CN1046740A - The single stage method technology for synthesizing cross-linked carboxymethyl hydroxypropyl cellulose complex ether - Google Patents
The single stage method technology for synthesizing cross-linked carboxymethyl hydroxypropyl cellulose complex ether Download PDFInfo
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- CN1046740A CN1046740A CN 89102682 CN89102682A CN1046740A CN 1046740 A CN1046740 A CN 1046740A CN 89102682 CN89102682 CN 89102682 CN 89102682 A CN89102682 A CN 89102682A CN 1046740 A CN1046740 A CN 1046740A
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 19
- -1 carboxymethyl hydroxypropyl Chemical group 0.000 title claims abstract description 14
- 238000005516 engineering process Methods 0.000 title claims description 12
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 title claims description 6
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 title claims description 6
- 239000001863 hydroxypropyl cellulose Substances 0.000 title claims description 5
- 230000002194 synthesizing effect Effects 0.000 title claims description 5
- 229920002678 cellulose Polymers 0.000 claims abstract description 30
- 239000001913 cellulose Substances 0.000 claims abstract description 25
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 21
- 239000003960 organic solvent Substances 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 12
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 6
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 5
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract 2
- 230000011987 methylation Effects 0.000 claims abstract 2
- 238000007069 methylation reaction Methods 0.000 claims abstract 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 11
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 claims description 8
- 238000004898 kneading Methods 0.000 claims description 6
- 238000004132 cross linking Methods 0.000 claims description 5
- 238000006266 etherification reaction Methods 0.000 claims description 5
- 239000012043 crude product Substances 0.000 claims description 4
- 239000000835 fiber Substances 0.000 claims description 4
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 244000025254 Cannabis sativa Species 0.000 claims description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims 1
- 150000003839 salts Chemical class 0.000 abstract description 17
- 239000008186 active pharmaceutical agent Substances 0.000 abstract description 6
- 229920003086 cellulose ether Polymers 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 35
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 235000010980 cellulose Nutrition 0.000 description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 239000012670 alkaline solution Substances 0.000 description 8
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 6
- 238000006467 substitution reaction Methods 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 229960000583 acetic acid Drugs 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 241000609240 Ambelania acida Species 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000010905 bagasse Substances 0.000 description 3
- 239000002826 coolant Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000008719 thickening Effects 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229920001131 Pulp (paper) Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 238000005815 base catalysis Methods 0.000 description 2
- 238000005553 drilling Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 1
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical group 0.000 description 1
- 230000001458 anti-acid effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 1
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- YLGXILFCIXHCMC-JHGZEJCSSA-N methyl cellulose Chemical compound COC1C(OC)C(OC)C(COC)O[C@H]1O[C@H]1C(OC)C(OC)C(OC)OC1COC YLGXILFCIXHCMC-JHGZEJCSSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
Abstract
The invention belongs to the synthetic field of water-soluble high-molecular cellulose ether.The invention provides a step finishes the synthesis technique of etherificate, crosslinked, purifying cellulose complex ether.In alkaline medium, utilize hydrophilic organic solvent to make thinner, Mierocrystalline cellulose and etherifying agent, linking agent reaction, dosage of crosslinking agent is that 0.1～3.5% (Mierocrystalline cellulose is heavy), hydroxypropyl etherifying agent consumption are 30～250% (Mierocrystalline cellulose is heavy), and the carboxyl methylation etherifying agent consumption is 10～94% (Mierocrystalline cellulose is heavy).This technological reaction is even, and organic thinner reclaims easily, and dosage of crosslinking agent is few, the product viscosity height, and thermostability, salt resistance, resistance to acid is good, and can produce the product of different DS and MS.
Description
The invention belongs to the water-soluble high-molecular cellulose ether synthesis technique.
The synthesis method of carboxymethyl hydroxypropyl cellulose complex ether (CMHPC) has after the first carboxymethylation method such as carboxymethylation behind hydroxypropylation or the first hydroxypropylation.But these two kinds of methods, not only etherificate is carried out in two steps, and the also purified processing of intermediate product, and synthetic route is long, and it is big to consume amount of chemicals used, and reaction time is long, and product falls that to gather degree big, and viscosity is low.And, in order to obtain to replace uniform product, often use the mixed organic solvent of big bath raio or many components to make thinner.Because separated from solvent reclaims difficulty, and economical effectiveness is dissatisfied.
The objective of the invention is two-step approach etherificate and two-step purifying, be reduced to a step etherificate, and finish crosslinking reaction simultaneously and do modification, single step purification is produced reaction evenly, high viscosity, the carboxymethyl hydroxypropyl cellulose complex ether that salt resistance is good.The cheap hydrophilic organic solvent of the low bath raio of this technology utilization is made thinner, etherificate efficient height.Because carboxymethylation and hydroxypropylation all carry out under base catalysis, so two kinds of substitution reactions can be carried out in one step of while.The crosslinked of hydroxyl between macromole also can be finished under base catalysis.So as long as suitable alkali number is arranged, carboxymethylation then, hydroxypropylation, and molecule crosslinked may finishing in a step do not cause a large amount of reactions of paying.Japanese Patent Publication 61-157,501 are used to prepare the high viscosity grade Xylo-Mucine of ionic with crosslinking reaction, crosslinked by realizing on the unsubstituted hydroxyl of Mierocrystalline cellulose.And the present invention is in addition, the crosslinked free hydroxyl group that still occurs on the hydroxypropyl that has replaced, and the old friend joins better effects if, and product viscosity improves more obvious.And what the present invention prepared is ion and non-ionic type complex ether, than the monoether superior performance in the above-mentioned patent documentation.Product has better anti-divalent salts, antiacid performance.This technology is alkalization, etherificate, and crosslinking reaction, all carries out in the same formula reactor of kneading.Adopt cheap moisture hydrophilic organic solvent to make thinner.Basifier is an alkali metal hydroxide, available hydrogen sodium oxide or potassium hydroxide.Because alkalization merges, two kinds of etherification reactions can play " crystalline substance disappears " effect again, so alkali charge is lower than two-step approach, and pair reaction is few.The alkali consumption is the 20-80%(cellulose amount), can adjust with different hydroxypropyl substitution value MS with producing different degree of substitution by carboxymethyl DS.Alkalization can at room temperature keep more than 20 minutes, can guarantee that then alkalization fully.Organic solvent can be used methyl alcohol, ethanol, Virahol, the trimethyl carbinol, acetone etc., and consumption is the heavy 0.8-5.0 of Mierocrystalline cellulose times.Etherification reaction carries out under vacuum, carboxymethylation ether agent monochloroacetic acid (MCA), be dissolved in a part of organic solvent, with hydroxypropyl etherifying agent propylene oxide (PO) and linking agent epoxy chloropropane (EP) but or trichoroacetic acid(TCA) nationality vacuum add in the reactor, consumption is looked the product of producing different degree of substitution and is different, the product of degree of substitution by carboxymethyl DS=0.03-0.94, the MCA consumption is heavy for the 10-94% Mierocrystalline cellulose.The product of hydroxypropyl substitution value MS=0.19-4.01, the PO consumption is heavy for the 30-250% Mierocrystalline cellulose, and dosage of crosslinking agent is heavy for the 0.1-3.5% Mierocrystalline cellulose.Alkaline coarse product after the etherificate can neutralize with mineral acid example hydrochloric acid, sulfuric acid, phosphoric acid or organic acid such as acetic acid.The neutral product can be used methyl alcohol, ethanol, acetone equal solvent washing purifying.
One-step synthesis process of the present invention, use mixed solvent low than the hydrophilic organic solvent polarity of single-component, more favourable to carboxymethylation, PO be organic thinner in two components be again the etherifying agent of hydroxypropylation, along with reaction is carried out, only there is single hydrophilic organic solvent in the system, the recovery of solvent and recycle very convenient.Therefore, the present invention had both had many components organic thinner can make etherification reaction even, avoids the characteristics of many components organic thinner difficult separation and recycling again.And dosage of crosslinking agent is few, the product viscosity height, and Heat stability is good does not influence the recovery of solvent.This technology can be produced different DS and MS product ion and the nonionic character with the control product, and makes it to have the character that can be dissolved in some moisture polar organic solvent.Technology of the present invention can adopt lint cellulose, and wood-cellulose or grass fiber element are raw material.The one-step synthesis process that is provided can also synthesizing crosslinked carboxyalkyl hydroxylalkyl cellulose complex ether.
Table 1 is that the product analysis index of single stage method of the present invention (example 1-10) and two step method compares.The two step method synthetic route is long, and product viscosity is low to moderate 24 and 40 centipoises, salt resistance, and resistance to acid, organic solvent dissolution is superior unlike single stage method.Single stage method product viscosity of the present invention is than much higher.Example 1-4 increases with linking agent EP consumption, and product viscosity improves, but salt resistance has downtrending.Promptly increase with dosage of crosslinking agent, salt viscosity, the sticking ratio of salt reduces, and the soltion viscosity that resistance to acid reaches at organic solvent dissolution also has similar phenomena.Example 5 is not owing to add linking agent, and viscosity is low than example 1-4 product, but still than two step method height.Although example 6 and 7 adopts low polymerization degree wood pulp or bagasse pulp to work as raw material, with the product that the present invention produces, viscosity is still much higher than the product made from the high-polymerization degree linter pulp in the two step method.Example 8-10 is to produce the product of different DS and MS with different etherificate dosage.Improve DS, ionic more outstanding, anti-monovalent salt performance is good, but anti-divalent salts performance weakens.Then nonionic is more outstanding to improve MS, anti-divalence salt, resistance to acid, organic solvent dissolution increase, but anti-monovalent salt performance weakens.
Table 2 is commercially available various ether of cellulose performance analysis indexs.As seen from the table, non-ionic celluloses ether HPC, HPMC, MC can only resist divalent salts, can not resist monovalent salt.The plain DRISPAC of ionic polyanion fiber type can only resist monovalence and can not resist divalent salts.Have only HEC that better comprehensive salt resistance and resistance to acid are just arranged, but organic solvent dissolution is relatively poor.Comparison sheet 1 and table 2 as seen, the crosslinked CMHPC of synthetic of the present invention has had both the advantage of ionic and non-ionic celluloses ether, has good comprehensive salt resistance, character such as resistance to acid and some organic solvent dissolution.
Because product has good anti-monovalence and divalent salts characteristic, is the mud conditioner of high salinity strata drilling engineering; This product has a good thermal stability through cross-linking modified, can be used as the mud conditioner of deep drilling engineering.Because the product viscosity height, can be used as the good thickening material of industry, suspension agent and stablizer, it is poor that it has overcome ionic TYLOSE 30000 resistance to acid, the shortcoming that in PH＜3 media, lost efficacy, thus make it above-mentioned applied range many.Owing to have the solvability and the thickening property of organic solvent, product of the present invention still can expand in the filed of daily-use chemical industry as the thickening material range of application again.
Example 1-4
Sodium hydroxide 139 grams are dissolved in the 180 gram water, with contain linking agent EP(example 1,2,3, the EP consumption is respectively 0.4,0.9 in 4, and 1.2,2.4 the mixed mutually alkaline solution that is mixed with of 95% ethanol, 300 grams gram), alkaline solution matches with 200 gram lint celluloses (polymerization degree 1450), sprays into respectively and drops in 5 liters of kneading machines, and excluding air is to vacuum tightness 680mmHg, the nationality vacuum adds 122.6 gram PO, keep alkalization temperature 13-19 ℃ with jacket water (J.W.), alkalized 20 minutes, add 140.7 gram MCA and be dissolved in 112 grams, 95% alcoholic acid solution, in 30 minutes, temperature is risen to 78 ℃, kept this temperature 120 minutes.Reaction terminating feeds the chuck water coolant and cools the temperature to 50 ℃, opens the atmospheric valve door, opening, the crude product that takes out neutralizes with 18% acetic acid, with 70% washing with alcohol twice, and each 1600ml, the mother liquor distillation of centrifugation is reclaimed, and product is 70 ℃ of dryings, and product analysis and character are listed in table 1.
Example 5
Remove the alkaline solution composition and change sodium hydroxide 158 grams into, water 160 grams, 95% ethanol, 324 grams do not add EP.Etherifying agent MCA changes 189 into and restrains outside the differences such as being dissolved in 150 grams, 95% ethanol, and surplus operation and example 1-4 are together altogether.Product analysis and character are listed in table 1.
Example 6
Remove the wood-cellulose (wood pulp) that raw material changes the polymerization degree 780 into, outside the differences such as EP consumption 1.8 grams, all the other are with example 1-4, and product analysis and character are listed in table 1.
Example 7
Bagasse fibre element (bagasse pulp) EP that changes the polymerization degree 750 except that raw material into changes into the differences such as 2.4 grams, and all the other are with example 1-4.Product analysis and character are listed in table 1.
Example 8
Sodium hydroxide 137 grams are dissolved in the 139 gram water, with 95% ethanol that contains linking agent EP1.8 gram, 300 grams mix, and are mixed with alkaline solution, alkaline solution matches with 200 gram lint celluloses, spray into respectively and drop in 5 liters of kneading machines, excluding air is kept alkalization temperature 14-22 ℃ to vacuum tightness 680mmHg with the chuck water coolant, alkalized 20 minutes, add 90.5 gram MCA and be dissolved in 72 grams, 95% alcoholic acid solution, and 367 gram PO, in 30 minutes, temperature is risen to 83 ℃, kept this temperature 135 minutes, PO, opening are reclaimed in the reaction terminating condensation, crude product neutralizes with Glacial acetic acid, with 70% washing with acetone twice, each 1500ml, the centrifugal refined products is 60-70 ℃ of vacuum-drying.Product analysis and character are listed in table 1.
Example 9
Sodium hydroxide 84 grams are dissolved in the 89 gram water, with gram 95% ethanol that contains the EP0.6 gram, 200 grams are hybridly prepared into alkaline solution mutually, alkaline solution matches with 200 gram lint celluloses, spray into respectively and drop in 5 liters of kneading machines, keep alkalization temperature 19-24 ℃ with the chuck water coolant, alkalized 20 fens, excluding air is to vacuum tightness 680mmHg, and the nationality vacuum adds 40.2 gram MCA, is dissolved in the ethanolic soln and the 409 gram PO of 32 grams 95%, intensification degree to 80 ℃ in 30 minutes, kept this temperature 150 minutes, reaction process, kneading machine is reduced to negative pressure gradually from malleation.Reaction terminating reclaims PO, and crude product neutralizes with Glacial acetic acid, and with 80% washing with acetone twice, 1500ml at every turn, centrifuge refining product be at 60-70 ℃, vacuum-drying, and product analysis and character are listed in table 1.
Example 10 removes the alkaline solution composition and changes sodium hydroxide 97 grams into, water 109 grams, 95% ethanol, 20 grams, EP1.8 gram.Etherifying agent changes the MCA20.1 gram into and is dissolved in 16 grams, 95% ethanol.The PO consumption changes into beyond the difference such as 510.6 grams, and all the other etherificates operations are with example 9, and reacting coarse product is neutralized to PH3 with 85% phosphoric acid, washs 3 times with the hot water canting method more than 90 ℃, uses hot water 1500ml at every turn, and product is 90 ℃ of oven dry.
Claims (6)
1, a kind of single stage method technology for synthesizing cross-linked carboxymethyl hydroxypropyl cellulose complex ether, it is included in moisture hydrophilic organic solvent and the alkaline medium, Mierocrystalline cellulose and etherifying agent, linking agent reaction, it is characterized by in the formula reactor of kneading single stage method and finish alkalization, two kinds of etherification reactions of carboxymethylation and hydroxypropylation and intermolecular cross-linking reaction, and a step finish the crude product purifying.Dosage of crosslinking agent is 0.1～3.5% (cellulose), and the hydroxypropyl etherifying agent consumption is 30～250% (cellulose), and the carboxyl methylation etherifying agent consumption is 10～94% (cellulose).
2, according to the technology described in the claim 1, it is characterized by the carboxymethyl etherification agent can be monochloroacetic acid or its sodium salt, and hydroxypropyl etherifying agent can be a propylene oxide.
3, according to the technology described in the claim 1, it is characterized by moisture hydrophilic organic solvent can be methyl alcohol, ethanol, Virahol, the trimethyl carbinol, and its consumption is a 0.8-5.0 times of cellulose.
4, according to the technology described in the claim 1, it is characterized by linking agent can be epoxy chloropropane, trichoroacetic acid(TCA).
5, according to the technology described in the claim 1, it is characterized by Mierocrystalline cellulose can be lint cellulose, or water material Mierocrystalline cellulose, or the grass fiber element.
6, technology according to claim 1, the one-step synthesis process that it is characterized by indication can synthesizing crosslinked carboxyalkyl hydroxylalkyl cellulose complex ether.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89102682 CN1016786B (en) | 1989-04-26 | 1989-04-26 | One-step technology for synthesizing cross-linked carboxymethyl hydroxypropyl cellulose complex ether |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89102682 CN1016786B (en) | 1989-04-26 | 1989-04-26 | One-step technology for synthesizing cross-linked carboxymethyl hydroxypropyl cellulose complex ether |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1046740A true CN1046740A (en) | 1990-11-07 |
| CN1016786B CN1016786B (en) | 1992-05-27 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 89102682 Expired CN1016786B (en) | 1989-04-26 | 1989-04-26 | One-step technology for synthesizing cross-linked carboxymethyl hydroxypropyl cellulose complex ether |
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| CN (1) | CN1016786B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102391380A (en) * | 2011-08-26 | 2012-03-28 | 大连工业大学 | Hemp stalk composite cellulose ether and preparation method thereof |
| CN104024277A (en) * | 2011-12-02 | 2014-09-03 | 实验室维维西公司 | Method for simultaneously substituting and cross-linking a polysaccharide by means of the hydroxyl functions thereof |
| CN104193829A (en) * | 2014-08-25 | 2014-12-10 | 四川北方硝化棉股份有限公司 | Production method of spherical cellulose acetate butyrate |
| CN113710708A (en) * | 2019-05-01 | 2021-11-26 | 陶氏环球技术有限责任公司 | Process for producing crosslinked cellulose ethers |
-
1989
- 1989-04-26 CN CN 89102682 patent/CN1016786B/en not_active Expired
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102391380A (en) * | 2011-08-26 | 2012-03-28 | 大连工业大学 | Hemp stalk composite cellulose ether and preparation method thereof |
| CN102391380B (en) * | 2011-08-26 | 2013-05-22 | 大连工业大学 | Hemp stalk composite cellulose ether and preparation method thereof |
| CN104024277A (en) * | 2011-12-02 | 2014-09-03 | 实验室维维西公司 | Method for simultaneously substituting and cross-linking a polysaccharide by means of the hydroxyl functions thereof |
| CN104024277B (en) * | 2011-12-02 | 2018-11-06 | 实验室维维西公司 | Replace the method with cross-linked polysaccharides simultaneously for the hydroxy functional group by polysaccharide |
| CN104193829A (en) * | 2014-08-25 | 2014-12-10 | 四川北方硝化棉股份有限公司 | Production method of spherical cellulose acetate butyrate |
| CN113710708A (en) * | 2019-05-01 | 2021-11-26 | 陶氏环球技术有限责任公司 | Process for producing crosslinked cellulose ethers |
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| Publication number | Publication date |
|---|---|
| CN1016786B (en) | 1992-05-27 |
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