CN104788575B - A kind of cellulose derivative of the structure containing DOPO and preparation method thereof - Google Patents
A kind of cellulose derivative of the structure containing DOPO and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of cellulose derivative containing DOPO structures and their preparation method.This method is initiation material using cellulose or cellulose derivative；Reaction is carried out in cellulose or the homogeneous phase solution of cellulose derivative；The plain derivative of fiber type containing DOPO is prepared by introducing double bond or other functional groups that can be reacted with DOPO in cellulose or cellulose derivative.The DOPO substitution values of products obtained therefrom can regulate and control in the range of 0.1 2.3；This, which contains the plain derivative of DOPO fiber types, to be dissolved in organic solvent, and is processed into transparent cellulose material, such as fiber, film or coating material, with important application value.
Description
Technical field
The present invention relates to a kind of method of modifying of natural macromolecular material, more particularly to a kind of fiber containing DOPO structures
Plain derivative and preparation method thereof.
Background technology
The day polluted with the non-renewable resources such as oil, coal increasingly depleted on the earth and environment for human survival is increasingly
How play, effectively have become one of principal focal point of countries in the world scientist concern using renewable resource.And it is used as nature
The maximum natural polymer of reserves in boundary, cellulose has the advantages that abundance because of it, renewable, degradable and pollution-free draw
The extensive concern of people is played.However, the characteristics of due to native cellulose self assemble state structure（Higher crystallinity, molecule
Between and intramolecular there are a large amount of hydrogen bonds）, cellulose, which can neither be melted, also is difficult to dissolving, and poor processability significantly limit day
The application of right cellulose.Containing three oh groups in each construction unit in cellulose, these oh groups are cellulose
Modification create superior condition.Hydroxyl is changed into other groups by chemically reacting, fiber can be not only substantially improved
The processability of element, and can also impart to cellulose some unique functions.At present, the reaction bag that people are carried out on cellulose
Include：Esterification, etherification reaction, Michael addition reactions, oxidation reaction and graft reaction etc..These cellulose derivatives
Appearance expanded the application field of cellulosic material significantly.Led such as cellulose esters is widely used in coating, plastics, spinning
Domain；Cellulose ether is then the important auxiliary agent in the fields such as food, daily use chemicals, medicine, printing and dyeing, concrete works, drilling project.
The content of the invention
It is an object of the invention to provide a kind of cellulose derivative containing DOPO structures and preparation method thereof.
The method of cellulose derivative of the preparation that the present invention is provided containing DOPO structures, is method A or method B；
Methods described A comprises the following steps：
1）By constitutional repeating unit compound shown in formula I and R1'-X reacts in solvent, obtains constitutional repeating unit
Midbody compound as shown in Formula II；
In the Formulas I, R is selected from least one of hydrogen, acetyl group, propiono, bytyry, methyl and ethyl；
In Formula II, R1' be C2-C4 alkylene；X is selected from least one of acid chloride group, anhydride group and NCO；
2）Under conditions of catalyst presence, by step 1）Intermediate compound of the gained constitutional repeating unit as shown in Formula II
Thing is reacted with DOPO in solvent, and reaction, which is finished, obtains the cellulose derivative containing DOPO structures；
Methods described B comprises the following steps：
3）By OCN-R2'-NCO and DOPO reacted in solvent, reaction, which is finished, obtains compound shown in formula III；
In the formula III, R2' selected from C1-C6 alkyl, phenyl, phenyl derivatives, naphthyl, cyclohexyl andAt least one of；
4）By step 3）Compound shown in gained formula III is with the compound of constitutional repeating unit shown in formula I in solvent
Reacted, reaction, which is finished, obtains the cellulose derivative containing DOPO structures；
In the Formulas I, R is selected from least one of hydrogen, acetyl group, propiono, bytyry, methyl and ethyl.
It is cellulose or cellulose derivative containing compound shown in formula I in the above method A and B；
It is cellulose containing compound shown in formula I when R is hydrogen in the definition of Formulas I；
When R is selected from least one of acetyl group, propiono, bytyry, methyl and ethyl, contain change shown in formula I
Compound is cellulose derivative；
Wherein, the cellulose be selected from microcrystalline cellulose, it is cotton pulp cellulose, wood pulp cellulose, bamboo pulp, absorbent cotton, sweet
Bagasse, timber and at least one of obtained cellulose from straw；
The cellulose derivative is selected from least one of the cellulose ether containing substituent and cellulose esters；Wherein,
At least one of the substituent in C1-C4 alkyl；It is chosen in particular from cellulose diacetate, cellulose acetate-butyrate, propionic acid
At least one of cellulose, cellulose butyrate, methylcellulose and ethyl cellulose；
DOPO used Chinese specification is named as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, is a kind of phosphorus
Luxuriant and rich with fragrance heterocyclic compound, with feature specific to phospho hetero phenanthrene group, such as non-co-planar, the phase with intramolecular or intermolecular group
Interaction, massive structure, molecular polarity etc..
The solvent is selected from ionic liquid, acetone, chloroform, N, N- dimethyl sulfoxide (DMSO)s, N,N-dimethylformamide, N, N-
At least one of dimethyl acetamide and pyridine；
Wherein, the ionic liquid is less than 100 DEG C for formed by imidazoles or pyridine type cation with anion, fusing point
Organic fuse salt；It is preferred that organic fuse salt of cellulose can be dissolved；It is further preferred that the present invention can use the ion of mixing
Liquid dissolve cellulose, wherein the ionic liquid of the mixing can be can dissolve cellulose ionic liquid or
The mixture of the ionic liquid of cellulose and the ionic liquid of insoluble cellulose can be dissolved；
Wherein, the cation be chosen in particular from 1- ethyl-3-methylimidazoles cation, 1- propyl group -3- methylimidazoles sun from
Son, 1- pi-allyl -3- methyl imidazolium cations, 1- butyl -3- methyl imidazolium cations, N- ethylpyridinium cations, N- butyl
Any one in pyridylium and N- n-hexyl pyridyliums；
Anion be chosen in particular from chlorion, bromide ion, formate ion, acetate ion, propionate ion, butyric acid root from
Son and any one in methyl orthophosphoric acid ion；
According to the present invention, the ionic liquid is used alone or as a mixture, or with DMSO, DMF, DMAc or N- methylpyrrole
The cosolvent such as alkanone are used in mixed way.
The R1'-X be selected from acryloyl chloride, methacrylic chloride, crotonyl chloride, acrylic anhydride, methacrylic anhydride, horse
Come at least one of acid anhydrides, itaconic anhydride, allyl isocyanate and vinyl isocyanate；
The catalyst is selected from least one of triethylamine, imidazoles and pyridine；
The OCN-R2'-NCO be selected from 4,4 '-methyl diphenylene diisocyanate（MDI）, 2,4 toluene diisocyanate,
At least one of hexamethylene diisocyanate, 1,5- naphthalene diisocyanates and trans- 1,4- cyclohexyl diisocyanates.
Methods described step A 1）In reactions steps, temperature be 0-150 DEG C, specially 30-80 DEG C, more specifically 50 DEG C, when
Between be 0.1-48 hours, specially 1-10 hours, more specifically 2 hours；
The step 2）In, the consumption of catalyst is the 0.01-30%, specially 1-15% of DOPO mass.
In reactions steps, temperature is 0-200 DEG C, and specially 80 DEG C, the time is 0.1-48 hours, specially 12 hours；
Constitutional repeating unit compound shown in formula I, R1'-X and DOPO mass ratio is 1：0.05-10.0：
0.01-10.0, specially 1：0.28：1.2、1：0.56：3.59、1：1.68：6、1：1.68：2、1：1.68：3.55 or 1：0.28-
1.68：1.2-3.55；
Methods described step B 3）In reactions steps, temperature be -20-200 DEG C, specially 10-50 DEG C, more specifically 30 DEG C,
Time is 0.1-48 hours, specially specially 1-20 hours, 8 hours；
The step 4）In reactions steps, temperature is 0-160 DEG C, and specially 50-100 DEG C, more specifically 80 DEG C, the time is
0.1-72 hours, more specifically specially 1-10 hours, 2 hours；
Constitutional repeating unit compound shown in formula I, OCN-R2'-NCO and DOPO amount ratio is 1g：0.05-
10.0g：0.01-10.0g, specially 1：0.1：0.09、1：0.4：0.4、1：0.5：0.4、1：0.8：0.7、1：1：0.9 or 1：
0.1-1：0.09-0.9；
In addition, the cellulose derivative containing DOPO structures that the method provided according to the invention described above is prepared,
Belong to protection scope of the present invention.Wherein, in the cellulose derivative containing DOPO structures, the substitution value of DOPO groups
（Number of the substituted radical in each glucose unit）Be 0.1-2.3, specially 0.12,0.16,0.17,0.33,0.56,
0.59th, 0.94,0.97,0.98 or 0.12-0.98.
The homogeneous phase solution that the cellulose derivative containing DOPO structures and organic solvent provided by the invention described above constitutes,
Protection scope of the present invention is also belonged to, wherein, the organic solvent is selected from DMSO, DMF, pyridine, chloroform, tetrahydrofuran and DMAc
At least one of；
The mass percentage concentration of the homogeneous phase solution is 1-40%, specially 3-30%.
In addition, the material being prepared by above-mentioned homogeneous phase solution, also belongs to protection scope of the present invention, wherein, it is described
Material is transparent material, specially film；The HRR of the membrane material is greatly reduced relative to raw material, and carbon residual volume
Greatly improve；During burning, the membrane material has obvious burning self-extinguishment phenomenon.
The method of cellulose derivative of the preparation that the present invention is provided containing DOPO structures, uses cellulose or cellulose
Derivative is initiation material, and is carried out in cellulose or the homogeneous phase solution of cellulose derivative；Will by bridging mode
DOPO is incorporated into cellulose or its derivative to prepare the plain derivative of fiber type containing DOPO.The fiber of this structure containing DOPO
Plain derivative can be dissolved in organic solvent and be processed into transparency cellulose sill, such as fiber, film or coating material, tool
There is important application value.
Brief description of the drawings
Fig. 1 is the plain derivative of obtained DOPO fiber types, cellulose-acrylate and DOPO in embodiment 31HNMR is composed
Figure.
Fig. 2 is the plain derivative of obtained DOPO fiber types in embodiment 81HNMR spectrograms.
It using ionic liquid AmimCl is cellulose membrane (left side) prepared by solvent and using DMF DOPO made from solvent that Fig. 3, which is,
Fiber type element derivatives membrane (right side).
Fig. 4 is the combustion phenomena of cellulose membrane (left side) and the plain derivatives membrane (right side) of DOPO fiber types.
Embodiment
With reference to specific embodiment, the present invention is further elaborated, but the present invention is not limited to following examples.Institute
It is conventional method unless otherwise instructed to state method.The raw material can be obtained from open commercial sources unless otherwise instructed.
The method that embodiment 1, method A prepare the cellulose derivative containing DOPO structures
（1）1g microcrystalline celluloses are added to 19g ionic liquid 1- pi-allyl -3- methylimidazole villaumites（AmimCl）In,
80 DEG C are dissolved 1 hour with 400 revs/min of mechanical agitation.In the oil bath that cellulose solution is placed in 50 DEG C, half an hour to be stablized
Afterwards, 0.28g acryloyl chloride is added thereto with 300 revs/min of mechanic whirl-nett reaction 2 hours.After reaction terminates, through precipitating,
Wash, be dried to obtain the intermediate product cellulose-acrylate that substitution value is 0.16.
（2）1.2g DOPO are dissolved in 5.0g DMSO, addition thereto accounts for the triethylamine of DOPO mass 1% as catalysis
Agent, takes step（1）In cellulose-acrylate 1g be dissolved in 19g DMSO, be slowly dropped in DOPO solution, in
80 DEG C are reacted 12 hours, methanol extraction, after scrubbed, drying, obtain the plain derivative of DOPO fiber types that substitution value is 0.16.
The method that embodiment 2, method A prepare the cellulose derivative containing DOPO structures
（1）1g microcrystalline celluloses are added to 19g ionic liquid 1- pi-allyl -3- methylimidazole villaumites（AmimCl）In,
80 DEG C are dissolved 1 hour with 400 revs/min of mechanical agitation.In the oil bath that cellulose solution is placed in 50 DEG C, half an hour to be stablized
Afterwards, 0.56g acryloyl chloride is added thereto with 300 revs/min of mechanic whirl-nett reaction 2 hours.After reaction terminates, through precipitating,
Wash, be dried to obtain the intermediate product cellulose-acrylate that substitution value is 0.56.
（2）3.59g DOPO are dissolved in 5.0g DMSO, addition thereto accounts for the triethylamine of DOPO mass 1% as catalysis
Agent, takes step（1）In cellulose-acrylate 1g be dissolved in 19g DMSO, be slowly dropped in DOPO solution, in
80 DEG C are reacted 12 hours, methanol extraction, after scrubbed, drying, obtain the plain derivative of DOPO fiber types that substitution value is 0.56.
The method that embodiment 3, method A prepare the cellulose derivative containing DOPO structures
（1）1g microcrystalline celluloses are added to 19g ionic liquid 1- pi-allyl -3- methylimidazole villaumites（AmimCl）In,
80 DEG C are dissolved 1 hour with 400 revs/min of mechanical agitation.In the oil bath that cellulose solution is placed in 50 DEG C, half an hour to be stablized
Afterwards, 1.68g acryloyl chloride is added thereto with 300 revs/min of mechanic whirl-nett reaction 2 hours.After reaction terminates, through precipitating,
Wash, be dried to obtain the intermediate product cellulose-acrylate that substitution value is 0.94.
（2）6.0g DOPO are dissolved in 9.0g DMSO, addition thereto accounts for the triethylamine of DOPO mass 1% as catalysis
Agent, takes step（1）In cellulose-acrylate 1g be dissolved in 19g DMSO, be slowly dropped in DOPO solution, in
80 DEG C are reacted 12 hours, methanol extraction, after scrubbed, drying, obtain the DOPO fiber types element that target product substitution value is 0.94
Derivative.
DOPO fiber types element derivative and intermediate compound chemical structure by1HNMR is confirmed（See accompanying drawing 1）.As composed
Shown in figure, the peak between δ=5.6-6.5ppm is the hydrogen on olefinic double bonds（3H）, the appearance proof acrylate success of this position
It is introduced on cellulose molecular chain；Peak between δ=7.0-8.3ppm is the hydrogen on DOPO molecules（10H）.It is possible thereby to demonstrate,prove
Bright, DOPO has been successfully introduced in cellulose molecular chain.
The method that embodiment 4, method A prepare the cellulose derivative containing DOPO structures
（1）3g wood pulp celluloses are added to 97g1- butyl -3- methylimidazole villaumites（BmimCl）In, at 80 DEG C with 400
Rev/min mechanical agitation dissolve 2 hours.In the oil bath that cellulose solution is placed in 50 DEG C, after half an hour is stablized, add thereto
Enter 5.04g acryloyl chloride with 300 revs/min of mechanic whirl-nett reaction 2 hours.Reaction terminate after, through precipitation, washing, drying can
Obtain the cellulose-acrylate that substitution value is 0.97.
（2）6.0g DOPO are dissolved in 9.0g DMSO, addition thereto accounts for the triethylamine of DOPO mass 1% and makees catalyst.
Take step（1）In cellulose-acrylate 1g be dissolved in 19g DMSO, be slowly dropped in DOPO solution.In 80 DEG C
Reaction 12 hours, methanol extraction obtains the plain derivative of DOPO fiber types that substitution value is 0.97 after scrubbed, drying.
The method that embodiment 5, method A prepare the cellulose derivative containing DOPO structures
（1）48g ionic liquid AmimCl are added in 2g cotton pulp celluloses, are dissolved at 80 DEG C with 400 revs/min of mechanical agitation
2 hours.In the oil bath that cellulose solution is placed in 50 DEG C, after half an hour is stablized, thereto add 3.36g acryloyl chloride with
300 revs/min of mechanic whirl-nett reaction 2 hours.It is 0.98 through water sedimentation, washing, the dry substitution value that can obtain after reaction terminates
Cellulose-acrylate.
（2）7.1g DOPO are dissolved in 10.0gDMSO, addition thereto accounts for the triethylamine of DOPO mass 1% and makees catalyst.
Take step（1）In cellulose-acrylate 1g be dissolved in 19g DMSO, be slowly dropped in DOPO solution.At 80 DEG C
Reaction 12 hours, methanol extraction obtains the plain derivative of DOPO fiber types that substitution value is 0.98 after scrubbed, drying.
The method that embodiment 6, method B prepare the cellulose derivative containing DOPO structures
1）0.07g DOPO are dissolved in 5g DMF, 0.08g4,4 '-methyl diphenylene diisocyanate（MDI）It is dissolved in 5g
In DMF；In the solution that DOPO solution is slowly added dropwise, react 8 hours, obtained containing DOPO structures in 30 DEG C of magnetic agitations
And end group is the compound of NCO.
2）0.76g cellulose diacetates are dissolved in 10g DMF, and the compound of the above-mentioned structure containing DOPO is added thereto,
80 DEG C are reacted 2 hours, methanol extraction, and the DOPO type cellulose acetates that substitution value is 0.04 are obtained after scrubbed, drying.
The method that embodiment 7, method B prepare the cellulose derivative containing DOPO structures
1）0.34g DOPO are dissolved in 10g DMF, 0.39g MDI are dissolved in 10g DMF；DOPO solution is slowly dripped
In the solution of addition, react 8 hours, obtained containing the change that DOPO structures and end group are NCO in 30 DEG C of magnetic agitations
Compound.
2）0.76g cellulose diacetates are dissolved in 10g DMF, and by step 1）Gained contains DOPO structures and end group is
The compound of NCO is added thereto, and 80 DEG C are reacted 2 hours, methanol extraction, and obtaining substitution value after scrubbed, drying is
0.17 DOPO type cellulose acetates.
The method that embodiment 8, method B prepare the cellulose derivative containing DOPO structures
1）0.67g DOPO are dissolved in 10g DMF, 0.77g MDI are dissolved in 10g DMF；DOPO solution is slowly dripped
In the solution of addition, react 8 hours, obtained containing the change that DOPO structures and end group are NCO in 30 DEG C of magnetic agitations
Compound.
2）0.76g cellulose diacetates are dissolved in 10g DMF, and by step 1）Gained contains DOPO structures and end group is
The compound of NCO is added thereto, and 80 DEG C are reacted 2 hours, methanol extraction, and obtaining substitution value after scrubbed, drying is
0.59 DOPO type cellulose acetates.
DOPO fiber types element derivative chemical constitution by1HNMR is confirmed（See accompanying drawing 2）.As shown in spectrogram, δ=
Peak between 7.0-8.8ppm is the proton peak on phenyl ring in DOPO and MDI.It is possible thereby to prove, DOPO has been successfully introduced
Into cellulose molecular chain.
The method that embodiment 9, method B prepare the cellulose derivative containing DOPO structures
1）0.67g DOPO are dissolved in 10g DMF, 0.77gMDI is dissolved in 10g DMF；DOPO solution is slowly dripped
In the solution for adding MDI, reacted 8 hours in 30 DEG C of magnetic agitations, obtain containing DOPO structures and end group is NCO
Compound.
2）0.76g cellulose diacetates are dissolved in 10g DMF, and by step 1）Gained contains DOPO structures and end group is
The compound of NCO is added thereto, and is reacted 2 hours in 80 DEG C, methanol extraction, and obtaining substitution value after scrubbed, drying is
0.58 DOPO type cellulose acetates.
The method that embodiment 10, method B prepare the cellulose derivative containing DOPO structures
1）0.17g DOPO are dissolved in 10g DMF, 0.20g MDI are dissolved in 10g DMF；DOPO solution is slowly dripped
In the solution for adding MDI, reacted 8 hours in 30 DEG C of magnetic agitations, obtain containing DOPO structures and end group is NCO
Compound.
2）0.47g ethyl celluloses（Ethyl substitution value is 2.6）It is dissolved in 10g DMF, and by step 1）Gained contains
DOPO structures and end group are added thereto for the compound of NCO, are reacted 2 hours in 80 DEG C, methanol extraction, scrubbed,
The DOPO type ethyl celluloses that substitution value is 0.12 are obtained after drying.
The method that embodiment 11, method B prepare the cellulose derivative containing DOPO structures
1）0.39g DOPO are dissolved in 10g DMF, 0.45g MDI are dissolved in 10g DMF；DOPO solution is slowly dripped
In the solution for adding MDI, reacted 8 hours in 30 DEG C of magnetic agitations, obtain containing DOPO structures and end group is NCO
Compound.
2）0.56g cellulose acetate-butyrates（Degree of substitution with acetyl group is 0.72, and bytyry substitution value is 1.36）It is dissolved in
In 10gDMF, and by step 1）Gained is added thereto containing DOPO structures and end group for the compound of NCO, in 80
DEG C reaction 2 hours, methanol extraction, it is scrubbed, dry after obtain substitution value be 0.33 DOPO type cellulose acetate-butyrates.
The dissolubility and transparent material product of the plain derivative of embodiment 12, DOPO fiber types：
DOPO fiber types element substantially improves the solubility property of cellulose after this macoradicals of DOPO are introduced.
By the gained DOPO substitution values of embodiment 4 for 0.97 the plain derivative of DOPO fiber types be dissolved in DMSO, DMF, pyridine and
In chloroform, it is seen that the compound can rapidly dissolve, and transparency cellulose basal lamina material can be processed into（See accompanying drawing 3）.Such as
Shown in figure, can be made for solvent using DMF has similar transparent membrane material to cellulose.
The micro combustions calorimetric test of the plain derivative of embodiment 13, DOPO fiber types and combustion phenomena：
Microcrystalline cellulose and embodiment 1,2,3,6,7 and the plain derivative of 8 gained DOPO fiber types are subjected to micro combustions amount
Thermal test（See attached list 1）.
The micro combustions calorimetric test data of the membrane material of the plain derivative of table 1, DOPO fiber types
Wherein, PHRR is maximum HRR；
TmaxFor maximum combustion temperature；
THR discharges for total heat；
HRC is Heat liberation unit.
As seen from table, the plain derivative of DOPO fiber types greatly reduces heat release speed after this macoradicals of DOPO are introduced
Rate, and carbon residual volume is then greatly improved.
Compared with raw material, the gained DOPO fiber types of embodiment 3 element derivative has obvious burning self-extinguishment phenomenon（See accompanying drawing
4）.
Claims (15)
1. a kind of method for preparing the cellulose derivative containing DOPO structures, is method A or method B；
Methods described A comprises the following steps：
1) by constitutional repeating unit compound shown in formula I and R1'-X reacts in solvent, obtains constitutional repeating unit such as formula
Midbody compound shown in II；
In the Formulas I, R is selected from least one of hydrogen, acetyl group, propiono, bytyry, methyl and ethyl；
The R1'-X be selected from acryloyl chloride, methacrylic chloride, crotonyl chloride, acrylic anhydride, methacrylic anhydride, maleic acid
At least one of acid anhydride, itaconic anhydride, allyl isocyanate and vinyl isocyanate；
2) under conditions of catalyst presence, by step 1) midbody compound of the gained constitutional repeating unit as shown in Formula II and
DOPO is reacted in solvent, and reaction, which is finished, obtains the cellulose derivative containing DOPO structures；
Methods described B comprises the following steps：
3) by OCN-R2'-NCO and DOPO reacted in solvent, reaction, which is finished, obtains compound shown in formula III；
In the formula III, R2At least one of ' alkyl, phenyl, phenyl derivatives, naphthyl and cyclohexyl selected from C1-C6；
4) by step 3) compound and the compound of constitutional repeating unit shown in formula I shown in gained formula III carry out in solvent
Reaction, reaction, which is finished, obtains the cellulose derivative containing DOPO structures；
In the Formulas I, R is selected from least one of hydrogen, acetyl group, propiono, bytyry, methyl and ethyl.
2. according to the method described in claim 1, it is characterised in that：In methods described A and B, contain constitutional repeating unit such as Formulas I
Shown compound is cellulose or cellulose derivative；
Wherein, the cellulose be selected from microcrystalline cellulose, cotton pulp cellulose, wood pulp cellulose, bamboo pulp, absorbent cotton, bagasse,
Timber and at least one of obtained cellulose from straw；
The cellulose derivative is selected from least one of the cellulose ether containing substituent and cellulose esters；Wherein, it is described
Substituent is selected from least one of acetyl group, propiono, bytyry, methyl and ethyl；
The solvent is selected from ionic liquid, acetone, chloroform, N, N- dimethyl sulfoxide (DMSO)s, N,N-dimethylformamide, N, N- diformazans
At least one of yl acetamide and pyridine；
Wherein, the ionic liquid is less than 100 DEG C for formed by imidazoles or pyridine type cation with anion, fusing point
Organic fuse salt；
Catalyst is selected from least one of triethylamine, imidazoles and pyridine；
In methods described B, OCN-R2'-NCO be selected from 4,4 '-methyl diphenylene diisocyanate, 2,4 toluene diisocyanate, 1,
At least one of hexamethylene-diisocyanate, 1,5- naphthalene diisocyanates and trans- 1,4- cyclohexyl diisocyanates.
3. method according to claim 2, it is characterised in that：The cellulose derivative is selected from cellulose diacetate, second
At least one of sour cellulose butyrate, cellulose propionate, cellulose butyrate, methylcellulose and ethyl cellulose；
The cation is selected from 1- ethyl-3-methylimidazoles cation, 1- propyl group -3- methyl imidazolium cations, 1- pi-allyls -3-
Methyl imidazolium cation, 1- butyl -3- methyl imidazolium cations, N- ethylpyridinium cations, N- butyl-pyridiniums cation and N-
Any one in n-hexyl pyridylium；
The anion is selected from chlorion, bromide ion, formate ion, acetate ion, propionate ion and butyrate ion
In any one.
4. method according to claim 1 or 2, it is characterised in that：Methods described step A 1) in reactions steps, temperature is
0-150 DEG C, the time is 0.1-48 hours；
The step 2) in, the consumption of catalyst is the 0.01-30% of DOPO mass；
The step 2) in, in reactions steps, temperature is 0-200 DEG C, and the time is 0.1-48 hours；
Constitutional repeating unit compound shown in formula I, R1'-X and DOPO mass ratio is 1：0.05-10.0：0.01-
10.0。
5. method according to claim 4, it is characterised in that：Methods described step A 1) in reactions steps, temperature is 30-
80 DEG C, the time is 1-10 hours；
The step 2) in, the consumption of catalyst is the 1-15% of DOPO mass；
The step 2) in, in reactions steps, temperature is 30-100 DEG C, and the time is 10-20 hours.
6. method according to claim 1 or 2, it is characterised in that：Methods described step B 3) in reactions steps, temperature for-
20-200 DEG C, the time is 0.1-48 hours,；
The step 4) in reactions steps, temperature is 0-160 DEG C, and the time is 0.1-72 hours；
Constitutional repeating unit compound shown in formula I, OCN-R2'-NCO and DOPO amount ratio is 1g：0.05-
10.0g：0.01-10.0g.
7. method according to claim 6, it is characterised in that：Methods described step B 3) in reactions steps, temperature is 10-
50 DEG C, the time is 1-20 hours；
The step 4) in reactions steps, temperature is 50-100 DEG C, and the time is 1-10 hours.
8. the cellulose derivative containing DOPO structures that any methods describeds of claim 1-7 are prepared.
9. cellulose derivative according to claim 8, it is characterised in that：The cellulose containing DOPO structures derives
In thing, the substitution value of DOPO groups is 0.1-2.3.
10. the cellulose derivative containing DOPO structures that is prepared by any methods describeds of claim 1-7 and organic molten
The homogeneous phase solution of agent composition.
11. homogeneous phase solution according to claim 10, it is characterised in that：The organic solvent be selected from DMSO, DMF, pyridine,
At least one of chloroform, tetrahydrofuran and DMAc；
The mass percentage concentration of the cellulose derivative homogeneous phase solution containing DOPO structures is 1-40%.
12. homogeneous phase solution according to claim 11, it is characterised in that：The cellulose derivative containing DOPO structures
The mass percentage concentration of homogeneous phase solution is 3-30%.
13. the cellulose derivative containing DOPO structures being prepared by any described homogeneous phase solutions of claim 10-12
Material.
14. the material of the cellulose derivative according to claim 13 containing DOPO structures, it is characterised in that：It is described to contain
The material for having the cellulose derivative of DOPO structures is transparent material.
15. the cellulose derivative material according to claim 14 containing DOPO structures, it is characterised in that：It is described containing
The material of the cellulose derivative of DOPO structures is film or coating material.
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| CN106008742B (en) * | 2016-05-18 | 2018-11-13 | 国家海洋局第三海洋研究所 | Marine biomass based flameproofing with fiber element structure |
| CN106632703B (en) * | 2016-09-29 | 2019-04-02 | 中国科学院宁波材料技术与工程研究所 | A kind of phosphorous starch of biology base and its preparation method and application |
| KR20190127898A (en) * | 2017-03-29 | 2019-11-13 | 이스트만 케미칼 컴파니 | Position-optionally substituted cellulose ester |
| CN109206670B (en) * | 2017-07-03 | 2020-04-24 | 中国科学院化学研究所 | Composition of polysaccharide derivative containing phenolic hydroxyl and preparation method and application thereof |
| CN107686560B (en) * | 2017-09-26 | 2020-11-06 | 南京林业大学 | Preparation method of cellulose flame-retardant modified composite phenolic foam |
| CN108559662B (en) * | 2017-12-27 | 2021-12-14 | 山东恒联新材料股份有限公司 | Cleaning agent for filter element of filter and use method thereof |
| DE102019213793A1 (en) * | 2019-09-11 | 2021-03-11 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Phosphorus-containing cellulose esters, process for their production, use and flame retardants |
| CN110587759B (en) * | 2019-10-25 | 2021-01-22 | 福建省顺昌县升升木业有限公司 | Flame-retardant modification treatment method for bamboo wood |
| CN110733093B (en) * | 2019-10-25 | 2021-01-19 | 福建省顺昌县升升木业有限公司 | Fir flame-retardant modification treatment method |
| CN115403674B (en) * | 2022-05-12 | 2023-11-21 | 盐城工学院 | Biomass-based enhanced flame retardant, and preparation method and application thereof |
| CN115107322B (en) * | 2022-07-18 | 2023-06-06 | 广东安拓普聚合物科技有限公司 | Environment-friendly flexible leather and preparation method thereof |
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