top to bottom using distilled water, slurries meet MJPZ,
Glass plate is put into cold water together with film and soaks 20min, takes out dry afterwards, it is fire-retardant to obtain the polyacrylonitrile that thickness is 2mm
Complexes membrane, as shown in Figure 2.Chitosan tetramethylene sulfuric acid phosphine fire retardant and polyacrylonitrile provided by the invention as shown in Figure 2
There is good interface compatibility, prepared fire proofing surface is uniform, non-blooming.
Embodiment 7~13
The phosphine solid powder of chitosan tetramethylene sulfuric acid described in embodiment 7~13 be respectively polyacrylonitrile quality 4%,
6%th, 8%, 10%, 12%, 15%, 20%, other conditions are same as Example 6.
Comparative example 1
DMF is added in reactor, by polyacrylonitrile：DMF=1:10 ratio
Polyacrylonitrile is added portionwise in reactor to mix with DMF and dissolved, the solution temperature is 50 DEG C.Poly- third
After alkene nitrile is completely dissolved, it is sufficiently stirred and disperses to obtain translucent stabilising system slurries.
Above-mentioned slurries are applied on inclined glass, slowly rinsed from top to bottom using distilled water, slurries meet MJPZ,
Glass plate is put into cold water together with film and soaks 20min, takes out dry afterwards, obtains the polyacrylonitrile film that thickness is 2mm.
Comparative example 2
DMF is added in reactor, by polyacrylonitrile：N, N-dimethylformamide=1:10 ratio
Polyacrylonitrile is added portionwise in reactor to mix with DMF and dissolved, the solution temperature is 50 DEG C.Poly- third
After alkene nitrile is completely dissolved, add chitosan, the chitosan be polyacrylonitrile quality 10%, be sufficiently stirred be dispersed to it is translucent
Stabilising system slurries.
Above-mentioned slurries are applied on inclined glass, slowly rinsed from top to bottom using distilled water, slurries meet MJPZ,
Glass plate is put into cold water together with film and soaks 20min, takes out dry afterwards, the polyacrylonitrile shell that thickness is 2mm is obtained and gathers
Saccharide complex film.
Comparative example 3
DMF is added in reactor, by polyacrylonitrile：N, N-dimethylformamide=1:10 ratio
Polyacrylonitrile is added portionwise in reactor to mix with DMF and dissolved, the solution temperature is 50 DEG C.Poly- third
Alkene nitrile system is condensed, and can not obtain slurries, as shown in Figure 3.
Flame retardant test is carried out according to the GB/T 5455-2014 films obtained to embodiment 6~13 and comparative example 1~3, is surveyed
Vertical combustion damage carbon length and the fire-retardant rank for obtaining film are as shown in table 2.
The film fire resistance test data of table 2
| Damage carbon length (cm) | Fire-retardant rank | |
| Comparative example 1 | 30 | — |
| Comparative example 2 | 30 | — |
| Embodiment 6 | 17.3 | B2 |
| Embodiment 7 | 12.5 | B1 |
| Embodiment 8 | 7.8 | B1 |
| Embodiment 9 | 5.6 | B1 |
| Embodiment 10 | 5.1 | B1 |
| Embodiment 11 | 4.3 | B1 |
| Embodiment 12 | 2.7 | B1 |
| Embodiment 13 | 1.2 | B1 |
After addition chitosan tetramethylene sulfuric acid phosphine fire retardant provided by the invention being can be seen that according to the data of table 2
The fire resistance of polyacrylonitrile is better than individually addition chitosan and individually adds the fire-retardant of the acrylonitrile of tetramethylene sulfuric acid phosphorus
Performance.
The polyacrylonitrile flame-retardant compounds film obtained in embodiment 6~13 and comparative example 1 and comparative example 2 is placed in normal-temperature water
In, 5min is soaked, taking-up is dried, and is designated as washing 1 time.Wash 20 times successively.
Using anti-microbial property of succusion (GB/T 20944.3-2008) the test polyacrylonitrile before and after fire-retardant and after washing
(antibiotic rate).Wherein the inoculum density of Escherichia coli is 2 × 107CFU/mL, the inoculum density of Staphylococcus aureus for 6 ×
106CFU/mL.UD:Inspection does not measure antibiotic property.
The film of table 3 is water-fastness and anti-microbial property test
Added it can be seen from the data of table 3 poly- after chitosan tetramethylene sulfuric acid phosphine fire retardant provided by the invention
Acrylonitrile has good anti-microbial property and wash durability.
As seen from the above embodiment, the fire retardant that preparation method provided by the present invention is prepared is free of halogen, has
Antibacterial action, and non-toxic degradable, it is green；Flame retardant molecule amount is high, it is linear to keep, non-volatility, water-fastness, resistance to moves
Move, compatibility is good, stability is high, good flame retardation effect.Embodiment result shows the resistance being prepared by technical scheme
Combustion agent charring rate is high, expansion multiple is high, flame retardant rating can reach B1 grades.
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (9)
1. a kind of preparation method of chitosan tetramethylene sulfuric acid phosphine fire retardant, is comprised the steps of：
Tetrakis hydroxymetyl phosphonium sulfuric and chitosan are subjected to Electrostatic Absorption in water, it is compound to obtain tetrakis hydroxymetyl phosphonium sulfuric/chitosan
Thing；
Tetrakis hydroxymetyl phosphonium sulfuric/the chitosan complexes are carried out to be dehydrated covalence graft reaction, obtain chitosan tetramethylene
Sulfuric acid phosphine fire retardant.
2. preparation method according to claim 1, it is characterised in that the quality of the tetrakis hydroxymetyl phosphonium sulfuric and chitosan
Than for 1：1~5：1, the mass ratio of the chitosan and water is 1：0.5~1.1.
3. preparation method according to claim 1 or 2, it is characterised in that the viscosity average molecular weigh of the chitosan be 30,000~
150000；The deacetylation of the chitosan is not less than 80%.
4. preparation method according to claim 1, it is characterised in that the temperature of the Electrostatic Absorption is 80~95 DEG C.
5. the preparation method according to claim 1 or 4, it is characterised in that the time of the Electrostatic Absorption is 1.5~3h.
6. preparation method according to claim 1, it is characterised in that the temperature of the dehydration covalence graft reaction is 140
~180 DEG C.
7. the preparation method according to claim 1 or 6, it is characterised in that the time of the dehydration covalence graft reaction is 2
~4h.
8. chitosan tetramethylene sulfuric acid phosphine fire retardant prepared by the preparation method described in claim 1~7 any one.
9. application of the chitosan tetramethylene sulfuric acid phosphine fire retardant as polyacrylonitrile fire retardant described in claim 8.
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| YOUYOU XIAO ET AL.: "Preparation of a Chitosan-Based Flame-Retardant Synergist and Its Application in Flame-Retardant Polypropylene", 《JOURNAL OF APPLIED POLYMER SCIENCE》 * |
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| CN108396557A (en) * | 2018-02-27 | 2018-08-14 | 湖北金利源大悟纺织服装股份有限公司 | A kind of preparation method of fire retardant |
| CN108395192A (en) * | 2018-03-09 | 2018-08-14 | 深圳摩盾环保新材料有限公司 | A kind of fire-type gypsum base sprayed on material and preparation method thereof |
| CN109370240A (en) * | 2018-10-15 | 2019-02-22 | 高秀阁 | Environment protection modified pitch and its production technology |
| CN109401343A (en) * | 2018-10-15 | 2019-03-01 | 高秀阁 | Spodumene powder modifier and its application in environmentally friendly fire resisting pitch |
| CN113248634A (en) * | 2021-07-09 | 2021-08-13 | 衡阳师范学院 | Chitosan-Schiff/DOPO flame retardant, preparation method thereof and modified epoxy resin |
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