CN102604131B - Preparation method of cross-linked sodium carboxymethyl cellulose - Google Patents
Preparation method of cross-linked sodium carboxymethyl cellulose Download PDFInfo
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- CN102604131B CN102604131B CN 201210045152 CN201210045152A CN102604131B CN 102604131 B CN102604131 B CN 102604131B CN 201210045152 CN201210045152 CN 201210045152 CN 201210045152 A CN201210045152 A CN 201210045152A CN 102604131 B CN102604131 B CN 102604131B
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- carboxymethyl cellulose
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- croscarmellose sodium
- silicon
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- 229920002785 Croscarmellose sodium Polymers 0.000 title claims abstract description 77
- 235000010947 crosslinked sodium carboxy methyl cellulose Nutrition 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000001767 crosslinked sodium carboxy methyl cellulose Substances 0.000 title abstract 7
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims abstract description 71
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 62
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 60
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 31
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 30
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 30
- 239000003377 acid catalyst Substances 0.000 claims abstract description 13
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 13
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000843 powder Substances 0.000 claims abstract description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000001035 drying Methods 0.000 claims abstract description 3
- 239000001301 oxygen Substances 0.000 claims abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 114
- 229960001681 croscarmellose sodium Drugs 0.000 claims description 49
- 229960001866 silicon dioxide Drugs 0.000 claims description 29
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 24
- 239000003795 chemical substances by application Substances 0.000 claims description 24
- GFYKQOQZUGAPHK-UHFFFAOYSA-M C(C=C)(=O)[O-].C(C(C)O)O.[Si+](=O)=O Chemical compound C(C=C)(=O)[O-].C(C(C)O)O.[Si+](=O)=O GFYKQOQZUGAPHK-UHFFFAOYSA-M 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 21
- 238000013019 agitation Methods 0.000 claims description 20
- 229920003123 carboxymethyl cellulose sodium Polymers 0.000 claims description 20
- 229940063834 carboxymethylcellulose sodium Drugs 0.000 claims description 20
- 238000005119 centrifugation Methods 0.000 claims description 20
- 239000002798 polar solvent Substances 0.000 claims description 20
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- 239000002114 nanocomposite Substances 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 12
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 11
- 238000006116 polymerization reaction Methods 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000010521 absorption reaction Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 2
- 238000004132 cross linking Methods 0.000 abstract description 12
- 230000008961 swelling Effects 0.000 abstract description 11
- 239000001768 carboxy methyl cellulose Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000003431 cross linking reagent Substances 0.000 abstract 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 abstract 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 abstract 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract 1
- 230000002378 acidificating effect Effects 0.000 abstract 1
- 239000002131 composite material Substances 0.000 abstract 1
- 239000002086 nanomaterial Substances 0.000 abstract 1
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 229910052710 silicon Inorganic materials 0.000 abstract 1
- 239000010703 silicon Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 39
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 36
- 239000003921 oil Substances 0.000 description 19
- OWIKHYCFFJSOEH-UHFFFAOYSA-N Isocyanic acid Chemical class N=C=O OWIKHYCFFJSOEH-UHFFFAOYSA-N 0.000 description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 229920002678 cellulose Polymers 0.000 description 8
- 235000010980 cellulose Nutrition 0.000 description 8
- 238000006392 deoxygenation reaction Methods 0.000 description 8
- 229910052500 inorganic mineral Inorganic materials 0.000 description 8
- 239000011707 mineral Substances 0.000 description 8
- 239000000376 reactant Substances 0.000 description 8
- 238000001179 sorption measurement Methods 0.000 description 8
- 239000001913 cellulose Substances 0.000 description 7
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 4
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 4
- 159000000013 aluminium salts Chemical class 0.000 description 3
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- -1 mining Substances 0.000 description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000003352 sequestering agent Substances 0.000 description 2
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 229940105329 carboxymethylcellulose Drugs 0.000 description 1
- 150000001768 cations Chemical group 0.000 description 1
- 229920006184 cellulose methylcellulose Polymers 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000015784 hyperosmotic salinity response Effects 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- LPUQAYUQRXPFSQ-DFWYDOINSA-M monosodium L-glutamate Chemical compound [Na+].[O-]C(=O)[C@@H](N)CCC(O)=O LPUQAYUQRXPFSQ-DFWYDOINSA-M 0.000 description 1
- 235000013923 monosodium glutamate Nutrition 0.000 description 1
- 239000004223 monosodium glutamate Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229940034610 toothpaste Drugs 0.000 description 1
- 239000000606 toothpaste Substances 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Landscapes
- Medicinal Preparation (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention relates to a preparation method of cross-linked sodium carboxymethyl cellulose. The preparation method of the cross-linked sodium carboxymethyl cellulose comprises the following steps of: adding an inorganic acid catalyst into sodium carboxymethyl cellulose solution to change a reaction system to be acidic; after reaction, adding a cross-linking agent; removing oxygen and charging nitrogen; prepolymerizing and polymerizing to obtain cross-linked carboxymethyl cellulose solution; dropwise adding alkalized ethanol-water solution to obtain cross-linked sodium carboxymethyl cellulose solution; and drying to obtain the cross-linked sodium carboxymethyl cellulose powder. According to the preparation method, a silicon dioxide composite nanomaterial, silicon dioxide-hydroxyl propyl acrylate, is used as the cross-linking agent, sodium carboxymethyl cellulose is used as a raw material, and cross-linking is performed under an alkaline condition to prepare the cross-linked sodium carboxymethyl cellulose. The cross-linked sodium carboxymethyl cellulose prepare by the invention has the characteristics of high transparence, high viscosity, high swelling degree and the like, and hasextremely high industrial application value.
Description
Technical field
The present invention relates to the method for the crosslinked preparation of nano composite material, relate in particular to the preparation method of croscarmellose sodium.
Background technology
Carboxymethyl cellulose (being called for short CMC) is the plain ether of a fibrid of production and selling amount maximum in the world wide, be widely used in aspects such as washing composition, food, toothpaste, weaving, printing and dyeing, papermaking, oil, mining, medicine, pottery, electronic component, rubber, coating, agricultural chemicals, makeup, leather, plastics and petroleum drilling, be described as " industrial monosodium glutamate ".According to the product of produced in conventional processes in exchange process easily and polyvalent cation form the salt of insoluble or indissoluble, and it is not enough that the product ubiquity replaces homogeneity, transparency rheology of solution, erosion resistance are not ideal enough, and the characteristics of salt tolerance, temperature tolerance difference.Crosslinked be functional modification Mierocrystalline cellulose and derivative thereof make things convenient for one of approach.Not destroying under its active prerequisite, adopt suitable linking agent, and the control degree of crosslinking, can significantly improve the cellulosic polymerization degree, improve the rerum natura of product.The research of this respect has many reports, is that 4505775 United States Patent (USP) has taken the lead in adopting crosslinked method as publication number.Publication number is 6531593 United States Patent (USP), takes the lead in disclosing Mierocrystalline cellulose is carried out the crosslinked ether of cellulose that obtains.Publication number is 3072635 United States Patent (USP), has introduced a kind of many aldehyde that utilize, and carries out crosslinked method as oxalic dialdehyde.But these methods mainly are to handle non-ionic celluloses ether, and also undesirable to the processing of anionic ether of cellulose such as CMC, HECMC.Publication number is 4309535 United States Patent (USP), has introduced with aluminium salt pair water-soluble ionic-type ether of cellulose and has handled.This treatment technology has formed cross-linking set between the ether of cellulose surface, and delayed hydration effect, and make particle before forming reunion, in the aqueous solution, begin to disperse, dissolving is by adding aluminium salt sequestrant fully, remove aluminum ion again, interrupt the undissolved cross-linking set of particle surface.This technology still is not ideal enough, because not only will form macromolecular solution, and will add aluminium salt sequestrant.Undesirable with the borate crosslinked effect, because borate just can be more effective to containing dihydric ether of cellulose, and CMC does not have cis-diol structure yet.
Summary of the invention
The objective of the invention is provides a kind of preparation method of croscarmellose sodium for solving prior art problems.
Above-mentioned purpose of the present invention is achieved by the following technical programs:
The preparation method of croscarmellose sodium, it may further comprise the steps:
1. with 50 mass parts aprotic polar solvents dissolving, 15～20 mass parts Xylo-Mucines, stirring and dissolving obtains the carboxymethylcellulose sodium solution of homogeneous;
2. adding inorganic acid catalyst in above-mentioned carboxymethylcellulose sodium solution, to make the pH of reaction system be 1.5～3.0, reacts 30～60min under the room temperature, obtains cmc soln;
3. get in the described cmc soln that 1.1～2.4 mass parts linking agents are scattered in 9.0 mass parts, must mix liquid, described mixed liquid row oxygen and filling nitrogen is placed on pre-polymerization 6～12h in the ultrasonic wave, and polyase 13 5～38h under 90～110 ℃ of conditions obtains crosslinked cmc soln then;
4. be cooled to room temperature, in above-mentioned crosslinked cmc soln, drip the ethanol-water solution that alkalizes, obtain croscarmellose sodium solution;
5. using the above-mentioned croscarmellose sodium solution of absolute ethanol washing, is 6～8 until pH, and drying obtains the croscarmellose sodium powder under 90～110 ℃ of conditions then.
Preferred as technique scheme, described linking agent is the silicon-dioxide-Propylene glycol monoacrylate of nano composite material.
Preferred as technique scheme, described silicon-dioxide-Propylene glycol monoacrylate prepares by the following method:
1. get the silicon-dioxide of 3.0 mass parts and the TDI of 3～3.2 mass parts, be dispersed in the dry toluene of 80～100 mass parts, vacuumize the back nitrogen protection, in ultrasonic wave, disperse l0～12min, constant temperature is 90～95 ℃ in the placement oil bath, reacts 5～6h under the magnetic agitation; Reaction finishes the back with the TDI of dry toluene flush away surface physics absorption, utilizes centrifugation method separation function silicon-dioxide;
2. the functionalized SiO 2 of getting 2.0 mass parts is dispersed in 5～80ml dry toluene; in ultrasonic wave, disperse 10～12min; drip the Propylene glycol monoacrylate of 0.5～0.6 mass parts then; vacuumize nitrogen protection; react 40～50h under 90 ℃ of magnetic agitation of oil bath, reaction finishes the back and obtains described linking agent silicon-dioxide-Propylene glycol monoacrylate with the centrifugation method separation.
In the technique scheme of the present invention, functionalized SiO 2 refers to SiO
2-TDI.TDI is Toluene-2,4-diisocyanate, 4-two isocyanic acids.
Preferred as technique scheme, described aprotic polar solvent is one or more in dimethyl sulfoxide (DMSO), tetrahydrofuran (THF) and the dimethyl formamide.
Preferred as technique scheme, described inorganic acid catalyst is sulfuric acid.
The present invention has the following effect of having a mind to:
The present invention uses silicon dioxide nano composite material silicon-dioxide-Propylene glycol monoacrylate to be linking agent, use Xylo-Mucine to be raw material, under alkaline condition, take place crosslinked, make croscarmellose sodium, the croscarmellose sodium of the present invention's preparation has transparence height, viscosity height, characteristics such as swelling capacity height have great industrial application value.
Embodiment
This specific embodiment only is explanation of the invention; it is not limitation of the present invention; those skilled in the art can make any modification to present embodiment as required after reading this specification sheets, but as long as all are subjected to the protection of patent law in claim scope of the present invention.
Embodiment one
The preparation method of croscarmellose sodium may further comprise the steps:
1. with the non-proton property polar solvent dissolving 15 gram Xylo-Mucines of 50 grams, stirring and dissolving obtains the homogeneous carboxymethylcellulose sodium solution;
2. add inorganic acid catalyst in above-mentioned carboxymethylcellulose sodium solution, make reactant be tied to form acidity, the pH value is 1.5, reacts 30min under the room temperature, obtains cmc soln;
3. get 1.1 gram linking agents and be scattered in the 9.0g cmc soln, place ultrasonic wave pre-polymerization 6h through deoxygenation towards nitrogen, in 90 ℃ of polyase 13 6h, obtain crosslinked carboxymethyl cellulose again;
4. be cooled to room temperature, 95% ethanol-water solution that dropwise drips alkalization in the above-mentioned cross-linked carboxymethyl cellulose solution that obtains obtains croscarmellose sodium, filters, and be 6 with absolute ethanol washing to pH value, dry 5h under 90 ℃ obtains the croscarmellose sodium powder.
The croscarmellose sodium that present embodiment makes, its swelling capacity are 7, and transparence is 93%, and water viscosity is 5610mPas in the time of 80 ℃.
Described linking agent is the silicon-dioxide-Propylene glycol monoacrylate of nano composite material.
Described silicon-dioxide-Propylene glycol monoacrylate prepares by the following method:
1. silicon-dioxide and Toluene-2,4-diisocyanate, 4-two isocyanic acids (TDI) reaction: get 3.0g silicon-dioxide and 3.1g Toluene-2,4-diisocyanate, 4-two isocyanic acids are dispersed in the 90mL dry toluene, vacuumize the back nitrogen protection, disperse 10min in ultrasonic wave, constant temperature is 90 ℃ in the placement oil bath, reacts 6h under the magnetic agitation, reaction finishes the back with the TDI of a large amount of dry toluene flush away surface physics absorption, utilizes centrifugation method separation function silicon-dioxide;
2. getting the 2.0g functionalized SiO 2 is dispersed in the 60ml dry toluene; in ultrasonic wave, disperse 10min, drip 0.5g Propylene glycol monoacrylate (HPA) then, vacuumize nitrogen protection; react 48h under 90 ℃ of magnetic agitation of oil bath, reaction finishes the back and separates crosslinking aid S iO with centrifugation method
2-HPA is with the HPA of a large amount of toluene flush away physical adsorptions.
Described non-proton property polar solvent is dimethyl sulfoxide (DMSO), and described mineral acid is sulfuric acid.
Embodiment two
The preparation method of croscarmellose sodium may further comprise the steps:
1. with the non-proton property polar solvent dissolving 16 gram Xylo-Mucines of 50 grams, stirring and dissolving obtains the homogeneous carboxymethylcellulose sodium solution;
2. add inorganic acid catalyst in above-mentioned carboxymethylcellulose sodium solution, make reactant be tied to form acidity, the pH value is 2.0, reacts 30min under the room temperature, obtains cmc soln;
3. get 1.1 gram linking agents and be scattered in the 9.0g cmc soln, place ultrasonic wave pre-polymerization 6h through deoxygenation towards nitrogen, with 100 ℃ of polyase 13 5h, obtain crosslinked carboxymethyl cellulose again.
4. be cooled to room temperature, 95% ethanol-water solution that dropwise drips alkalization in the above-mentioned cross-linked carboxymethyl cellulose solution that obtains obtains croscarmellose sodium, filters, and be 7 with absolute ethanol washing to pH value, dry 5h under 110 ℃ obtains the croscarmellose sodium powder.
The croscarmellose sodium that present embodiment makes, its swelling capacity are 8, and transparence is 96%, and water viscosity is 6380mPas in the time of 80 ℃.
Described linking agent is the silicon-dioxide-Propylene glycol monoacrylate of nano composite material.
Described silicon-dioxide-Propylene glycol monoacrylate prepares by the following method:
1. silicon-dioxide and Toluene-2,4-diisocyanate, 4-two isocyanic acids (TDI) reaction: get 3.0g silicon-dioxide and 3.12g Toluene-2,4-diisocyanate, 4-two isocyanic acids are dispersed in the 90mL dry toluene, vacuumize the back nitrogen protection, disperse 10min in ultrasonic wave, constant temperature is 90 ℃ in the placement oil bath, reacts 6h under the magnetic agitation, reaction finishes the back with the TDI of a large amount of dry toluene flush away surface physics absorption, utilizes centrifugation method separation function silicon-dioxide;
2. getting the 2.0g functionalized SiO 2 is dispersed in the 55ml dry toluene; in ultrasonic wave, disperse 10min, drip 0.55g Propylene glycol monoacrylate (HPA) then, vacuumize nitrogen protection; react 48h under 90 ℃ of magnetic agitation of oil bath, reaction finishes the back and separates crosslinking aid S iO with centrifugation method
2-HPA is with the HPA of a large amount of toluene flush away physical adsorptions.
Described non-proton property polar solvent is tetrahydrofuran (THF), and described mineral acid is hydrochloric acid.
Embodiment three
The preparation method of croscarmellose sodium is characterized in that it may further comprise the steps:
1. with the non-proton property polar solvent dissolving 17 gram Xylo-Mucines of 50 grams, stirring and dissolving obtains the homogeneous carboxymethylcellulose sodium solution;
2. add inorganic acid catalyst in above-mentioned carboxymethylcellulose sodium solution, make reactant be tied to form acidity, the pH value is 2.5, reacts 60min under the room temperature, obtains cmc soln;
3. get 1.2 gram linking agents and be scattered in the 9.0 gram cmc solns, place ultrasonic wave pre-polymerization 6h through deoxygenation towards nitrogen, obtain crosslinked carboxymethyl cellulose with 90 ℃ of polyase 13 6h. again.
4. be cooled to room temperature, 95% ethanol-water solution that dropwise drips alkalization in the above-mentioned cross-linked carboxymethyl cellulose solution that obtains obtains croscarmellose sodium, filters, and be 8 with absolute ethanol washing to pH value, dry 8h under 90 ℃ obtains the croscarmellose sodium powder.
The croscarmellose sodium that present embodiment makes, its swelling capacity are 10, and transparence is 98%, and water viscosity is 6698mPas in the time of 80 ℃.
Described linking agent is the silicon-dioxide-Propylene glycol monoacrylate of nano composite material.
Described silicon-dioxide-Propylene glycol monoacrylate prepares by the following method:
1. silicon-dioxide and Toluene-2,4-diisocyanate, 4-two isocyanic acids (TDI) reaction: get 3.0g silicon-dioxide and 3.15g Toluene-2,4-diisocyanate, 4-two isocyanic acids, be dispersed in the 90mL dry toluene, vacuumize the back nitrogen protection, the middle 12min that disperses in ultrasonic wave, constant temperature is 95 ℃ in the placement oil bath, react 6h under the magnetic agitation, reaction finishes the back with the TDI of a large amount of dry toluene flush away surface physics absorption, utilizes centrifugation method separation function silicon-dioxide;
2. getting the 2.0g functionalized SiO 2 is dispersed in the 70ml dry toluene; in ultrasonic wave, disperse 10min, drip 0.5g Propylene glycol monoacrylate (HPA) then, vacuumize nitrogen protection; react 48h under 90 ℃ of magnetic agitation of oil bath, reaction finishes the back and separates crosslinking aid S iO with centrifugation method
2-HPA is with the HPA of a large amount of toluene flush away physical adsorptions.
Described non-proton property polar solvent is dimethyl formamide, and described mineral acid is sulfuric acid.
Embodiment four
The preparation method of croscarmellose sodium, it may further comprise the steps:
1. with 50 gram aprotic polar solvent dissolvings, 18 gram Xylo-Mucines, stirring and dissolving obtains the carboxymethylcellulose sodium solution of homogeneous;
2. add inorganic acid catalyst in above-mentioned carboxymethylcellulose sodium solution, make reactant be tied to form acidity, the pH value is 2.0, reacts 60min under the room temperature, obtains cmc soln;
3. get 2.4 gram linking agents and be scattered in the 9.0 gram cmc solns, place ultrasonic wave pre-polymerization 12h through deoxygenation towards nitrogen, with 110 ℃ of polyase 13 8h, obtain crosslinked carboxymethyl cellulose again;
4. be cooled to room temperature, 95% ethanol-water solution that dropwise drips alkalization in the above-mentioned cross-linked carboxymethyl cellulose solution that obtains obtains croscarmellose sodium, filters, and be 8 with absolute ethanol washing to pH value, dry 5h under 90 ℃ obtains the croscarmellose sodium powder.
The croscarmellose sodium that present embodiment makes, its swelling capacity are 10, and transparence is 98%, and water viscosity is 7080mPas in the time of 80 ℃.
Described linking agent is the silicon-dioxide-Propylene glycol monoacrylate of nano composite material.
Described silicon-dioxide-Propylene glycol monoacrylate prepares by the following method:
1. silicon-dioxide and Toluene-2,4-diisocyanate, 4-two isocyanic acids (TDI) reaction: get 3.0g silicon-dioxide and 3.2g Toluene-2,4-diisocyanate, 4-two isocyanic acids are dispersed in the 90mL dry toluene, vacuumize the back nitrogen protection, disperse 10min in ultrasonic wave, constant temperature is 90 ℃ in the placement oil bath, reacts 6h under the magnetic agitation, reaction finishes the back with the TDI of a large amount of dry toluene flush away surface physics absorption, utilizes centrifugation method separation function silicon-dioxide;
2. getting the 2.0g functionalized SiO 2 is dispersed in the 60ml dry toluene; in ultrasonic wave, disperse 10min, drip 0.6g Propylene glycol monoacrylate (HPA) then, vacuumize nitrogen protection; react 48h under 95 ℃ of magnetic agitation of oil bath, reaction finishes the back and separates crosslinking aid S iO with centrifugation method
2-HPA is with the HPA of a large amount of toluene flush away physical adsorptions.
Described non-proton property polar solvent is the mixture of dimethyl sulfoxide (DMSO) and dimethyl formamide, and described mineral acid is sulfuric acid.
Embodiment five
The preparation method of croscarmellose sodium may further comprise the steps:
1. with 50 gram aprotic polar solvent dissolvings, 19 gram Xylo-Mucines, stirring and dissolving obtains the carboxymethylcellulose sodium solution of homogeneous;
2. add inorganic acid catalyst in above-mentioned carboxymethylcellulose sodium solution, make reactant be tied to form acidity, the pH value is 2.5, reacts 60min under the room temperature, obtains cmc soln;
3. get 2.0 gram linking agents and be scattered in the 9.0 gram cmc solns, place ultrasonic wave pre-polymerization 10h through deoxygenation towards nitrogen, with 100 ℃ of polyase 13 8h, obtain crosslinked carboxymethyl cellulose again;
4. be cooled to room temperature, 95% ethanol-water solution that dropwise drips alkalization in the above-mentioned cross-linked carboxymethyl cellulose solution that obtains obtains croscarmellose sodium, filters, and be 8 with absolute ethanol washing to pH value, dry 6h under 110 ℃ obtains the croscarmellose sodium powder.
The croscarmellose sodium that present embodiment makes, its swelling capacity are 15, and transparence is 98%, and water viscosity is 7016mPas in the time of 80 ℃.
Described linking agent is the silicon-dioxide-Propylene glycol monoacrylate of nano composite material.
Described silicon-dioxide-Propylene glycol monoacrylate prepares by the following method:
1. silicon-dioxide and Toluene-2,4-diisocyanate, 4-two isocyanic acids (TDI) reaction: get 3.0g silicon-dioxide and 3.13g Toluene-2,4-diisocyanate, 4-two isocyanic acids are dispersed in the 90mL dry toluene, vacuumize the back nitrogen protection, disperse 10min in ultrasonic wave, constant temperature is 90 ℃ in the placement oil bath, reacts 6h under the magnetic agitation, reaction finishes the back with the TDI of a large amount of dry toluene flush away surface physics absorption, utilizes centrifugation method separation function silicon-dioxide;
2. getting the 2.0g functionalized SiO 2 is dispersed in the 60ml dry toluene; in ultrasonic wave, disperse 10min, drip 0.55g Propylene glycol monoacrylate (HPA) then, vacuumize nitrogen protection; react 48h under 90 ℃ of magnetic agitation of oil bath, reaction finishes the back and separates crosslinking aid S iO with centrifugation method
2-HPA is with the HPA of a large amount of toluene flush away physical adsorptions.
Described non-proton property polar solvent is tetrahydrofuran (THF), and described mineral acid is sulfuric acid.
Embodiment six
The preparation method of croscarmellose sodium may further comprise the steps:
1. dissolve 15 mass parts Xylo-Mucines with 50 mass parts aprotic polar solvents, stirring and dissolving obtains the carboxymethylcellulose sodium solution of homogeneous;
2. add inorganic acid catalyst in above-mentioned carboxymethylcellulose sodium solution, make reactant be tied to form acidity, the pH value is 3.0, reacts 60min under the room temperature, obtains cmc soln;
3. get 1.8 gram linking agents and be scattered in the 9.0 gram cmc solns, place ultrasonic wave pre-polymerization 12h through deoxygenation towards nitrogen, with 110 ℃ of polyase 13 8h, obtain crosslinked carboxymethyl cellulose again;
4. be cooled to room temperature, 95% ethanol-water solution that dropwise drips alkalization in the above-mentioned cross-linked carboxymethyl cellulose solution that obtains obtains croscarmellose sodium, filters, and be 7 with absolute ethanol washing to pH value, dry 5h under 90 ℃ obtains the croscarmellose sodium powder.
The croscarmellose sodium that present embodiment makes, its swelling capacity are 12, and transparence is 98%, and water viscosity is 7080mPas in the time of 80 ℃.
Described linking agent is the silicon-dioxide-Propylene glycol monoacrylate of nano composite material.
Described silicon-dioxide-Propylene glycol monoacrylate prepares by the following method:
1. silicon-dioxide and Toluene-2,4-diisocyanate, 4-two isocyanic acids (TDI) reaction: get 3.0g silicon-dioxide and 3.1g Toluene-2,4-diisocyanate, 4-two isocyanic acids are dispersed in the 90mL dry toluene, vacuumize the back nitrogen protection, disperse 10min in ultrasonic wave, constant temperature is 90 ℃ in the placement oil bath, reacts 6h under the magnetic agitation, reaction finishes the back with the TDI of a large amount of dry toluene flush away surface physics absorption, utilizes centrifugation method separation function silicon-dioxide;
2. getting the 2.0g functionalized SiO 2 is dispersed in the 60ml dry toluene; in ultrasonic wave, disperse 10min, drip 0.55g Propylene glycol monoacrylate (HPA) then, vacuumize nitrogen protection; react 48h under 90 ℃ of magnetic agitation of oil bath, reaction finishes the back and separates crosslinking aid S iO with centrifugation method
2-HPA is with the HPA of a large amount of toluene flush away physical adsorptions.
Described non-proton property polar solvent is tetrahydrofuran (THF), and described mineral acid is sulfuric acid.
Embodiment seven
The preparation method of croscarmellose sodium may further comprise the steps:
1. with 50 gram aprotic polar solvent dissolvings, 18 gram Xylo-Mucines, stirring and dissolving obtains the carboxymethylcellulose sodium solution of homogeneous;
2. add inorganic acid catalyst in above-mentioned carboxymethylcellulose sodium solution, make reactant be tied to form acidity, the pH value is 3.0, reacts 60min under the room temperature, obtains cmc soln;
3. get 2.0 gram linking agents and be scattered in the 9.0 gram cmc solns, place ultrasonic wave pre-polymerization 12h through deoxygenation towards nitrogen, with 100 ℃ of polyase 13 7h, obtain crosslinked carboxymethyl cellulose again;
4. be cooled to room temperature, 95% ethanol-water solution that dropwise drips alkalization in the above-mentioned cross-linked carboxymethyl cellulose solution that obtains obtains croscarmellose sodium, filters, and be 7 with absolute ethanol washing to pH value, dry 6h under 110 ℃ obtains the croscarmellose sodium powder.
The croscarmellose sodium that present embodiment makes, its swelling capacity are 14, and transparence is 98%, and water viscosity is 6990mPas in the time of 80 ℃.
Described linking agent is the silicon-dioxide-Propylene glycol monoacrylate of nano composite material.
Described silicon-dioxide-Propylene glycol monoacrylate prepares by the following method:
1. silicon-dioxide and Toluene-2,4-diisocyanate, 4-two isocyanic acids (TDI) reaction: get 3.0g silicon-dioxide and 3.13g Toluene-2,4-diisocyanate, 4-two isocyanic acids are dispersed in the 90mL dry toluene, vacuumize the back nitrogen protection, disperse 10min in ultrasonic wave, constant temperature is 90 ℃ in the placement oil bath, reacts 6h under the magnetic agitation, reaction finishes the back with the TDI of a large amount of dry toluene flush away surface physics absorption, utilizes centrifugation method separation function silicon-dioxide;
2. getting the 2.0g functionalized SiO 2 is dispersed in the 60ml dry toluene; in ultrasonic wave, disperse 10min, drip 0.55g Propylene glycol monoacrylate (HPA) then, vacuumize nitrogen protection; react 48h under 90 ℃ of magnetic agitation of oil bath, reaction finishes the back and separates crosslinking aid S iO with centrifugation method
2-HPA is with the HPA of a large amount of toluene flush away physical adsorptions.
Described non-proton property polar solvent is tetrahydrofuran (THF), and described mineral acid is sulfuric acid.
Embodiment eight
The preparation method of croscarmellose sodium may further comprise the steps:
1. with 50 gram aprotic polar solvent dissolvings, 20 gram Xylo-Mucines, stirring and dissolving obtains the carboxymethylcellulose sodium solution of homogeneous;
2. add inorganic acid catalyst in above-mentioned carboxymethylcellulose sodium solution, make reactant be tied to form acidity, the pH value is 3.0, reacts 60min under the room temperature, obtains cmc soln;
3. get 2.4 gram linking agents and be scattered in the 9.0 gram cmc solns, place ultrasonic wave pre-polymerization 12h through deoxygenation towards nitrogen, with 100 ℃ of polyase 13 6h, obtain crosslinked carboxymethyl cellulose again;
4. be cooled to room temperature, 95% ethanol-water solution that dropwise drips alkalization in the above-mentioned cross-linked carboxymethyl cellulose solution that obtains obtains croscarmellose sodium, filters, and be 7 with absolute ethanol washing to pH value, dry 8h under 110 ℃ obtains the croscarmellose sodium powder.
The croscarmellose sodium that present embodiment makes, its swelling capacity are 12, and transparence is 98%, and water viscosity is 7012mPas in the time of 80 ℃.
Described linking agent is the silicon-dioxide-Propylene glycol monoacrylate of nano composite material.
Described silicon-dioxide-Propylene glycol monoacrylate prepares by the following method:
1. silicon-dioxide and Toluene-2,4-diisocyanate, 4-two isocyanic acids (TDI) reaction: get 3.0g silicon-dioxide and 3.13g Toluene-2,4-diisocyanate, 4-two isocyanic acids are dispersed in the 90mL dry toluene, vacuumize the back nitrogen protection, disperse 10min in ultrasonic wave, constant temperature is 90 ℃ in the placement oil bath, reacts 6h under the magnetic agitation, reaction finishes the back with the TDI of a large amount of dry toluene flush away surface physics absorption, utilizes centrifugation method separation function silicon-dioxide;
2. getting the 2.0g functionalized SiO 2 is dispersed in the 60ml dry toluene; in ultrasonic wave, disperse 10min, drip 0.55g Propylene glycol monoacrylate (HPA) then, vacuumize nitrogen protection; react 48h under 90 ℃ of magnetic agitation of oil bath, reaction finishes the back and separates crosslinking aid S iO with centrifugation method
2-HPA is with the HPA of a large amount of toluene flush away physical adsorptions.
Described non-proton property polar solvent is dimethyl sulfoxide (DMSO), and described mineral acid is sulfuric acid.
By the croscarmellose sodium that prior art makes, its swelling capacity, transparence and in the time of 80 ℃ water viscosity, can accomplish 12 respectively, 95% and 6000mPas, but seldom have product can reach above-mentioned performance perameter simultaneously.The present invention not only can reach simultaneously or near above-mentioned performance perameter, also obviously be better than above-mentioned parameter on performances such as viscosity.
Claims (4)
1. the preparation method of croscarmellose sodium is characterized in that it may further comprise the steps:
1. with 50 mass parts aprotic polar solvents dissolving, 15～20 mass parts Xylo-Mucines, stirring and dissolving obtains the carboxymethylcellulose sodium solution of homogeneous;
2. adding inorganic acid catalyst in above-mentioned carboxymethylcellulose sodium solution, to make the pH of reaction system be 1.5～3.0, reacts 30～60min under the room temperature, obtains cmc soln;
3. get in the described cmc soln that 1.1～2.4 mass parts linking agents are scattered in 9.0 mass parts, must mix liquid, described mixed liquid row oxygen and filling nitrogen is placed on pre-polymerization 6～12h in the ultrasonic wave, and polyase 13 5～38h under 90～110 ℃ of conditions obtains crosslinked cmc soln then;
4. be cooled to room temperature, in above-mentioned crosslinked cmc soln, drip the ethanol-water solution that alkalizes, obtain croscarmellose sodium solution;
5. using the above-mentioned croscarmellose sodium solution of absolute ethanol washing, is 6～8 until pH, and drying obtains the croscarmellose sodium powder under 90～110 ℃ of conditions then;
Described linking agent is the silicon-dioxide-Propylene glycol monoacrylate of nano composite material.
2. the preparation method of croscarmellose sodium according to claim 1 is characterized in that, described silicon-dioxide-Propylene glycol monoacrylate prepares by the following method:
1. get the silicon-dioxide of 3.0 mass parts and the TDI of 3～3.2 mass parts, be dispersed in the dry toluene of 80～100 mass parts, vacuumize the back nitrogen protection, in ultrasonic wave, disperse l0～12min, constant temperature is 90～95 ℃ in the placement oil bath, reacts 5～6h under the magnetic agitation; Reaction finishes the back with the TDI of dry toluene flush away surface physics absorption, utilizes centrifugation method separation function silicon-dioxide;
2. the functionalized SiO 2 of getting 2.0 mass parts is dispersed in 5～80ml dry toluene; in ultrasonic wave, disperse 10～12min; drip the Propylene glycol monoacrylate of 0.5～0.6 mass parts then; vacuumize nitrogen protection; react 40～50h under 90 ℃ of magnetic agitation of oil bath, reaction finishes the back and obtains described linking agent silicon-dioxide-Propylene glycol monoacrylate with the centrifugation method separation.
3. the preparation method of croscarmellose sodium according to claim 1 and 2, it is characterized in that: described aprotic polar solvent is one or more in dimethyl sulfoxide (DMSO), tetrahydrofuran (THF) and the dimethyl formamide.
4. the preparation method of croscarmellose sodium according to claim 1 and 2, it is characterized in that: described inorganic acid catalyst is sulfuric acid.
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| CN104262649A (en) * | 2014-09-28 | 2015-01-07 | 泸州北方化学工业有限公司 | Sodium croscarmellose and preparation method thereof |
| CN107419599B (en) * | 2017-06-28 | 2020-03-10 | 徐州力志纤维素科技有限公司 | Carboxymethyl cellulose modified nano silicon dioxide |
| CN114541133B (en) * | 2022-03-21 | 2024-05-07 | 浙江隆腾医用新材料有限公司 | Preparation method of crosslinked sodium carboxymethyl cellulose fiber |
| CN117164728A (en) * | 2023-09-06 | 2023-12-05 | 山东扬子生物科技有限公司 | Production process for preparing CMC (CMC) for lithium battery by slurry method |
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