CN102766917A - 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 cellulose LiCl/DMAc (lithium chloride/N; The N-dimethylacetylamide) homogeneous phase solution system; After making cellulose and butyl methacrylate make cellulose/butyl methacrylate graft copolymer through ATRP method single step reaction; With its dissolving, preparation contains the spinnable solution of crosslinking agent, adopts the dry-wet spinning technology to prepare the method for cellulose/butyl methacrylate graft copolymer oil suction fibre again.
Technical background
Along with the raising of industrial expansion and people's living standard, the sump oil discharge capacity is increasing, and river, ocean and human habitat have been brought serious threat.According to statistics, have at least every year 5000000-1,000 ten thousand tons of oils to get into water body by all means in the world, become the major pollutants of water body, caused people's very big concern.
In many greasy dirt processing methods, based on the absorption method of oil absorption material have efficiently, economic, the characteristics being convenient to promote the use of and extensively being adopted.Researcher has been developed multiple oil absorption material, like clay, silica, pearl layer iron, the lime of mineral-type; Organic type paper pulp, kapok, peat; Synthetic type polystyrene fabric, polypropylene non-woven fabric, polyacrylate series high oil-absorbing resin etc.Wherein, High oil-absorbing resin be one type by the specific function macromolecular material of oleophylic monomer through the appropriately crosslinked tool tridimensional network that forms; Compare with other oil absorption materials, high oil-absorbing resin has that the oil suction kind is many, speed is fast, oil suction/suction selectivity is good and have advantages such as good heat resistance and cold resistance.Yet because said material, it is synthetic to be based on petroleum chemicals on the one hand mostly, and not only price grows to even greater heights, and be difficult to natural degradation after discarded, is to burn or landfill all might cause secondary pollution; On the other hand; Because such oil-absorbing resin is the pelletized product with three-dimensional netted cross-linked structure mostly, the limitation of shape can make its application in many aspects be restricted; Compare with it; The specific area of oil suction fibre is bigger, can be processed into the goods of various forms as required, and Application Areas can be widened greatly; And three-dimensional netted cross-linked structure makes oil-absorbing resin have insoluble not molten characteristics again, is difficult to the traditional spin processes of utilization 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 absorbency is suitable with high oil-absorbing resin, and the wider cellulose base intrinsic oil suction fibre of Application Areas, are of great practical significance.
Research about the intrinsic oil suction fibre abroad still is not reported.Domestic Tianjin University of Technology carried out research to this; Employing hydroxyethyl methacrylate such as obturage is a latent crosslinker; After synthesizing linearity that oil absorbency contains latent crosslinker preferably and becoming fine copolymerization methacrylate; It is modulated into spinning solution, adopts the dry-wet spinning technology to spin copolymerization methacrylic acid ester fiber; Xu Naiku etc. are monomer with BMA, Jia Jibingxisuanβ-Qiang Yizhi (HEMA), after the employing suspension polymerization synthesizes the BMA/HEMA copolymer, have spinned the BMA/HEMA copolymer fibre with the highly concentrated solution spin processes.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 of diameter for 200-5000nm on the basis of ethylene propylene diene rubber, then with the three-dimensional netted oil suction fibre material of wave radiation technology preparation.But,, also do not see the research report with regard to the intrinsic oil suction fibre of cellulose base.
Summary of the invention
The object of the present invention is to provide the preparation method of a kind of cellulose/butyl methacrylate graft copolymer oil suction fibre.This method at first is that cellulose fully is dissolved in lithium chloride/N; After making cellulosic solution in the N-dimethylacetylamide double solvents system; At cellulose/lithium chloride/N; In the N-dimethylacetylamide homogeneous phase solution system, make cellulose and butyl methacrylate prepare cellulose/butyl methacrylate graft copolymer, then with its dissolving through ATRP method single step reaction; Preparation contains the spinnable solution of crosslinking agent, adopts dry-wet spinning technology preparation cellulose/butyl methacrylate graft copolymer oil suction fibre again.
This method is simple to operate; Reaction condition is gentle; Shortcoming such as can not only overcome that heterogeneous glycerol polymerization legal system is equipped with that cellulose-based oil-absorption material exists that reagent dosage is big, long flow path, reaction are difficult to control and product is inhomogeneous; And can control the product percent grafting according to the network structure requirement of final products easily; The oleophylic segment is evenly distributed on the cellulosic matrix, and good because of gained cellulose/butyl methacrylate graft copolymer solubility property simultaneously, the preparation of spinning solution and spinning process afterwards all make things convenient for easy to operate.
The preparation method of a kind of cellulose of the present invention/butyl methacrylate graft copolymer oil suction fibre follows these steps to carry out:
A, the cellulose cotton pulp is torn into the small pieces that the length of side is 1-1.5cm, adds DMAC N,N; Stirring and refluxing 2 is cooled to 100 ℃ as a child, add anhydrous Lithium chloride, continues to stir cooling; At room temperature stirred preparation cellulose LiCl/DMAc solution 10 hours;
B, cellulose LiCl/DMAc solution among the step a is cooled to 0-10 ℃, stirs and add the triethylamine alkalization, and be added dropwise to the lysate of paratoluensulfonyl chloride in DMAC N,N, isothermal reaction 8-24 hour;
C, with after adding initator benzoyl peroxide or azo-bis-isobutyl cyanide in the step b reaction system, stir and be warming up to 50-75 ℃, and add the grafted monomers butyl methacrylate, the constant temperature stirring reaction is 4-8 hour under nitrogen protection;
D, pour step c reactant liquor in pure water post precipitation, fully wash with pure water and ethanol, 40 ℃ of oven dry down obtain cellulose/butyl methacrylate graft copolymer;
E, with steps d graft copolymerization product heating for dissolving at N, form the graft copolymer solution of homogeneous transparent in dinethylformamide or the DMAC N,N solvent after; Add initator benzoyl peroxide or azo-bis-isobutyl cyanide; And crosslinking agent N, N '-methylene-bisacrylamide is under nitrogen protection; After stirring 2-3 hour at a slow speed under 70-80 ℃, the room temperature standing and defoaming was handled 24 hours;
F, the treatment fluid among the step e filtered after; Suppress with nitrogen, the measuring pump suction makes it extrude the back by spinneret orifice and gets into N; Dinethylformamide/water or N; Solidify in N-dimethylacetylamide/water coagulating bath, after stretching is bathed in washing, dry preparation cellulose/butyl methacrylate graft copolymer oil suction fibre down again in 150-180 ℃.
The degree of polymerization of the pulp of cellulose cotton described in the step a is 250-1000, and the consumption of DMAC N,N is 20-40 a times of cellulose quality, and the consumption of anhydrous Lithium chloride is 2.5-3.5 a times of cellulose quality.
Among the step b amount of substance of triethylamine be cellulosic amount of substance 7-11 doubly, the amount of substance of paratoluensulfonyl chloride be cellulosic amount of substance 3-7 doubly, the isothermal reaction temperature is 0-10 ℃, the isothermal reaction time is 8-24 hour.。
Among the step c amount of substance of initator be cellulosic amount of substance 0.3-0.7 doubly, the amount of substance of grafted monomers butyl methacrylate be cellulosic amount of substance 1-5 doubly, the isothermal reaction temperature is 50-75 ℃, the isothermal reaction time is 4-8 hour.
The used pure water temperature of precipitation reaction liquid is 25-35 ℃ in the steps d, and the pure water temperature of cleaning product is 35-50 ℃.
Cellulose among the step e-butyl methacrylate graft copolymer is dissolved in N; Dinethylformamide or N; The solution quality umber that forms in the N-dimethylacetamide solvent is 7-15%, and the consumption of initator is the 1-5% of cellulose/butyl methacrylate graft copolymerization amount, and dosage of crosslinking agent is the 3-10% of cellulose/butyl methacrylate graft copolymerization amount; The cross-linking reaction temperature is 70-80 ℃, and cross-linking reaction time is 2-3 hour.
Coagulation bath temperature is 30-50 ℃ among the step f, and the 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 the preparation method of a kind of cellulose/butyl methacrylate graft copolymer oil suction fibre, and this method has:
(1) utilize plant cellulose to be base material; Adopt ATRP method single step reaction to make cellulose/butyl methacrylate graft copolymer; With its dissolving, after preparation contains the spinnable solution of crosslinking agent, adopt dry-wet spinning technology preparation cellulose/butyl methacrylate graft copolymer oil suction fibre.Compare with the oil suction fibre of the heterogeneous glycerol polymerization method preparation of Traditional use; Not only reagent dosage reduces; The homopolymers that does not influence the product oil absorbency produces, and can the oleophylic segment is evenly distributed on the cellulosic matrix according to the network architecture requirement control product percent grafting of fiber; And then the plain body of controlling fiber and oil suction prop up the cross-linked network structure of interchain, makes the oil absorbency of oil suction fibre obtain increasing substantially.
(2) the intrinsic good characteristic of the existing cellulose of cellulose graft copolymer; Has the new capability that the synthetic polymer side chain is given again; So, the oil suction fibre that the present invention utilizes cellulose and the synthetic graft copolymer solvent spinning of butyl methacrylate to prepare, existing cellulosic biodegradable; Possessed the high oil-absorbing ability of long-chain ester again, thereby solved the difficulty that general oil absorption material can not solve high oil-absorbing and biological degradability simultaneously.
The specific embodiment
Further specify the present invention below in conjunction with embodiment
Embodiment 1
A, to take by weighing the degree of polymerization be that 250 cellulose cotton pulp, 16.20 grams (0.1 mole) are torn into the small pieces that the length of side is 1.5cm; Add 324 milliliters of DMAC N,Ns, stirring and refluxing 2 is cooled to 100 ℃ as a child; Add anhydrous Lithium chloride 40.5 grams; Continue to stir cooling, at room temperature stirred 10 hours, obtain faint yellow transparent cellulose LiCl/DMAc solution;
B, above-mentioned cellulose LiCl/DMAc solution is cooled to 10 ℃, stirs and add 0.7 mole of (97.6 milliliters) triethylamine alkalization down, and be added dropwise to 0.3 mole of (57.2 gram) paratoluensulfonyl chloride at 100 milliliters of N; Lysate in the N-dimethylacetylamide, isothermal reaction add 0.03 mole of (7.3 gram) initator benzoyl peroxide after 8 hours, stir and be warming up to 75 ℃; And add 0.1 mole of (15.9 milliliters) grafted monomers butyl methacrylate, under nitrogen protection, the constant temperature stirring reaction is after 6 hours; This reactant liquor poured in 25 ℃ of pure water precipitate; Filter, with 35 ℃ of pure water washings repeatedly, use washing with alcohol at last 2 times again; 40 ℃ of oven dry down obtain cellulose/butyl methacrylate graft copolymer;
C, take by weighing 16.6 gram above-mentioned cellulose/butyl methacrylate graft copolymer products, adds 100 milliliters of (94 restrain) N, dinethylformamide; Be heated with stirring to 70 ℃; Make cellulose/butyl methacrylate graft copolymer fully be dissolved in N, form mass fraction in the dinethylformamide and be 15% solution after, add 0.83 gram initator benzoyl peroxide and 1.66 gram crosslinking agent N; N '-methylene-bisacrylamide; Under nitrogen protection, after 3 hours, the room temperature standing and defoaming was handled 24 hours in 70 ℃ of following cross-linking reactions;
D, above-mentioned treatment fluid is filtered, and suppress the measuring pump suction with nitrogen; Making it extrude back entering temperature by spinneret orifice is 30 ℃; N solidifies in dinethylformamide/water coagulating bath, again after temperature is 30 ℃ washing bath stretching; In 180 ℃ of oven dry down, both got target product cellulose/butyl methacrylate graft copolymer oil suction fibre.This product has reached 34.4g/g to the oil absorbency of carrene.
Embodiment 2
A, to take by weighing the degree of polymerization be that 521 cellulose cotton pulp, 16.20 grams (0.1 mole) are torn into the small pieces that the length of side is 1.2cm; Add 486 milliliters of DMAC N,Ns, stirring and refluxing 2 is cooled to 100 ℃ as a child; Add anhydrous Lithium chloride 48.6 grams; Continue to stir cooling, at room temperature stirred 10 hours, obtain faint yellow transparent cellulose LiCl/DMAc solution;
B, above-mentioned cellulose LiCl/DMAc solution is cooled to 5 ℃, stirs and add 0.9 mole of (125.4 milliliters) triethylamine alkalization down, and be added dropwise to 0.5 mole of (95.3 gram) paratoluensulfonyl chloride at 100 milliliters of N; Lysate in the N-dimethylacetylamide, isothermal reaction add 0.05 mole of (8.2 gram) initator azo-bis-isobutyl cyanide after 14 hours, stir and be warming up to 50 ℃; And add 0.3 mole of (47.7 milliliters) grafted monomers butyl methacrylate, under nitrogen protection, the constant temperature stirring reaction is after 4 hours; This reactant liquor poured in 30 ℃ of pure water precipitate; Filter, with 40 ℃ of pure water washings repeatedly, use washing with alcohol at last 2 times again; 40 ℃ of oven dry down obtain cellulose/butyl methacrylate graft copolymer;
C, take by weighing 10.4 gram above-mentioned cellulose/butyl methacrylate graft copolymer products, adds 100 milliliters of (94 restrain) N, dinethylformamide; Be heated with stirring to 75 ℃; Make cellulose/butyl methacrylate graft copolymer fully be dissolved in N, form mass fraction in the dinethylformamide and be 10% solution after, add 0.31 gram initator azo-bis-isobutyl cyanide and 0.52 gram crosslinking agent N; N '-methylene-bisacrylamide; Under nitrogen protection, after 2.5 hours, the room temperature standing and defoaming was handled 24 hours in 75 ℃ of following cross-linking reactions;
D, above-mentioned treatment fluid is filtered, and suppress the measuring pump suction with nitrogen; Making it extrude back entering temperature by spinneret orifice is 50 ℃; N solidifies in dinethylformamide/water coagulating bath, again after temperature is 50 ℃ washing bath stretching; In 170 ℃ of oven dry down, both got target product cellulose/butyl methacrylate graft copolymer oil suction fibre.This product has reached 36.8g/g to the oil absorbency of carrene.
Embodiment 3
A, to take by weighing the degree of polymerization be that 738 cellulose cotton pulp, 16.20 grams (0.1 mole) are torn into the small pieces that the length of side is 1cm; Add 567 milliliters of DMAC N,Ns, stirring and refluxing 2 is cooled to 100 ℃ as a child; Add anhydrous Lithium chloride 51.84 grams; Continue to stir cooling, at room temperature stirred 10 hours, obtain faint yellow transparent cellulose LiCl/DMAc solution;
B, above-mentioned cellulose LiCl/DMAc solution is cooled to 7 ℃, stirs and add 0.8 mole of (111.5 milliliters) triethylamine alkalization down, and be added dropwise to 0.4 mole of (76.3 gram) paratoluensulfonyl chloride at 100 milliliters of N; Lysate in the N-dimethylacetylamide, isothermal reaction add 0.045 mole of (7.4 gram) initator azo-bis-isobutyl cyanide after 20 hours, stir and be warming up to 58 ℃; And add 0.4 mole of (63.6 milliliters) grafted monomers butyl methacrylate, under nitrogen protection, the constant temperature stirring reaction is after 5.5 hours; This reactant liquor poured in 35 ℃ of pure water precipitate; Filter, with 50 ℃ of pure water washings repeatedly, use washing with alcohol at last 2 times again; 40 ℃ of oven dry down obtain cellulose/butyl methacrylate graft copolymer;
C, take by weighing 8.7 gram above-mentioned cellulose/butyl methacrylate graft copolymer products, adds 100 milliliters of (93.7 restrain) DMAC N,Ns; Be heated with stirring to 76 ℃; Cellulose/butyl methacrylate graft copolymer fully being dissolved in the DMAC N,N form mass fraction is behind 8.5% the solution, to add 0.174 gram initator azo-bis-isobutyl cyanide and 0.34 gram crosslinking agent N; N '-methylene-bisacrylamide; Under nitrogen protection, after 2.4 hours, the room temperature standing and defoaming was handled 24 hours in 76 ℃ of following cross-linking reactions;
D, above-mentioned treatment fluid is filtered, and suppress the measuring pump suction with nitrogen; Making it extrude back entering temperature by spinneret orifice is 40 ℃; Solidify in DMAC N,N/water coagulating bath, again after temperature is 25 ℃ washing bath stretching; In 160 ℃ of oven dry down, both got target product cellulose/butyl methacrylate graft copolymer oil suction fibre.This product has reached 37.4g/g to the oil absorbency of carrene.
Embodiment 4
A, to take by weighing the degree of polymerization be that 1000 cellulose cotton pulp, 16.20 grams (0.1 mole) are torn into the small pieces that the length of side is 1cm; Add 648 milliliters of DMAC N,Ns, stirring and refluxing 2 is cooled to 100 ℃ as a child; Add anhydrous Lithium chloride 56.7 grams; Continue to stir cooling, at room temperature stirred 10 hours, obtain faint yellow transparent cellulose LiCl/DMAc solution;
B, above-mentioned cellulose LiCl/DMAc solution is cooled to 0 ℃, stirs and add 1.1 moles of (153.3 milliliters) triethylamines alkalization down, and be added dropwise to 0.7 mole of (133.5 gram) paratoluensulfonyl chloride at 100 milliliters of N; Lysate in the N-dimethylacetylamide, isothermal reaction add 0.07 mole of (16.96 gram) initator benzoyl peroxide after 24 hours, stir and be warming up to 65 ℃; And add 0.5 mole of (79.4 milliliters) grafted monomers butyl methacrylate, under nitrogen protection, the constant temperature stirring reaction is after 8 hours; This reactant liquor poured in 28 ℃ of pure water precipitate; Filter, with 45 ℃ of pure water washings repeatedly, use washing with alcohol at last 2 times again; 40 ℃ of oven dry down obtain cellulose/butyl methacrylate graft copolymer;
C, take by weighing 7.05 gram above-mentioned cellulose/butyl methacrylate graft copolymer products, adds 100 milliliters of (93.7 restrain) DMAC N,Ns; Be heated with stirring to 80 ℃; Cellulose/butyl methacrylate graft copolymer fully being dissolved in the DMAC N,N form mass fraction is behind 7% the solution, to add 0.07 gram initator benzoyl peroxide and 0.21 gram crosslinking agent N; N '-methylene-bisacrylamide; Under nitrogen protection, after 2 hours, the room temperature standing and defoaming was handled 24 hours in 80 ℃ of following cross-linking reactions;
D, above-mentioned treatment fluid is filtered, and suppress the measuring pump suction with nitrogen; Making it extrude back entering temperature by spinneret orifice is 45 ℃; Solidify in DMAC N,N/water coagulating bath, again after temperature is 40 ℃ washing bath stretching; In 150 ℃ of oven dry down, both got target product cellulose/butyl methacrylate graft copolymer oil suction fibre.This product has reached 35.6g/g to the oil absorbency of carrene.
Claims (7)
1. the preparation method of cellulose/butyl methacrylate graft copolymer oil suction fibre is characterized in that following these steps to carrying out:
A, the cellulose cotton pulp is torn into the small pieces that the length of side is 1-1.5cm, adds DMAC N,N; Agitating heating; Refluxing 2 stops heating after as a child, adds anhydrous Lithium chloride after being cooled to 100 ℃, continues to stir cooling; At room temperature stirred the cellulose LiCl/DMAc solution that is fully dissolved 10 hours;
B, cellulose LiCl/DMAc solution among the step a is cooled to 0-10 ℃, stir add the triethylamine alkalization after, be added dropwise to the lysate of paratoluensulfonyl chloride in DMAC N,N, isothermal reaction 8-24 hour;
C, with after adding initator benzoyl peroxide or azo-bis-isobutyl cyanide in the step b reaction system, stir and be warming up to 50-75 ℃, and add the grafted monomers butyl methacrylate, the constant temperature stirring reaction is 4-8 hour under nitrogen protection;
D, pour step c reactant liquor in pure water post precipitation, fully wash with pure water and ethanol, 40 ℃ of oven dry down obtain cellulose/butyl methacrylate graft copolymer;
E, with steps d graft copolymerization product heating for dissolving at N, form the graft copolymer solution of homogeneous transparent in dinethylformamide or the DMAC N,N solvent after; Add initator benzoyl peroxide or azo-bis-isobutyl cyanide; And crosslinking agent N, N '-methylene-bisacrylamide is under nitrogen protection; After 70-80 ℃ of following cross-linking reaction 2-3 hour, the room temperature standing and defoaming was handled 24 hours;
F, with the treatment fluid among the step e after filtration; Suppress with nitrogen, the measuring pump suction makes it extrude the back by spinneret orifice and gets into N; Dinethylformamide/water or N; Solidify in N-dimethylacetylamide/water coagulating bath, after stretching was bathed in washing, oven dry promptly got cellulose/butyl methacrylate graft copolymer oil suction fibre under 150-180 ℃ again.
2. method according to claim 1; The degree of polymerization that it is characterized in that cellulose cotton pulp described in the step a is 250-1000; The consumption of DMAC N,N is 20-40 a times of cellulose quality, and the consumption of anhydrous Lithium chloride is 2.5-3.5 a times of cellulose quality.
3. method according to claim 1; The amount of substance that it is characterized in that triethylamine among the step b is 7-11 a times of cellulosic amount of substance; The amount of substance of paratoluensulfonyl chloride is 3-7 a times of cellulosic amount of substance, and the 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 initator among the step c is 0.3-0.7 a times of cellulosic amount of substance; The amount of substance of grafted monomers butyl methacrylate is 1-5 a times of cellulosic amount of substance; The 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 the used pure water temperature of precipitation reaction liquid is 25-35 ℃ in the steps d, and the pure water temperature of cleaning product is 35-50 ℃.
6. method according to claim 1; It is characterized in that cellulose among the step e/butyl methacrylate graft copolymer is dissolved in N; Dinethylformamide or N; The solution quality umber that forms in the N-dimethylacetamide solvent is 7-15%, and the consumption of initator is the 1-5% of cellulose/butyl methacrylate graft copolymerization amount, and dosage of crosslinking agent is the 3-10% of cellulose/butyl methacrylate graft copolymerization amount; The cross-linking reaction temperature is 70-80 ℃, and cross-linking reaction time is 2-3 hour.
7. method according to claim 1 is characterized in that coagulation bath temperature is 30-50 ℃ among the step f, and the washing bath temperature is 25-50 ℃, and the bake out temperature of final oil suction fibre product is 150-180 ℃.
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| CN107361506A (en) * | 2017-07-27 | 2017-11-21 | 张艳雪 | A kind of macromolecule material powder puff with oil suction effect and preparation method thereof |
| CN113122951A (en) * | 2019-12-31 | 2021-07-16 | 中国石油化工股份有限公司 | Fiber filament prepared from graft polymer of cellulose and PET |
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| WO2023130830A1 (en) * | 2022-01-05 | 2023-07-13 | 广东邦普循环科技有限公司 | Preparation method for and use of lithium silicate-based adsorbent |
| US11986794B1 (en) | 2022-01-05 | 2024-05-21 | Guangdong Brunp Recycling Technology Co., Ltd. | Preparation method for and use of lithium silicate-based adsorbent |
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