CN104558423A - Method for preparing thermoplastic cellulose based copolymer and application of thermoplastic cellulose based copolymer - Google Patents
Method for preparing thermoplastic cellulose based copolymer and application of thermoplastic cellulose based copolymer Download PDFInfo
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Abstract
The invention discloses a method for preparing a thermoplastic cellulose based copolymer and application of the thermoplastic cellulose based copolymer. The method comprises the following steps: (1) sufficiently dissolving dried cellulose in ionic liquid, paraformaldehyde/dimethyl sulfoxide or lithium chloride/N'N'-dimethyl formamide to obtain a cellulose solution having a concentration of 5-15wt%; (2) adding a solvent I into a reaction container, removing air dissolved in the solvent I, adding a chain transfer agent and an initiator, adding a mixture of a second monomer and the cellulose solution, and reacting at 50-90 DEG C for 4-24 hours under a stirring condition to obtain a reaction mixture; precipitating with deionized water, sequentially washing with deionized water and a solvent II, and drying to obtain the thermoplastic cellulose based copolymer. The method is simple in process, easy to control, high in production efficiency, wide in application range and convenient for practical application. The prepared product can be used for preparing fibers or films, the preparation process is simple, and the product quality is good.
Description
Technical field
The present invention relates to cellulose base multipolymer, particularly relate to a kind of preparation method and its usage of thermoplastic cellulose base co-polymer.
Background technology
Mierocrystalline cellulose is one of renewable resources that reserves are the abundantest in the world, a kind of linear polymeric be formed by connecting by β-Isosorbide-5-Nitrae-D-glycosidic link by cellobiose repeating unit.Molecular chain existing a large amount of hydroxyls and impart the good water absorbability of Mierocrystalline cellulose, ventilation property, dyeability and high-strength, the feature such as Gao Mo, light weight, is a kind of excellent natural high polymer.Because cellulose molecular chain is completely linear, there is no branch, in intermolecular and molecule, there is very strong hydrogen bond action, make its fusing point higher than decomposition temperature, not there is melt-processible.Therefore, adopt viscose process production technique in industrial production always.The principle of viscose process production technique is: first Mierocrystalline cellulose and alkali reaction generate soda cellulose, then soda cellulose reacts with dithiocarbonic anhydride and generates cellulose xanthate ester, cellulose xanthate ester is dissolved in aqueous sodium hydroxide solution becomes viscose solution, viscose solution through deaeration, filter after can spinning or blown film, fiber or membrane product decomposition-reduction in acid coagulating bath becomes regenerated cellulose.Although adhering process is successful Application century more than one, but macro-corrosion solvent to be used in the course of processing, as sodium hydroxide, dithiocarbonic anhydride etc., environmental pollution is serious, and Production Flow Chart is long, energy consumption is large, production cost is higher, constrains development and the large-scale application of cellulose based degradable material.Therefore, realize cellulosic melt-processable and there is far-reaching social effect and economic implications.
The method of the Mierocrystalline cellulose melting modification reported at present mainly contains following three kinds: 1, add a large amount of monomerics, as glycerine, ethylene glycol, dimethyl phthalate etc., in melt-spinning process, softening agent oozes out in a large number and volatilizees, and the fiber number of fiber is difficult to control and physical and mechanical properties is poor; 2, open loop graft polymerization, adopt the open loop such as 6-caprolactone, lactic acid graft polymerization to derivatived cellulose, as cellulose acetate, Cellulose diacetate etc., skeleton on, adopt cellulosic matrix mostly to be cellulosic derivative, although there is not the problem that external plasticizer exosmoses, but derivatived cellulose material cost is higher, and graft side chain polycaprolactone, poly(lactic acid) thermodynamic stability are poor, there is side chain flowing in product, cannot meet the requirement of melt-spinning technology to melt thermodynamic stability at a lower temperature; , there is the problem such as solvent recuperation and environmental pollution in 3, ionic liquid plasticising.
Chinese invention patent (CN102277642) discloses one and methyl acrylate and carboxymethyl cellulose graft copolymerization is carried out thermoplastic modification to Mierocrystalline cellulose, is then dissolved in organic solvent by thermoplastic cellulose derivative and carries out electrospun nanofibers.Melt modification is carried out in the aliphatic polyester and the cellulose ester graft polymerization that disclose the repeating unit by having carbonatoms 2 ~ 5 in the patent (PCT/JP02/06336) of Tokyo Co., Ltd. application, and the rate of loss of thermoplastic cellulose derivative at 200 DEG C is lower than 5wt%.Above-mentioned two applications for a patent for invention are all matrix with derivatived cellulose, and material cost is high.Chinese invention patent (CN103193964) discloses a kind of one kettle way by Mierocrystalline cellulose esterification and the preparation method of grafted aliphatic polyester multipolymer; although adopt raw material for the cellulose resource such as cotton pulp pool, Mierocrystalline cellulose cheap and easy to get; but preparation process will adopt the acylating reagents such as diacetyl oxide, propionic anhydride, Acetyl Chloride 98Min. to prepare cellulose ester; one kettle way technique synchronously carries out the graft reaction of acylation reaction and aliphatic polyester; acylating reagent cost is higher; and in reaction process, acylating reagent and aliphatic polyester are formed and compete, and add the uncontrollability of reaction process.
Summary of the invention
First object of the present invention is: the preparation method providing a kind of thermoplastic cellulose base co-polymer, and the method technique is simple, and easily control, production efficiency is high, applied widely, is convenient to practical application.
Second object of the present invention is: provide the thermoplastic cellulose base co-polymer utilizing aforesaid method to obtain to prepare the method for fiber or film.
For this reason, technical scheme of the present invention is as follows:
A preparation method for thermoplastic cellulose base co-polymer, comprises the steps:
1) by after Mierocrystalline cellulose drying, 65 ~ 95 DEG C, be fully dissolved in ionic liquid, paraformaldehyde/dimethyl sulfoxide (DMSO) or lithium chloride/N ' N '-dimethyl methane amide under agitation condition and obtain cellulose solution, the concentration of this cellulose solution is 5 ~ 15wt%;
2) in the reaction vessel that condenser and agitator be housed, solvent I is added, remove the air wherein dissolved, then in reaction vessel, chain-transfer agent and initiator is added, add second comonomer and step 1 again) mixture of cellulose solution that obtains, 50 ~ 90 DEG C, reaction 4 ~ 24h obtains reaction mixture under agitation condition; Described reaction mixture is precipitated in deionized water, with deionized water repetitive scrubbing throw out, removes residual solvent I; Then again through solvent II washing, the homopolymer of removing second comonomer and unreacted second comonomer, finally carry out vacuum-drying, obtain described thermoplastic cellulose base co-polymer;
Wherein: the mol ratio of the glucose unit ring that the Mierocrystalline cellulose in described second comonomer and cellulose solution contains is: 1 ~ 6:1;
The addition of described chain-transfer agent is 0.05 ~ 5.0mol% of the molar weight sum of glucose unit ring in described second comonomer and Mierocrystalline cellulose;
The addition of described initiator is 0.1 ~ 20.0mol% of the molar weight sum of glucose unit ring in described second comonomer and Mierocrystalline cellulose;
Described Mierocrystalline cellulose is Microcrystalline Cellulose, Cotton Pulp, linters, cotton, wood pulps, bamboo pulp, cellulosic filter paper or absorbent cotton;
Described second comonomer is the esters monomer containing unsaturated double-bond or the imidazoles monomer containing unsaturated double-bond;
Described solvent I is N ' N '-dimethyl methane amide, N ' N '-dimethyl ethanamide, dimethyl sulfoxide (DMSO) or step 1) any one in described ionic liquid; Described solvent II is the homopolymer of second comonomer and the cosolvent of unreacted second comonomer.
The described esters monomer containing unsaturated double-bond is methyl acrylate, ethyl propenoate, propyl acrylate, butyl acrylate, stearyl acrylate acid esters, lauryl acrylate, isopropyl acrylate, isobutyl acrylate, tert-butyl acrylate, Isooctyl acrylate monomer, isodecyl acrylate, Hydroxyethyl acrylate, Propylene glycol monoacrylate, hy-droxybutyl, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, n propyl methacrylate, n-BMA, lauryl methacrylate(LMA), stearyl methacrylate, ethyl methyl acrylate, dimethyl maleate, ethyl maleate, dibutyl maleinate, diallyl maleate, vinyl-acetic ester, any one in ethene diethyl ester and maleopimaric acid allyl ester,
The described imidazoles monomer containing unsaturated double-bond is vinyl imidazole or N-allyl imidazole.
Described chain-transfer agent is any one in lauryl mercaptan, N-octyl mercaptan, β-thioglycol and Virahol.
Described initiator be benzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, hydrogen peroxide to the Meng alkane, dilauroyl peroxide, dibenzoyl peroxide, di-isopropyl peroxydicarbonate, any one in azo-bis-isobutyl cyanide and azo two cyanogen in different heptan.
Step 1) mass ratio of paraformaldehyde and dimethyl sulfoxide (DMSO) is 1:8 ~ 12 in described paraformaldehyde/dimethyl sulfoxide (DMSO); In described lithium chloride/N ' N '-dimethyl methane amide, the mass ratio of lithium chloride and N ' N '-dimethyl methane amide is 1:8 ~ 12.
Step 1) described ionic liquid is glyoxaline ion liquid.Described glyoxaline ion liquid is 1-methyl-3-ethyl imidazol(e) phosphoric acid salt, 1-ethyl-3-methylimidazole acetate, 1-butyl-3-methyl-imidazoles villaumite or 1-allyl group-3-Methylimidazole villaumite.
Described solvent II is any one in formic acid, methyl alcohol, tetrahydrofuran (THF), methylene dichloride, acetone, chloroform, toluene, dimethylbenzene and benzene.
The addition means of described cellulose solution and second comonomer mixture is once add, drip or add several times after both mix.
Step 1) cellulosic drying conditions is: dry 6 ~ 24h under DEG C condition of room temperature ~ 90 in vacuum drying oven.
Utilize obtained thermoplastic cellulose base co-polymer to prepare the method for fiber or film, comprise following steps:
1. by after obtained thermoplastic cellulose base co-polymer drying, mix with the thermo-stabilizer accounting for its quality 0 ~ 40% and obtain raw material;
2. described raw material is carried out melt extruding spinning or blown film, namely the cellulosic fibre that can degrade or film is obtained, wherein below more than the fusing point of thermoplastic cellulose base co-polymer 1. selected between step of melt processing temperature 5 ~ 30 DEG C of Sum decomposition temperature between 5 ~ 30 DEG C.
Described thermo-stabilizer is 2,6-tert-butyl-4-methyl-Phenol (oxidation inhibitor-264), four (4-hydroxyl-3,5-di-tert-butyl-phenyl propionic acid) pentaerythritol ester (oxidation inhibitor-1010), the positive octadecyl ester of 3,5-di-t-butyl-4-hydroxy phenylpropionic acid (oxidation inhibitor-1076), the positive triphenylmethyl methacrylate of phosphorous acid (TPP), the positive three nonyl phenyl esters (TNP) of phosphorous acid, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate (DOP), alkyl imidazole ionic liquid, haloalkyl glyoxaline ion liquid, haloalkyl borate ion liquid, multi-substituent glyoxaline ion liquid, pyrrolidyl ionic liquid, halogenated pyrrole alkyl ionic liquid, quaternary ammonium ionic liquid, halo quaternary ammonium ionic liquid, perchloryl quaternary ammonium ionic liquid, maleic anhydride list lauryl alcohol ester, maleic anhydride list tetradecyl alcohol ester, maleic anhydride list hexadecanol ester, maleic anhydride list octadecyl, the two lauryl alcohol ester of maleic anhydride, the two tetradecyl alcohol ester of maleic anhydride, the two hexadecanol ester of maleic anhydride or the two octadecyl of maleic anhydride.
The Mierocrystalline cellulose that the present invention selects all belongs to natural high moleculer eompound, but not adopts oil to be the polymkeric substance of Material synthesis.After soil is embedding, the equal degradable of these macromolecular compounds is lower-molecular substance, can not cause burden, have the feature of environmental protection to environment.
Preparation method of the present invention take Mierocrystalline cellulose as raw material, without the need to adding acylating reagent, directly adopts solution polymerization can obtain thermoplastic cellulose base co-polymer material; have technique simple, environmental pollution is little, and production efficiency is high; cost is lower, is easy to the advantages such as industrializing implementation.The melt temperature of the thermoplastic cellulose base co-polymer that this preparation method obtains is 100 DEG C ~ 220 DEG C, and heat decomposition temperature is 300 ~ 480 DEG C.Melt temperature, lower than heat decomposition temperature, is suitable for melt-processed.It can be processed into different shape with different thermoplastic polymers is blended, as fiber, non-woven, fabric etc., is then widely used in the fields such as filtering material, medical material, household and clothes.
The fiber surface that the thermoplastic cellulose base co-polymer utilizing this preparation method to obtain obtains is smooth, and do not have obvious skin-core structure, subsurface defect is few, and tensile break strength is large.Described thermoplastic cellulose base co-polymer is easy to processing, and can prepare the fiber of the various structures such as special crosssection, compound and hollow by changing spinning pack, adaptability is good, and production technique is economized on water and production cost is relatively low.
The film surface that the thermoplastic cellulose base co-polymer utilizing this preparation method to obtain obtains is smooth, and defect is few, high temperature resistant, good toughness, and intensity is large, and cost is low, has a good application prospect and economical, societal benefits.
Embodiment
First the method that the performance of the thermoplastic cellulose base co-polymer that the present invention obtains is characterized is provided; except indicating especially; all use equipment below and method: adopt NETZSCH DSC200F3 differential scanning calorimeter (DSC); under nitrogen protection; the test temperature-rise period of 10 DEG C/min and the DSC scanning curve of-10 DEG C/min temperature-fall period, obtain melt temperature.Adopt NETZSCH, STA409PC/PGTG-DTA thermogravimetric analyzer (TG) with 10 DEG C/min temperature-rise period, record the dry aerial heat decomposition temperature of thermoplastic cellulose base co-polymer (temperature of weightless 5wt%).
Below in conjunction with embodiment, technical scheme of the present invention is described in detail.
Embodiment 1
A preparation method for thermoplastic cellulose base co-polymer, comprises the steps:
1) by Microcrystalline Cellulose dry 12h at 60 DEG C in vacuum drying oven.Get a certain amount of dried Microcrystalline Cellulose and be dissolved in dimethyl sulfoxide (DMSO)/paraformaldehyde (DMSO/PF) (wherein, the mass ratio of DMSO and PF is 12:1) in solution, the concentration of Microcrystalline Cellulose is 5wt%, mechanical stirring at 95 DEG C, until become homogeneous system, obtains cellulose solution.
2) in the reaction vessel being provided with condenser and powerful motor stirrer, add N ' N '-dimethyl methane amide (DMF), logical nitrogen 30min, removes the air dissolved in DMF; Then in reaction vessel, add chain-transfer agent-lauryl mercaptan and initiator-azo-bis-isobutyl cyanide, then add step 1 wherein) mixture of obtained cellulose solution and second comonomer-methyl acrylate; The glucose unit ring that wherein in cellulose solution, Microcrystalline Cellulose contains and the molar ratio of methyl acrylate are 1:6, and the addition of lauryl mercaptan is the 0.05mol% of the molar weight sum of glucose unit ring and methyl acrylate in Microcrystalline Cellulose; The addition of azo-bis-isobutyl cyanide is the 10mol% of the molar weight sum of glucose unit ring and methyl acrylate in Microcrystalline Cellulose; Controlling temperature of reaction is 50 DEG C, starts stirring, and reaction 24h obtains reaction mixture; By described reaction mixture in deionized water repetitive scrubbing precipitation 2 ~ 3 times, remove solvent DMF, and after soak 3h through methanol wash, the removing homopolymer of methyl acrylate and unreacted methyl acrylate, finally carry out vacuum-drying, obtain described thermoplastic cellulose base co-polymer.
Adopt differential scanning calorimeter and thermogravimetric analyzer test to test the melt temperature Sum decomposition temperature of gained thermoplastic cellulose base co-polymer respectively, experimental result shows, the fusing point of gained thermoplastic cellulose base co-polymer is 135 DEG C, and heat decomposition temperature is 321 DEG C.
The thermoplastic cellulose base co-polymer that the present embodiment of 100g drying is obtained mixes with 10g thermo-stabilizer 1-allyl group-3-Methylimidazole villaumite, at 180 DEG C, utilize twin screw extruder to melt extrude make rounded section nascent fibre, after excess temperature is first draw roll of 100 DEG C and temperature is second draw roll of 80 DEG C, at 90 DEG C of dryness finalizations, the cellulosic fibre of finished product can be obtained.
Test shows: the mechanical property adopting single fiber strength tester test gained fiber, fiber number is 3.2dtex, and tensile break strength is 5.3cN/dtex, and extension at break is 31%, best in quality.
Embodiment 2
A preparation method for thermoplastic cellulose base co-polymer, comprises the steps:
1) after Cotton Pulp being pulverized in vacuum drying oven dry 24h under room temperature.Get a certain amount of dried Cotton Pulp to be dissolved in 1-butyl-3-methyl-imidazoles chloride salt ions liquid, the concentration of Cotton Pulp is 12wt%, and mechanical stirring at 90 DEG C, until become homogeneous system, obtains cellulose solution;
2) in the reaction vessel being provided with condenser and powerful motor stirrer, add dimethyl sulfoxide (DMSO) (DMSO), logical nitrogen 30min, removes the air dissolved in DMSO; Then in reaction vessel, chain-transfer agent-β-thioglycol and initiator-azo two cyanogen in different heptan is added, by step 1) obtained cellulose solution and vinyl imidazole point add in reaction vessel 4 times after mixing; Wherein, in Cotton Pulp, the molar ratio of glucose unit ring and vinyl imidazole is 1:1; The addition of β-thioglycol is the 5mol% of the molar weight sum of glucose unit ring and vinyl imidazole in Cotton Pulp, and the addition of azo two cyanogen in different heptan is the 0.1mol% of the molar weight sum of glucose unit ring and vinyl imidazole in Cotton Pulp.Controlling temperature of reaction is 90 DEG C, starts stirring, and reaction 4h obtains reaction mixture; By described reaction mixture in deionized water repetitive scrubbing precipitation 2 ~ 3 times, remove solvent DMSO, and after soak 4h through washing with acetone, the removing homopolymer of vinyl imidazole and unreacted vinyl imidazole, finally carry out vacuum-drying, obtain described thermoplastic cellulose base co-polymer.
Adopt differential scanning calorimeter and thermogravimetric analyzer test to test the melt temperature Sum decomposition temperature of gained thermoplastic cellulose base co-polymer respectively, experimental result shows, the fusing point of gained thermoplastic cellulose base co-polymer is 162 DEG C, and heat decomposition temperature is 311 DEG C.
The thermoplastic cellulose base co-polymer obtained using 100g the present embodiment and 40g thermo-stabilizer maleic anhydride list octadecyl are as thermo-stabilizer, at 200 DEG C, utilize twin screw extruder to melt extrude, make trefoil fiber element nascent fibre, nascent fibre, after the second draw roll of first draw roll of 125 DEG C and 90 DEG C, obtains finished fiber at 100 DEG C of dryness finalizations.
Test shows: the mechanical property adopting single fiber strength tester test gained fiber, the fiber number of fiber is 2.5dtex, and tensile break strength is 4.4cN/dtex, and extension at break is 31%.
Embodiment 3
A preparation method for thermoplastic cellulose base co-polymer, comprises the steps:
1) after wood pulps being pulverized in vacuum drying oven dry 12h at 70 DEG C, getting a certain amount of dried wood pulps is dissolved in N ' N '-dimethyl methane amide/lithium chloride (N ' mass ratio of N '-dimethyl methane amide and lithium chloride be 8:1) solution, the concentration of wood pulps is 8wt%, mechanical stirring at 80 DEG C, until become homogeneous system, obtains cellulose solution;
2) in the container being provided with condenser and powerful motor stirrer, add N ' N '-dimethyl methane amide (DMF), logical nitrogen 30min, removes the air dissolved in DMF; Then in reaction vessel, add chain-transfer agent-Virahol and initiator-dilauroyl peroxide, then add step 1 at twice wherein) mixture of obtained cellulose solution and second comonomer-dimethyl maleate; Wherein, in wood pulps, the molar ratio of glucose unit ring and dimethyl maleate is 1:3, the addition of Virahol is the 0.05mol% of the molar weight sum of glucose unit ring and dimethyl maleate in wood pulps, and the addition of dilauroyl peroxide is the 7.2mol% of the molar weight sum of glucose unit ring and dimethyl maleate in wood pulps; Controlling temperature of reaction is 50 DEG C, starts stirring, and reaction 18h obtains reaction mixture; By described reaction mixture in deionized water repetitive scrubbing precipitation 2 ~ 3 times, remove solvent DMF, and after soak 7h through chloroform, removing dimethyl maleate homopolymer and unreacted dimethyl maleate, finally carry out vacuum-drying, obtain described thermoplastic cellulose base co-polymer.
Adopt differential scanning calorimeter and thermogravimetric analyzer test to test the melt temperature Sum decomposition temperature of gained thermoplastic cellulose base co-polymer respectively, experimental result shows, the fusing point of gained thermoplastic cellulose base co-polymer is 187 DEG C, and heat decomposition temperature is 346 DEG C.
The thermoplastic cellulose base co-polymer that the present embodiment of 100g drying is obtained mixes with 40g thermo-stabilizer dibutyl phthalate, join in twin screw extruder and melt extrude, each section of temperature of twin screw extruder is respectively: 90 DEG C, 140 DEG C, 190 DEG C, 220 DEG C.The material of discharging, 220 DEG C of blowings, then after the operations such as cooling, insulation, subdivision, elimination electrostatic, rolling, obtains cellulosefilm of the present invention.
Test shows: the mechanical property adopting film tensile strength instrument test gained film, tensile strength is 32.8MPa, and extensibility is 360%.
Embodiment 4
A preparation method for thermoplastic cellulose base co-polymer, comprises the steps:
1) after bamboo pulp being pulverized in vacuum drying oven dry 18h at 40 DEG C, getting a certain amount of dried bamboo pulp is dissolved in 1-allyl group-3-Methylimidazole chloride solution, the concentration of bamboo pulp is 9wt%, and mechanical stirring at 70 DEG C, until become homogeneous system, obtains cellulose solution;
2) in the container being provided with condenser and powerful motor stirrer, add 1-allyl group-3-Methylimidazole villaumite, logical nitrogen 30min, removes the air wherein dissolved; Then in reaction vessel, add chain-transfer agent-Virahol and initiator-benzoyl peroxide, then divide three times to add step 1 wherein) mixture of obtained cellulose solution and second comonomer-Hydroxyethyl acrylate; Wherein, glucose unit ring in bamboo pulp and the molar ratio of Hydroxyethyl acrylate are 1:5, the addition of Virahol is the 3.0mol% of the molar weight sum of glucose unit ring in bamboo pulp and Hydroxyethyl acrylate, and the addition of benzoyl peroxide is the 15.5mol% of the molar weight sum of glucose unit ring in bamboo pulp and Hydroxyethyl acrylate; Controlling temperature of reaction is 75 DEG C, starts stirring, and reaction 8h obtains reaction mixture; By described reaction mixture in deionized water repetitive scrubbing precipitation 2 ~ 3 times, remove solvent 1-allyl group-3-Methylimidazole villaumite, and after through chloroform, removing Hydroxyethyl acrylate homopolymer and unreacted Hydroxyethyl acrylate, finally carry out vacuum-drying to constant weight, obtain described thermoplastic cellulose base co-polymer.
Adopt differential scanning calorimeter and thermogravimetric analyzer test to test the melt temperature Sum decomposition temperature of gained thermoplastic cellulose base co-polymer respectively, experimental result shows, the fusing point of gained thermoplastic cellulose base co-polymer is 201 DEG C, and heat decomposition temperature is 384 DEG C.
After the abundant drying of thermoplastic cellulose base co-polymer obtained by the present embodiment, at 235 DEG C, utilize twin screw extruder to melt extrude make nascent fibre, after temperature is first draw roll of 135 DEG C and temperature is second draw roll of 118 DEG C, at 150 DEG C of dryness finalizations, obtain the cellulosic fibre of finished product.
Test shows: the mechanical property adopting single fiber strength tester test gained fiber, fiber number is 2.5dtex, and tensile break strength is 4.4cN/dtex, and extension at break is 31%.
Embodiment 5
A preparation method for thermoplastic cellulose base co-polymer, comprises the steps:
1) by Microcrystalline Cellulose dry 8h at 60 DEG C in vacuum drying oven, getting a certain amount of dried Microcrystalline Cellulose is dissolved in 1-butyl-3-methyl-imidazoles chloride salt ions liquid, the concentration of Microcrystalline Cellulose is 15wt%, mechanical stirring at 95 DEG C, until become homogeneous system, obtains cellulose solution;
2) in the reaction vessel being provided with condenser and powerful motor stirrer, dimethyl sulfoxide (DMSO) (DMSO) is added, logical nitrogen 30min, remove the air dissolved in DMSO, then in reaction vessel, add chain-transfer agent-N-octyl mercaptan and initiator-di-isopropyl peroxydicarbonate, then divide 10 times to add step 1 wherein) mixture of obtained cellulose solution and second comonomer n propyl methacrylate; Glucose unit ring wherein in Microcrystalline Cellulose and the molar ratio of n propyl methacrylate are 1:5, the addition of N-octyl mercaptan is the 0.7mol% of the molar weight sum of glucose unit ring in Mierocrystalline cellulose and n propyl methacrylate, and the addition of di-isopropyl peroxydicarbonate is the 18.2mol% of the molar weight sum of glucose unit ring in Mierocrystalline cellulose and n propyl methacrylate; Obtain reaction mixture; By described reaction mixture in deionized water repetitive scrubbing precipitation 2 ~ 3 times, remove solvent DMSO, and after through toluene wash, removing n propyl methacrylate homopolymer and unreacted n propyl methacrylate, then vacuum-drying is to constant weight, obtains described thermoplastic cellulose base co-polymer.
Adopt differential scanning calorimeter and thermogravimetric analyzer test to test the melt temperature Sum decomposition temperature of gained thermoplastic cellulose base co-polymer respectively, experimental result shows, the fusing point of gained thermoplastic cellulose base co-polymer is 196 DEG C, and heat decomposition temperature is 403 DEG C.
The cellulose copolymer obtained by the present embodiment of 100g drying and 30g thermo-stabilizer 2,6-tert-butyl-4-methyl-Phenol 30g mixes, join in twin screw extruder and melt extrude, each section of temperature is respectively: 90 DEG C, 140 DEG C, 200 DEG C, 230 DEG C.The material of discharging, 220 DEG C of blowings, after the operations such as cooling, insulation, subdivision, elimination electrostatic, rolling, obtains cellulosefilm of the present invention.
Test shows: the mechanical property adopting film tensile strength instrument test gained film, tensile strength is 35.8MPa, and extensibility is 320%.
Embodiment 6
A preparation method for thermoplastic cellulose base co-polymer, comprises the steps:
1) by absorbent cotton dry 24h under room temperature in vacuum drying oven, dried absorbent cotton is dissolved in 1-ethyl-3-methylimidazole acetate ionic liquid, the concentration of absorbent cotton is 10wt%, and mechanical stirring at 70 DEG C, until become homogeneous system, obtains cellulose solution;
2) in the reaction vessel being provided with condenser and powerful motor stirrer, add dimethyl sulfoxide (DMSO) (DMSO), logical nitrogen 30min removes the air dissolved in DMSO; Then in reaction vessel, chain-transfer agent-N-octyl mercaptan and initiator-dicumyl peroxide is added, add the mixture of cellulose solution and second comonomer-methyl methacrylate more wherein, the absorbent cotton wherein in cellulose solution is 1:4 containing the molar ratio of glucose unit ring and methyl methacrylate; The addition of N-octyl mercaptan is absorbent cotton in cellulose solution containing the 1.2mol% of the molar weight sum of glucose unit ring and methyl methacrylate; The addition of dicumyl peroxide is absorbent cotton in cellulose solution containing the 1.5mol% of the molar weight sum of glucose unit ring and methyl methacrylate; Controlling temperature of reaction is 75 DEG C, starts stirring, and reaction 16h obtains reaction mixture; By described reaction mixture in deionized water repetitive scrubbing precipitation 2 ~ 3 times, remove solvent DMSO, and after through washing with acetone soak 10h, removing imperplex and unreacted methyl methacrylate, then vacuum-drying is to constant weight, obtains described thermoplastic cellulose base co-polymer.
Adopt differential scanning calorimeter and thermogravimetric analyzer test to test the melt temperature Sum decomposition temperature of gained thermoplastic cellulose base co-polymer respectively, experimental result shows, the fusing point of gained thermoplastic cellulose base co-polymer is 167 DEG C, and heat decomposition temperature is 341 DEG C.
Two to thermoplastic cellulose base co-polymer obtained for the present embodiment of 100g drying and 12g thermo-stabilizer-maleic anhydride octadecyl is mixed, at 200 DEG C, utilize twin screw extruder to melt extrude make nascent fibre, nascent fibre is after the second draw roll of first draw roll of 165 DEG C and 110 DEG C, at 110 DEG C of dryness finalizations, the cellulosic fibre of finished product can be obtained.
Test shows: the mechanical property adopting single fiber strength tester test gained fiber, fiber number is 2.1dtex, and tensile break strength is 1.7cN/dtex, and extension at break is 26%.
Embodiment 7
A preparation method for thermoplastic cellulose base co-polymer, comprises the steps:
1) by linters dry 12h at 70 DEG C in vacuum drying oven, getting a certain amount of dried linters is dissolved in 1-allyl group-3-Methylimidazole chloride salt ions liquid, the concentration of linters is 13wt%, and mechanical stirring at 85 DEG C, until become homogeneous system, obtains cellulose solution;
2) in the container being provided with condenser and powerful motor stirrer, add 1-allyl group-3-Methylimidazole chloride salt ions liquid, logical nitrogen 30min, removes the air wherein dissolved; Then in reaction vessel, add chain-transfer agent-lauryl mercaptan and initiator-di-isopropyl peroxydicarbonate, then divide 9 times to add step 1 wherein) mixture of the cellulose solution that obtains and ethyl methyl acrylate; Wherein, linters in cellulose solution is 1:4.3 containing the molar ratio of glucose unit ring and ethyl methyl acrylate, lauryl mercaptan be linters in cellulose solution containing the 4.5mol% of glucose unit ring with the molar weight sum of ethyl methyl acrylate, di-isopropyl peroxydicarbonate is the 18.5mol% that linters in cellulose solution contains the molar weight sum of glucose unit ring and ethyl methyl acrylate; Controlling temperature of reaction is 70 DEG C, starts stirring, and reaction 18h obtains reaction mixture; By described reaction mixture in deionized water repetitive scrubbing precipitation 2 ~ 3 times, remove solvent 1-allyl group-3-Methylimidazole chloride salt ions liquid, and after wash through tetrahydrofuran (THF), removing ethyl methyl acrylate homopolymer and unreacted ethyl methyl acrylate, then vacuum-drying is to constant weight, obtains described thermoplastic cellulose base co-polymer.
Adopt differential scanning calorimeter and thermogravimetric analyzer test to test the melt temperature Sum decomposition temperature of gained thermoplastic cellulose base co-polymer respectively, experimental result shows, the fusing point of gained thermoplastic cellulose base co-polymer is 215 DEG C, and heat decomposition temperature is 480 DEG C.
Two to thermoplastic cellulose base co-polymer obtained for the present embodiment of 100g drying and 20g thermo-stabilizer-maleic anhydride tetradecyl alcohol ester is mixed, at 250 DEG C, utilize twin screw extruder to melt extrude to make the nascent fibre of rounded section, nascent fibre, after the second draw roll of first draw roll of 185 DEG C and 145 DEG C, obtains the cellulosic fibre of finished product at 150 DEG C of dryness finalizations.
Test shows: the mechanical property adopting single fiber strength tester test gained fiber, fiber number is 2.6dtex, and tensile break strength is 2.7cN/dtex, and extension at break is 35%.
Embodiment 8
A preparation method for thermoplastic cellulose base co-polymer, comprises the steps:
1) by cotton dry 12h at 50 DEG C in vacuum drying oven, getting a certain amount of dried cotton is dissolved in 1-ethyl-3-methylimidazole acetate ionic liquid, the concentration of cotton is 15wt%, and mechanical stirring at 95 DEG C, until become homogeneous system, obtains cellulose solution;
2) in the container being provided with condenser and powerful motor stirrer, add N ' N '-dimethyl ethanamide (DMAc), logical nitrogen 30min, removes the air dissolved in DMAc, then in reaction vessel, chain-transfer agent-lauryl mercaptan and initiator-Diisopropyl azodicarboxylate is added, add step 1 wherein again) mixture of the cellulose solution that obtains and second comonomer-diallyl maleate, wherein in cellulose solution, cotton is 1:3.5 containing the molar ratio of glucose unit ring and diallyl maleate, the addition of lauryl mercaptan is cotton in cellulose solution containing the 5.0mol% of the molar weight sum of glucose unit ring and diallyl maleate, the addition of Diisopropyl azodicarboxylate is cotton in cellulose solution containing the 15.7mol% of the molar weight sum of glucose unit ring and diallyl maleate, controlling temperature of reaction is 80 DEG C, starts stirring, and reaction 6h obtains reaction mixture, by described reaction mixture in deionized water repetitive scrubbing precipitation 2 ~ 3 times, remove solvent DMAc, and after through chloroform, removing diallyl maleate homopolymer and unreacted diallyl maleate, then vacuum-drying is to constant weight, obtains described thermoplastic cellulose base co-polymer.
Adopt differential scanning calorimeter and thermogravimetric analyzer test to test the melt temperature Sum decomposition temperature of gained thermoplastic cellulose base co-polymer respectively, experimental result shows, the fusing point of gained thermoplastic cellulose base co-polymer is 132 DEG C, and heat decomposition temperature is 300 DEG C.
After the abundant drying of thermoplastic cellulose base co-polymer obtained by the present embodiment, at 165 DEG C, utilize twin screw extruder to melt extrude make nascent fibre, after temperature is first draw roll of 105 DEG C and temperature is second draw roll of 90 DEG C, obtain finished fiber cellulose fiber at 100 DEG C of dryness finalizations.
Test shows: the mechanical property adopting single fiber strength tester test gained fiber, fiber number is 2.3dtex, and tensile break strength is 3.1cN/dtex, and extension at break is 32%.
Embodiment 9
A preparation method for thermoplastic cellulose base co-polymer, comprises the steps:
1) after cellulosic filter paper being pulverized, dry 12h at 55 DEG C in vacuum drying oven, getting a certain amount of dried cellulosic filter paper is dissolved in 1-methyl-3-ethyl imidazol(e) phosphate ion liquid, cellulosic concentration is 14wt%, mechanical stirring at 95 DEG C, until become homogeneous system, obtains cellulose solution;
2) in the container being provided with condenser and powerful motor stirrer, add N ' N '-dimethyl ethanamide (DMAc), logical nitrogen 30min removes the air dissolved in DMAc; Then in reaction vessel, chain-transfer agent-N-octyl mercaptan and initiator-2,2'-Azobis(2,4-dimethylvaleronitrile) is added, divide wherein again and add step 16 times) cellulose solution that obtains and second comonomer-maleopimaric acid allyl ester, wherein, the molar ratio in cellulose solution is 1:4.8; The addition of N-octyl mercaptan is the 2.5mol% that cellulosic filter paper contains the molar weight sum of glucose unit ring and maleopimaric acid allyl ester; The addition of 2,2'-Azobis(2,4-dimethylvaleronitrile) is the 9.6mol% that cellulosic filter paper contains the molar weight sum of glucose unit ring and maleopimaric acid allyl ester; Controlling temperature of reaction is 85 DEG C, starts stirring, and reaction 8h obtains reaction mixture; By described reaction mixture in deionized water repetitive scrubbing precipitation 2 ~ 3 times, remove solvent DMAc, and after through chloroform, removing maleopimaric acid allyl ester homopolymer and unreacted maleopimaric acid allyl ester, then vacuum-drying is to constant weight, obtains described thermoplastic cellulose base co-polymer.
Adopt differential scanning calorimeter and thermogravimetric analyzer test to test the melt temperature Sum decomposition temperature of gained thermoplastic cellulose base co-polymer respectively, experimental result shows, the fusing point of gained thermoplastic cellulose base co-polymer is 220 DEG C, and heat decomposition temperature is 456 DEG C.
The thermoplastic cellulose base co-polymer that the present embodiment of 100g drying is obtained mixes with the positive triphenylmethyl methacrylate of 15g thermo-stabilizer phosphorous acid (TPP), at 255 DEG C, utilize twin screw extruder to melt extrude make nascent fibre, after temperature is first draw roll of 145 DEG C and temperature is second draw roll of 118 DEG C, 120 DEG C of dryness finalizations, can obtain the cellulosic fibre of finished product.
Test shows: the mechanical property adopting single fiber strength tester test gained fiber, fiber number is 2.4dtex, and tensile break strength is 2.0cN/dtex, and extension at break is 33%.
Embodiment 10
A preparation method for thermoplastic cellulose base co-polymer, comprises the steps:
1) by Microcrystalline Cellulose dry 24h at 30 DEG C in vacuum drying oven, getting a certain amount of dried Microcrystalline Cellulose is dissolved in 1-allyl group-3-Methylimidazole chloride salt ions liquid, the concentration of Microcrystalline Cellulose is 5.5wt%, mechanical stirring at 50 DEG C, until become homogeneous system, obtains cellulose solution;
2) in the container being provided with condenser and powerful motor stirrer, add 1-allyl group-3-Methylimidazole villaumite, logical nitrogen 30min, removes the air wherein dissolved; Then in reaction vessel, chain-transfer agent-N-octyl mercaptan and initiator-2,2'-Azobis(2,4-dimethylvaleronitrile) is added, divide 5 times again and add step 1 wherein) mixture of the cellulose solution that obtains and second comonomer-lauryl methacrylate(LMA), wherein the glucose unit ring of Microcrystalline Cellulose and the molar ratio of lauryl methacrylate(LMA) are 1:6; The addition of N-octyl mercaptan is the 3.2mol% of the glucose unit ring of Microcrystalline Cellulose and the molar weight sum of lauryl methacrylate(LMA); The addition of 2,2'-Azobis(2,4-dimethylvaleronitrile) is the 11.7mol% of the glucose unit ring of Microcrystalline Cellulose and the molar weight sum of lauryl methacrylate(LMA); Controlling temperature of reaction is 80 DEG C, starts stirring, and reaction 12h obtains reaction mixture; By described reaction mixture in deionized water repetitive scrubbing precipitation 2 ~ 3 times, remove solvent 1-allyl group-3-Methylimidazole villaumite, and after through toluene wash, removing lauryl methacrylate(LMA) homopolymer and unreacted lauryl methacrylate(LMA), then vacuum-drying is to constant weight, obtains described thermoplastic cellulose base co-polymer.
Adopt differential scanning calorimeter and thermogravimetric analyzer test to test the melt temperature Sum decomposition temperature of gained thermoplastic cellulose base co-polymer respectively, experimental result shows, the fusing point of gained thermoplastic cellulose base co-polymer is 147 DEG C, and heat decomposition temperature is 355 DEG C.
Joined in twin screw extruder by the thermoplastic cellulose base co-polymer that the present embodiment is obtained and melt extrude, each section of temperature is respectively: 80 DEG C, 130 DEG C, 160 DEG C, 185 DEG C.The material of discharging, 190 DEG C of blowings, after the operations such as cooling, insulation, subdivision, elimination electrostatic, rolling, obtains cellulosefilm of the present invention.
Test shows: the mechanical property adopting film tensile strength instrument test gained film, tensile strength is 38.5MPa, and extensibility is 270%.
Claims (10)
1. a preparation method for thermoplastic cellulose base co-polymer, is characterized in that comprising the steps:
1) by after Mierocrystalline cellulose drying, 65 ~ 95 DEG C, be fully dissolved in ionic liquid, paraformaldehyde/dimethyl sulfoxide (DMSO) or lithium chloride/N ' N '-dimethyl methane amide under agitation condition and obtain cellulose solution, the concentration of this cellulose solution is 5 ~ 15wt%;
2) in the reaction vessel that condenser and agitator be housed, solvent I is added, remove the air wherein dissolved, then in reaction vessel, chain-transfer agent and initiator is added, add second comonomer and step 1 again) mixture of cellulose solution that obtains, 50 ~ 90 DEG C, reaction 4 ~ 24h obtains reaction mixture under agitation condition; Described reaction mixture is precipitated in deionized water, with deionized water repetitive scrubbing throw out, removes residual solvent I; Then again through solvent II washing, the homopolymer of removing second comonomer and unreacted second comonomer, finally carry out vacuum-drying, obtain described thermoplastic cellulose base co-polymer;
Wherein: the mol ratio of the glucose unit ring that the Mierocrystalline cellulose in described second comonomer and cellulose solution contains is: 1 ~ 6:1;
The addition of described chain-transfer agent is 0.05 ~ 5.0mol% of the molar weight sum of glucose unit ring in described second comonomer and Mierocrystalline cellulose;
The addition of described initiator is 0.1 ~ 20.0mol% of the molar weight sum of glucose unit ring in described second comonomer and Mierocrystalline cellulose;
Described Mierocrystalline cellulose is Microcrystalline Cellulose, Cotton Pulp, linters, cotton, wood pulps, bamboo pulp, cellulosic filter paper or absorbent cotton;
Described second comonomer is the esters monomer containing unsaturated double-bond or the imidazoles monomer containing unsaturated double-bond;
Described solvent I is N ' N '-dimethyl methane amide, N ' N '-dimethyl ethanamide, dimethyl sulfoxide (DMSO) or step 1) any one in described ionic liquid; Described solvent II is the homopolymer of second comonomer and the cosolvent of unreacted second comonomer.
2. the preparation method of thermoplastic cellulose base co-polymer as claimed in claim 1, it is characterized in that: the described esters monomer containing unsaturated double-bond is methyl acrylate, ethyl propenoate, propyl acrylate, butyl acrylate, stearyl acrylate acid esters, lauryl acrylate, isopropyl acrylate, isobutyl acrylate, tert-butyl acrylate, Isooctyl acrylate monomer, isodecyl acrylate, Hydroxyethyl acrylate, Propylene glycol monoacrylate, hy-droxybutyl, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, n propyl methacrylate, n-BMA, lauryl methacrylate(LMA), stearyl methacrylate, ethyl methyl acrylate, dimethyl maleate, ethyl maleate, dibutyl maleinate, diallyl maleate, vinyl-acetic ester, any one in ethene diethyl ester and maleopimaric acid allyl ester,
The described imidazoles monomer containing unsaturated double-bond is vinyl imidazole or N-allyl imidazole.
3. the preparation method of thermoplastic cellulose base co-polymer as claimed in claim 1, is characterized in that: described chain-transfer agent is any one in lauryl mercaptan, N-octyl mercaptan, β-thioglycol and Virahol.
4. the preparation method of thermoplastic cellulose base co-polymer as claimed in claim 1, is characterized in that: described initiator be benzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, hydrogen peroxide to the Meng alkane, dilauroyl peroxide, dibenzoyl peroxide, di-isopropyl peroxydicarbonate, any one in azo-bis-isobutyl cyanide and azo two cyanogen in different heptan.
5. the preparation method of thermoplastic cellulose base co-polymer as claimed in claim 1, is characterized in that: step 1) mass ratio of paraformaldehyde and dimethyl sulfoxide (DMSO) is 1:8 ~ 12 in described paraformaldehyde/dimethyl sulfoxide (DMSO); In described lithium chloride/N ' N '-dimethyl methane amide, the mass ratio of lithium chloride and N ' N '-dimethyl methane amide is 1:8 ~ 12.
6. the preparation method of thermoplastic cellulose base co-polymer as claimed in claim 1, is characterized in that: step 1) described ionic liquid is glyoxaline ion liquid.
7. the preparation method of thermoplastic cellulose base co-polymer as claimed in claim 6, is characterized in that: described glyoxaline ion liquid is 1-methyl-3-ethyl imidazol(e) phosphoric acid salt, 1-ethyl-3-methylimidazole acetate, 1-butyl-3-methyl-imidazoles villaumite or 1-allyl group-3-Methylimidazole villaumite.
8. the preparation method of thermoplastic cellulose base co-polymer as claimed in claim 1, is characterized in that: described solvent II is any one in formic acid, methyl alcohol, tetrahydrofuran (THF), methylene dichloride, acetone, chloroform, toluene, dimethylbenzene and benzene.
9. the preparation method of thermoplastic cellulose base co-polymer as claimed in claim 1, is characterized in that: the addition means of cellulose solution and second comonomer for both mix after once add, drip or add several times.
10. utilize the obtained thermoplastic cellulose base co-polymer of claim 1 to prepare the method for fiber or film, it is characterized in that comprising following steps:
1. by after thermoplastic cellulose base co-polymer drying obtained for claim 1, mix with the thermo-stabilizer accounting for its quality 0 ~ 40% and obtain raw material;
2. described raw material is carried out melt extruding spinning or blown film, namely the cellulosic fibre that can degrade or film is obtained, wherein below more than the fusing point of thermoplastic cellulose base co-polymer 1. selected between step of melt processing temperature 5 ~ 30 DEG C of Sum decomposition temperature between 5 ~ 30 DEG C.
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