CN102766917B - Method for preparing cellulose/butyl methacrylate (BMA) graft copolymer oil absorbent fibers - Google Patents
Method for preparing cellulose/butyl methacrylate (BMA) graft copolymer oil absorbent fibers Download PDFInfo
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Abstract
The invention relates to a method for preparing cellulose/BMA graft copolymer oil absorbent fibers. The method includes dissolving the cellulose fully in a lithium chloride/N, N- dimethylacetamide composite solvent system to obtain a cellulose solution, further reacting the cellulose and the BMA through an atom transfer radical polymerization (ATRP) method to prepare the cellulose/the BMA graft copolymers in a cellulose/lithium chloride/dimethylacetamide homogeneous solution system, dissolving the copolymers, preparing a spinning solution with a cross-linking agent, and preparing the cellulose/BMA graft copolymer oil absorbent fibers by using a dry-and-wet method spinning technology. The method is simple to operate, the reaction condition is mild, defects of large reagent consumption, long technological process, difficult reaction control, uneven resultant and the like existing in heterogeneous graft polymerization method for preparing cellulose base oil absorption materials can be overcome, the resultant grafting rate can be controlled conveniently according to mesh structure requirements of final products, and lipophilic segments can be distributed on a cellulose matrix evenly; and because the used basic material is the cellulose, the obtained resultant has both the biodegradability of the cellulose and the high oil absorption performance of a lipophilic monomer, so that the difficult problem that ordinary oil absorption materials cannot have high oil absorption performances and biodegradability simultaneously is solved.
Description
Technical field
The present invention relates to a kind of employing Mierocrystalline cellulose LiCl/DMAc (lithium chloride/N, N-N,N-DIMETHYLACETAMIDE) homogeneous phase solution system, Mierocrystalline cellulose and butyl methacrylate are made after Mierocrystalline cellulose/butyl methacrylate graft copolymer by ATRP method single step reaction, by its dissolving, the spinnable solution that preparation contains linking agent, then adopt dry-wet spinning technology to prepare the method for Mierocrystalline cellulose/butyl methacrylate graft copolymer oil suction fibre.
Technical background
Along with the raising of industrial expansion and people's living standard, sump oil quantity discharged is increasing, and river, ocean and human habitat have been brought to serious threat.According to statistics, have at least every year in the world 5,000,000-1,000 ten thousand tons of oils to enter by all means water body, become the principal pollutant of water body, arouse great concern.
In many greasy dirt treatment processs, the absorption method based on oil absorption material has efficiently, economic, the feature being convenient to promote the use of and being widely adopted.Researcher has been developed multiple oil absorbency material, as the clay of mineral-type, silicon-dioxide, pearl layer iron, lime; The paper pulp of organic, kapok, peat; The polystyrene fabric of synthetic class, polypropylene non-woven fabric, polyacrylate(s) series high oil absorbing resin etc.Wherein, high oil absorbing resin be a class by oleophylic monomer the specific function macromolecular material through the appropriately crosslinked tool tridimensional network forming, compare with other oil absorption materials, high oil absorbing resin has that oil suction kind is many, speed is fast, oil suction/water suction selectivity is good and have the advantages such as good thermotolerance and winter hardiness.Yet due to such material, on the one hand mostly synthetic based on petroleum chemicals, not only price grows to even greater heights, and is difficult to natural degradation after discarded, be to burn or landfill all likely causes secondary pollution; On the other hand, due to such oil-absorbing resin, be mostly the granulated product with three-dimensional netted crosslinking structure, the limitation of shape can make its application in many aspects be restricted, in contrast, the specific surface area of oil suction fibre is larger, can be processed into as required the goods of various forms, and Application Areas can be widened greatly; And three-dimensional netted crosslinking structure makes again oil-absorbing resin have insoluble not molten feature, be difficult to use traditional spin processes that oil-absorbing resin is spun into well behaved oil suction fibre.Therefore, develop reproducible plant cellulose resource, preparation and Environmental compatibility are good and oil absorptiveness is suitable with high oil absorbing resin, and the wider cellulose base intrinsic oil suction fibre of Application Areas, are of great practical significance.
About the research of intrinsic oil suction fibre, there is not yet report abroad.Domestic Tianjin University of Technology carried out research to this, the employing hydroxyethyl methylacrylate such as obturage is latent crosslinker, synthesize oil absorptiveness preferably containing after the linear fibroblast copolymethacrylate of latent crosslinker, be modulated into spinning solution, adopt dry-wet spinning technology to spin copolymethacrylate fiber; It is monomer that Xu Naiku etc. be take BMA, β-hydroxyethyl methacrylate (HEMA), adopts suspension polymerization to synthesize after BMA/HEMA multipolymer, by highly concentrated solution spin processes, has spinned BMA/HEMA copolymer fibre.In addition, Donghua University also did the research of this respect, and Liu Yanping etc. utilize electrostatic spinning to prepare the supertine oil absorption fibre that diameter is 200-5000nm on the basis of terpolymer EP rubber, then by wave radiation technology, prepare three-dimensional netted oil suction fibre material.But, with regard to the intrinsic oil suction fibre of cellulose base, yet there are no research report.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of Mierocrystalline cellulose/butyl methacrylate graft copolymer oil suction fibre.First the method is that Mierocrystalline cellulose is fully dissolved in to lithium chloride/N, in N-N,N-DIMETHYLACETAMIDE double solvents system, make after cellulosic solution, at Mierocrystalline cellulose/lithium chloride/N, in N-N,N-DIMETHYLACETAMIDE homogeneous phase solution system, make Mierocrystalline cellulose and butyl methacrylate prepare Mierocrystalline cellulose/butyl methacrylate graft copolymer by ATRP method single step reaction, then by its dissolving, the spinnable solution that preparation contains linking agent, then adopt dry-wet spinning technology to prepare Mierocrystalline cellulose/butyl methacrylate graft copolymer oil suction fibre.
The method is simple to operate, reaction conditions is gentle, can not only overcome Heterogeneous Radical Grafting legal system for cellulose-based oil-absorption material have that reagent dosage is large, long flow path, the shortcoming such as reaction is difficult to control and product is inhomogeneous, and can according to the reticulated structure of the finished product, require to control product percentage of grafting easily, oleophylic segment is evenly distributed on cellulosic matrix, simultaneously good because of gained Mierocrystalline cellulose/butyl methacrylate graft copolymer solubility property, the preparation of spinning solution and spinning process afterwards all facilitate easy to operate.
The preparation method of a kind of Mierocrystalline cellulose/butyl methacrylate graft copolymer oil suction fibre of the present invention, follows these steps to carry out:
A, cellulose cotton pulp is torn into the small pieces that the length of side is 1-1.5cm, adds N,N-dimethylacetamide, stirring and refluxing 2 was as a child cooled to 100 ℃ afterwards, added Lithium chloride (anhydrous), continued to stir cooling, at room temperature stir 10 hours, prepare Mierocrystalline cellulose LiCl/DMAc solution;
B, Mierocrystalline cellulose LiCl/DMAc solution in step a is cooled to 0-10 ℃, stirs and add triethylamine alkalization, and be added dropwise to the lysate of Tosyl chloride in N,N-dimethylacetamide, isothermal reaction 8-24 hour;
C, will in step b reaction system, add after initiator benzoyl peroxide or azo-bis-isobutyl cyanide, stir and be warming up to 50-75 ℃, and add grafted monomer butyl methacrylate, constant temperature stirring reaction 4-8 hour under nitrogen protection;
D, step c reaction solution is poured in pure water after precipitation, with pure water and ethanol, fully washed, oven dry at 40 ℃, obtains Mierocrystalline cellulose/butyl methacrylate graft copolymer;
E, by steps d graft copolymerization product heating for dissolving at N, dinethylformamide or N, in N-dimethylacetamide solvent, form after the graft copolymer solution of homogeneous transparent, add initiator benzoyl peroxide or azo-bis-isobutyl cyanide, and linking agent N, N '-methylene-bisacrylamide, under nitrogen protection, at 70-80 ℃, after low rate mixing 2-3 hour, room temperature standing and defoaming is processed 24 hours;
F, treatment solution in step e is filtered after, with nitrogen, suppress, volume pump suction, after being extruded by orifice, it enters N, dinethylformamide/water or N, in the precipitation bath of N-N,N-DIMETHYLACETAMIDE/water, solidify, then after water washing bath stretches, at 150-180 ℃, dry and prepare Mierocrystalline cellulose/butyl methacrylate graft copolymer oil suction fibre.
The polymerization degree of the pulp of cellulose cotton described in step a is 250-1000, and the consumption of N,N-dimethylacetamide is 20-40 times of Mierocrystalline cellulose quality, and the consumption of Lithium chloride (anhydrous) is 2.5-3.5 times of Mierocrystalline cellulose quality.
In step b the amount of substance of triethylamine be cellulosic amount of substance 7-11 doubly, the amount of substance of Tosyl chloride be cellulosic amount of substance 3-7 doubly, isothermal reaction temperature is 0-10 ℃, the isothermal reaction time is 8-24 hour.。
In step c the amount of substance of initiator be cellulosic amount of substance 0.3-0.7 doubly, the amount of substance of grafted monomer butyl methacrylate be cellulosic amount of substance 1-5 doubly, isothermal reaction temperature is 50-75 ℃, the isothermal reaction time is 4-8 hour.
In steps d, precipitin reaction liquid pure water temperature used is 25-35 ℃, and the pure water temperature of cleaning product is 35-50 ℃.
In step e, Mierocrystalline cellulose-butyl methacrylate graft copolymer is dissolved in N, dinethylformamide or N, the solution quality umber forming in N-dimethylacetamide solvent is 7-15%, the consumption of initiator is the 1-5% of Mierocrystalline cellulose/butyl methacrylate graft copolymerization amount, dosage of crosslinking agent is the 3-10% of Mierocrystalline cellulose/butyl methacrylate graft copolymerization amount, crosslinking reaction temperature is 70-80 ℃, and cross-linking reaction time is 2-3 hour.
In step f, coagulation bath temperature is 30-50 ℃, and water washing bath temperature is 25-50 ℃, and the bake out temperature of final oil suction fibre product is 150-180 ℃.
Of the present invention is a kind of preparation method of Mierocrystalline cellulose/butyl methacrylate graft copolymer oil suction fibre, and the method has:
(1) utilize plant cellulose for base material, adopt ATRP method single step reaction to make Mierocrystalline cellulose/butyl methacrylate graft copolymer, by its dissolving, after the spinnable solution that preparation contains linking agent, adopt dry-wet spinning technology to prepare Mierocrystalline cellulose/butyl methacrylate graft copolymer oil suction fibre.Compare with the oil suction fibre that traditional employing Heterogeneous Radical Grafting legal system is standby, not only reagent dosage reduces, the homopolymer that does not affect product oil absorbency produces, and can control product percentage of grafting according to the network architecture requirement of fiber, oleophylic segment is evenly distributed on cellulosic matrix, and then control the cross-linked network structure that interchain is propped up in Mierocrystalline cellulose body and oil suction, make the oil absorptiveness of oil suction fibre obtain increasing substantially.
(2) the intrinsic good characteristic of the existing Mierocrystalline cellulose of cellulose graft copolymer, there is again the new capability that synthetic polymer side chain is given, so, the oil suction fibre that the present invention utilizes Mierocrystalline cellulose and the synthetic graft copolymer solvent spinning of butyl methacrylate to prepare, existing cellulosic biodegradable, possessed again the high oil absorbency energy of long-chain ester, thereby solved the difficulty that general oil absorption material can not solve high oil absorbency and biological degradability simultaneously.
Embodiment
Below in conjunction with embodiment, further illustrate the present invention
Embodiment 1
A, to take the polymerization degree be that 250 cellulose cotton pulp 16.20 grams (0.1 moles) is torn into the small pieces that the length of side is 1.5cm, add N, 324 milliliters of N-N,N-DIMETHYLACETAMIDEs, stirring and refluxing 2 was as a child cooled to 100 ℃ afterwards, add 40.5 grams of Lithium chloride (anhydrous)s, continue to stir cooling, at room temperature stir 10 hours, obtain faint yellow transparent Mierocrystalline cellulose LiCl/DMAc solution;
B, above-mentioned Mierocrystalline cellulose LiCl/DMAc solution is cooled to 10 ℃, under stirring, add 0.7 mole of (97.6 milliliters) triethylamine alkalization, and be added dropwise to 0.3 mole of (57.2 grams) Tosyl chloride at 100 milliliters of N, lysate in N-N,N-DIMETHYLACETAMIDE, isothermal reaction adds 0.03 mole of (7.3 grams) initiator benzoyl peroxide after 8 hours, stirring is warming up to 75 ℃, and add 0.1 mole of (15.9 milliliters) grafted monomer butyl methacrylate, under nitrogen protection, after constant temperature stirring reaction 6 hours, this reaction solution is poured in 25 ℃ of pure water and precipitated, filter, again with 35 ℃ of pure water washings repeatedly, finally use washing with alcohol 2 times, at 40 ℃, dry, obtain Mierocrystalline cellulose/butyl methacrylate graft copolymer,
C, take 16.6 grams of above-mentioned Mierocrystalline cellulose/butyl methacrylate graft copolymer products, add 100 milliliters of (94 grams) N, dinethylformamide, be heated with stirring to 70 ℃, make Mierocrystalline cellulose/butyl methacrylate graft copolymer fully be dissolved in N, in dinethylformamide, form massfraction and be after 15% solution, add 0.83 gram of initiator benzoyl peroxide and 1.66 grams of linking agent N, N '-methylene-bisacrylamide, under nitrogen protection, at 70 ℃, crosslinking reaction is after 3 hours, and room temperature standing and defoaming is processed 24 hours;
D, above-mentioned treatment solution is filtered, and suppress with nitrogen, volume pump suction, after it is extruded by orifice, entering temperature is 30 ℃, in the precipitation bath of DMF/water, solidify, then after the water washing bath stretching that is 30 ℃ through temperature, at 180 ℃, dry, both obtained target product Mierocrystalline cellulose/butyl methacrylate graft copolymer oil suction fibre.This product has reached 34.4g/g to the oil absorbency of methylene dichloride.
Embodiment 2
A, to take the polymerization degree be that 521 cellulose cotton pulp 16.20 grams (0.1 moles) is torn into the small pieces that the length of side is 1.2cm, add N, 486 milliliters of N-N,N-DIMETHYLACETAMIDEs, stirring and refluxing 2 was as a child cooled to 100 ℃ afterwards, add 48.6 grams of Lithium chloride (anhydrous)s, continue to stir cooling, at room temperature stir 10 hours, obtain faint yellow transparent Mierocrystalline cellulose LiCl/DMAc solution;
B, above-mentioned Mierocrystalline cellulose LiCl/DMAc solution is cooled to 5 ℃, under stirring, add 0.9 mole of (125.4 milliliters) triethylamine alkalization, and be added dropwise to 0.5 mole of (95.3 grams) Tosyl chloride at 100 milliliters of N, lysate in N-N,N-DIMETHYLACETAMIDE, isothermal reaction adds 0.05 mole of (8.2 grams) initiator azo-bis-isobutyl cyanide after 14 hours, stirring is warming up to 50 ℃, and add 0.3 mole of (47.7 milliliters) grafted monomer butyl methacrylate, under nitrogen protection, after constant temperature stirring reaction 4 hours, this reaction solution is poured in 30 ℃ of pure water and precipitated, filter, again with 40 ℃ of pure water washings repeatedly, finally use washing with alcohol 2 times, at 40 ℃, dry, obtain Mierocrystalline cellulose/butyl methacrylate graft copolymer,
C, take 10.4 grams of above-mentioned Mierocrystalline cellulose/butyl methacrylate graft copolymer products, add 100 milliliters of (94 grams) N, dinethylformamide, be heated with stirring to 75 ℃, make Mierocrystalline cellulose/butyl methacrylate graft copolymer fully be dissolved in N, in dinethylformamide, form massfraction and be after 10% solution, add 0.31 gram of initiator azo-bis-isobutyl cyanide and 0.52 gram of linking agent N, N '-methylene-bisacrylamide, under nitrogen protection, at 75 ℃, crosslinking reaction is after 2.5 hours, and room temperature standing and defoaming is processed 24 hours;
D, above-mentioned treatment solution is filtered, and suppress with nitrogen, volume pump suction, after it is extruded by orifice, entering temperature is 50 ℃, in the precipitation bath of DMF/water, solidify, then after the water washing bath stretching that is 50 ℃ through temperature, at 170 ℃, dry, both obtained target product Mierocrystalline cellulose/butyl methacrylate graft copolymer oil suction fibre.This product has reached 36.8g/g to the oil absorbency of methylene dichloride.
Embodiment 3
A, to take the polymerization degree be that 738 cellulose cotton pulp 16.20 grams (0.1 moles) is torn into the small pieces that the length of side is 1cm, add N, 567 milliliters of N-N,N-DIMETHYLACETAMIDEs, stirring and refluxing 2 was as a child cooled to 100 ℃ afterwards, add 51.84 grams of Lithium chloride (anhydrous)s, continue to stir cooling, at room temperature stir 10 hours, obtain faint yellow transparent Mierocrystalline cellulose LiCl/DMAc solution;
B, above-mentioned Mierocrystalline cellulose LiCl/DMAc solution is cooled to 7 ℃, under stirring, add 0.8 mole of (111.5 milliliters) triethylamine alkalization, and be added dropwise to 0.4 mole of (76.3 grams) Tosyl chloride at 100 milliliters of N, lysate in N-N,N-DIMETHYLACETAMIDE, isothermal reaction adds 0.045 mole of (7.4 grams) initiator azo-bis-isobutyl cyanide after 20 hours, stirring is warming up to 58 ℃, and add 0.4 mole of (63.6 milliliters) grafted monomer butyl methacrylate, under nitrogen protection, after constant temperature stirring reaction 5.5 hours, this reaction solution is poured in 35 ℃ of pure water and precipitated, filter, again with 50 ℃ of pure water washings repeatedly, finally use washing with alcohol 2 times, at 40 ℃, dry, obtain Mierocrystalline cellulose/butyl methacrylate graft copolymer,
C, take 8.7 grams of above-mentioned Mierocrystalline cellulose/butyl methacrylate graft copolymer products, add 100 milliliters of (93.7 grams) N, N-N,N-DIMETHYLACETAMIDE, be heated with stirring to 76 ℃, make Mierocrystalline cellulose/butyl methacrylate graft copolymer fully be dissolved in N, in N-N,N-DIMETHYLACETAMIDE, form massfraction and be after 8.5% solution, add 0.174 gram of initiator azo-bis-isobutyl cyanide and 0.34 gram of linking agent N, N '-methylene-bisacrylamide, under nitrogen protection, at 76 ℃, crosslinking reaction is after 2.4 hours, and room temperature standing and defoaming is processed 24 hours;
D, above-mentioned treatment solution is filtered, and suppress with nitrogen, volume pump suction, after it is extruded by orifice, entering temperature is 40 ℃, in the precipitation bath of N,N-dimethylacetamide/water, solidify, then after the water washing bath stretching that is 25 ℃ through temperature, at 160 ℃, dry, both obtained target product Mierocrystalline cellulose/butyl methacrylate graft copolymer oil suction fibre.This product has reached 37.4g/g to the oil absorbency of methylene dichloride.
Embodiment 4
A, to take the polymerization degree be that 1000 cellulose cotton pulp 16.20 grams (0.1 moles) is torn into the small pieces that the length of side is 1cm, add N, 648 milliliters of N-N,N-DIMETHYLACETAMIDEs, stirring and refluxing 2 was as a child cooled to 100 ℃ afterwards, add 56.7 grams of Lithium chloride (anhydrous)s, continue to stir cooling, at room temperature stir 10 hours, obtain faint yellow transparent Mierocrystalline cellulose LiCl/DMAc solution;
B, above-mentioned Mierocrystalline cellulose LiCl/DMAc solution is cooled to 0 ℃, under stirring, add 1.1 moles of (153.3 milliliters) triethylamine alkalization, and be added dropwise to 0.7 mole of (133.5 grams) Tosyl chloride at 100 milliliters of N, lysate in N-N,N-DIMETHYLACETAMIDE, isothermal reaction adds 0.07 mole of (16.96 grams) initiator benzoyl peroxide after 24 hours, stirring is warming up to 65 ℃, and add 0.5 mole of (79.4 milliliters) grafted monomer butyl methacrylate, under nitrogen protection, after constant temperature stirring reaction 8 hours, this reaction solution is poured in 28 ℃ of pure water and precipitated, filter, again with 45 ℃ of pure water washings repeatedly, finally use washing with alcohol 2 times, at 40 ℃, dry, obtain Mierocrystalline cellulose/butyl methacrylate graft copolymer,
C, take 7.05 grams of above-mentioned Mierocrystalline cellulose/butyl methacrylate graft copolymer products, add 100 milliliters of (93.7 grams) N, N-N,N-DIMETHYLACETAMIDE, be heated with stirring to 80 ℃, make Mierocrystalline cellulose/butyl methacrylate graft copolymer fully be dissolved in N, in N-N,N-DIMETHYLACETAMIDE, form massfraction and be after 7% solution, add 0.07 gram of initiator benzoyl peroxide and 0.21 gram of linking agent N, N '-methylene-bisacrylamide, under nitrogen protection, at 80 ℃, crosslinking reaction is after 2 hours, and room temperature standing and defoaming is processed 24 hours;
D, above-mentioned treatment solution is filtered, and suppress with nitrogen, volume pump suction, after it is extruded by orifice, entering temperature is 45 ℃, in the precipitation bath of N,N-dimethylacetamide/water, solidify, then after the water washing bath stretching that is 40 ℃ through temperature, at 150 ℃, dry, both obtained target product Mierocrystalline cellulose/butyl methacrylate graft copolymer oil suction fibre.This product has reached 35.6g/g to the oil absorbency of methylene dichloride.
Claims (7)
1. a preparation method for Mierocrystalline cellulose/butyl methacrylate graft copolymer oil suction fibre, is characterized in that following these steps to carrying out:
A, cellulose cotton pulp is torn into the small pieces that the length of side is 1-1.5cm, add N, N-N,N-DIMETHYLACETAMIDE, stirring heating, reflux and after 2 hours, stop heating, add Lithium chloride (anhydrous) after being cooled to 100 ℃, continue to stir cooling, at room temperature stir 10 hours, obtain the Mierocrystalline cellulose LiCl/DMAc solution fully dissolving;
B, Mierocrystalline cellulose LiCl/DMAc solution in step a is cooled to 0-10 ℃, stirs and add after triethylamine alkalization, be added dropwise to the lysate of Tosyl chloride in N,N-dimethylacetamide, isothermal reaction 8-24 hour;
C, will in step b reaction system, add after initiator benzoyl peroxide or azo-bis-isobutyl cyanide, stir and be warming up to 50-75 ℃, and add grafted monomer butyl methacrylate, constant temperature stirring reaction 4-8 hour under nitrogen protection;
D, step c reaction solution is poured in pure water after precipitation, with pure water and ethanol, fully washed, oven dry at 40 ℃, obtains Mierocrystalline cellulose/butyl methacrylate graft copolymer;
E, by steps d graft copolymerization product heating for dissolving at N, dinethylformamide or N, in N-dimethylacetamide solvent, form after the graft copolymer solution of homogeneous transparent, add initiator benzoyl peroxide or azo-bis-isobutyl cyanide, and linking agent N, N '-methylene-bisacrylamide, under nitrogen protection, at 70-80 ℃, after crosslinking reaction 2-3 hour, room temperature standing and defoaming is processed 24 hours;
F, by the treatment solution in step e after filtration, with nitrogen, suppress, volume pump suction, after being extruded by orifice, it enters N, dinethylformamide/water or N, in the precipitation bath of N-N,N-DIMETHYLACETAMIDE/water, solidify, then after water washing bath stretches, at 150-180 ℃, dry and obtain Mierocrystalline cellulose/butyl methacrylate graft copolymer oil suction fibre.
2. method according to claim 1, the polymerization degree that it is characterized in that cellulose cotton pulp described in step a is 250-1000, the consumption of N,N-dimethylacetamide is 20-40 times of Mierocrystalline cellulose quality, and the consumption of Lithium chloride (anhydrous) is 2.5-3.5 times of Mierocrystalline cellulose quality.
3. method according to claim 1, the amount of substance that it is characterized in that triethylamine in step b is 7-11 times of cellulosic amount of substance, the amount of substance of Tosyl chloride is 3-7 times of cellulosic amount of substance, and isothermal reaction temperature is 0-10 ℃, and the isothermal reaction time is 8-24 hour.
4. method according to claim 1, the amount of substance that it is characterized in that initiator in step c is 0.3-0.7 times of cellulosic amount of substance, the amount of substance of grafted monomer butyl methacrylate is 1-5 times of cellulosic amount of substance, isothermal reaction temperature is 50-75 ℃, and the isothermal reaction time is 4-8 hour.
5. method according to claim 1, is characterized in that in steps d, precipitin reaction liquid pure water temperature used is 25-35 ℃, and the pure water temperature of cleaning product is 35-50 ℃.
6. method according to claim 1, it is characterized in that in step e, Mierocrystalline cellulose/butyl methacrylate graft copolymer is dissolved in N, dinethylformamide or N, the solution quality umber forming in N-dimethylacetamide solvent is 7-15%, the consumption of initiator is the 1-5% of Mierocrystalline cellulose/butyl methacrylate graft copolymerization amount, dosage of crosslinking agent is the 3-10% of Mierocrystalline cellulose/butyl methacrylate graft copolymerization amount, crosslinking reaction temperature is 70-80 ℃, and cross-linking reaction time is 2-3 hour.
7. method according to claim 1, is characterized in that in step f, coagulation bath temperature is 30-50 ℃, and water washing bath temperature is 25-50 ℃, and the bake out temperature of final oil suction fibre product is 150-180 ℃.
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