CN102219863B - Process for modifying hydroxyethylcellulose (HEC) by high-carbon alkylation - Google Patents
Process for modifying hydroxyethylcellulose (HEC) by high-carbon alkylation Download PDFInfo
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- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 15
- 230000029936 alkylation Effects 0.000 title claims abstract description 9
- 238000005804 alkylation reaction Methods 0.000 title claims abstract description 9
- 238000000034 method Methods 0.000 title abstract description 6
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 title abstract 10
- 239000004354 Hydroxyethyl cellulose Substances 0.000 title abstract 10
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 title abstract 10
- 238000005516 engineering process Methods 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims description 107
- 238000005406 washing Methods 0.000 claims description 72
- 239000001913 cellulose Substances 0.000 claims description 26
- 229920002678 cellulose Polymers 0.000 claims description 26
- 239000007788 liquid Substances 0.000 claims description 26
- 239000011343 solid material Substances 0.000 claims description 25
- 239000002904 solvent Substances 0.000 claims description 25
- 238000001704 evaporation Methods 0.000 claims description 24
- 230000008020 evaporation Effects 0.000 claims description 24
- 238000000926 separation method Methods 0.000 claims description 24
- 238000000935 solvent evaporation Methods 0.000 claims description 24
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 claims description 14
- 229960001231 choline Drugs 0.000 claims description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 13
- 239000003513 alkali Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 238000006386 neutralization reaction Methods 0.000 claims description 12
- 238000012856 packing Methods 0.000 claims description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 8
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 7
- 230000004048 modification Effects 0.000 claims description 7
- 238000012986 modification Methods 0.000 claims description 7
- KOFZTCSTGIWCQG-UHFFFAOYSA-N 1-bromotetradecane Chemical compound CCCCCCCCCCCCCCBr KOFZTCSTGIWCQG-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- PBLNBZIONSLZBU-UHFFFAOYSA-N 1-bromododecane Chemical group CCCCCCCCCCCCBr PBLNBZIONSLZBU-UHFFFAOYSA-N 0.000 claims description 5
- HNTGIJLWHDPAFN-UHFFFAOYSA-N 1-bromohexadecane Chemical compound CCCCCCCCCCCCCCCCBr HNTGIJLWHDPAFN-UHFFFAOYSA-N 0.000 claims description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 230000001476 alcoholic effect Effects 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 238000010298 pulverizing process Methods 0.000 claims 1
- 239000000839 emulsion Substances 0.000 abstract description 10
- 239000003973 paint Substances 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- 238000010276 construction Methods 0.000 abstract description 2
- 239000012847 fine chemical Substances 0.000 abstract description 2
- 241000233866 Fungi Species 0.000 abstract 1
- 238000003889 chemical engineering Methods 0.000 abstract 1
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 46
- 239000000463 material Substances 0.000 description 31
- 238000010410 dusting Methods 0.000 description 10
- 235000008979 vitamin B4 Nutrition 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
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Abstract
The invention discloses a process for modifying hydroxyethylcellulose (HEC) by high-carbon alkylation, and relates to the field of fine chemical engineering. The hydroxyethylcellulose (HEC) is modified by high-carbon alkyl, so that the stability of the hydroxyethylcellulose (HEC) in application of emulsion paint is improved greatly, construction splatter is reduced, the fungus resistance of products can be improved by 20 to 30 percent, the shelf life of the produced emulsion paint is prolonged by 3 to 5 months, and the using effect of the hydroxyethylcellulose (HEC) in the emulsion paint can completely reach the same level in foreign countries. Due to the adoption of a computer control technology, the labor intensity of workers is reduced, labor is reduced, and the labor efficiency and production safety are improved.
Description
Technical field
The present invention relates to field of fine chemical, the technology of specifically a kind of high-carbon alkylation modification Natvosol (HEC).
Background technology
Natvosol (HEC) be with natural cellulose under the effect of solvent and alkali; Make with reacting ethylene oxide, at present, the Natvosol of most domestic enterprise production (HEC) substitution value generally can only reach 1.5-2.0; The effect of product in rubber-emulsion paint is bad; The stability in storage of rubber-emulsion paint is low, is easy to generate in the brushing process of rubber-emulsion paint and splashes, so the present domestic rubber-emulsion paint production unit that possesses scale has the Natvosol of 80% employing import.
Summary of the invention
For solving the technical problem of above-mentioned existence; The present invention provides the technology of a kind of high-carbon alkylation modification Natvosol (HEC); Utilize the high-carbon moieties to replace the residual hydroxyl in Natvosol (HEC) structure, improve the substituted degree of uniformity of polymer, improve the stability of product.
For achieving the above object, the technical scheme that the present invention adopts is following:
The technology of a kind of high-carbon alkylation modification Natvosol (HEC), realized by following step:
1) pulverize: the refined cellulose of getting 1000 mass parts is pulverized, is separated, and reaches 0.03-0.15mm (about 80 orders), tails dedusting;
2) alkalization: in reaction kettle, add the alcoholic solution of 5000-12000 mass parts, stir, add the sheet alkali of 200-280 mass parts; Be warmed up to 50-70 ℃ of choline; Cooling to normal temperature after choline finishes, add above-mentioned refined cellulose, is alkalization 0.5-1.5 hour under 15-35 ℃ the situation in temperature;
3) reaction: the high-carbon alkyl bromide that in reaction kettle, adds the 10-50 mass parts; Stirred 30-60 minute; The oxyethane that adds the 900-1300 mass parts then, reaction process divide two stages, and the fs is to be reaction 0.5-3.5 hour under 50-60 ℃ the situation in temperature; Subordinate phase is to be reaction 0.5-4 hour under 65-80 ℃ the situation in temperature, and reaction process is carried out time variable control by computingmachine;
4) neutralization: be under 40-60 ℃ the situation in temperature, the pH value that uses the acid solution of 300-500 mass parts to adjust above-mentioned gained solution is 5.5-8.5, in and the time be 0.5-1 hour;
5) flash liberation: gained solution in the aforesaid reaction vessel is carried out flash liberation, and solid materials gets into the washing still, and evaporation gets into reaction kettle to liquid solvent through the solvent evaporation device, recycles;
6) washing: in the washing still, the fixedly material in the step 5) is washing 1-2 hour under 20-35 ℃ the situation in temperature;
7) secondary separation: the solution that will wash in the still carries out secondary separation, and solid materials gets into the washing still, and evaporation gets into the washing still to liquid solvent through the solvent evaporation device, recycles.
8) drying, packing.
Described alcoholic solution can be Virahol, n-propyl alcohol, isopropylcarbinol, propyl carbinol.
Described acid solution can be hydrochloric acid, oxalic acid, acetic acid, phosphoric acid.
Described high-carbon alkyl bromide can be lauryl bromide, tetradecyl bromine, hexadecyl bromine.
The present invention adopts the high-carbon alkyl to come modified hydroxyethylcellulosadsorbing (HEC); Improved the stability of its Natvosol (HEC) in rubber-emulsion paint is used greatly; Having reduced construction splashes; The midew proof of its product can improve 20%-30%, and the rubber-emulsion paint shelf life extension 3-5 of production month, the result of use in rubber-emulsion paint can reach external peer-level fully; Adopt Computer Control Technology, reduced intensity of workers, reduced manual work simultaneously, improved efficiency and production security.
Description of drawings
Accompanying drawing is a process flow sheet of the present invention.
Embodiment
Describe the present invention below in conjunction with accompanying drawing and specific embodiment:
Embodiment 1:
1) pulverize: the natural refined cellulose that will become bag is got 1000 mass parts through opening bag, pulverizes with rotating knife formula kibbler, separates through cyclonic separator, reaches 0.03-0.15mm (about 80 orders), and tail gas is through bag-type dusting;
2) alkalization: in reaction kettle, add the aqueous isopropanol of 5000 mass parts, stir, add the sheet alkali of 280 mass parts, be warmed up to 50 ℃ of cholines, choline cools to normal temperature after finishing, and adds above-mentioned refined cellulose, is alkalization 0.5 hour under 35 ℃ the situation in temperature;
3) reaction: the lauryl bromide that in reaction kettle, adds 50 mass parts; Stirred 30 minutes; The oxyethane that adds 1300 mass parts then, reaction process divide two stages, and the fs is to be reaction 1.5 hours under 50 ℃ the situation in temperature; Subordinate phase is to be reaction 3 hours under 65 ℃ the situation in temperature, and reaction process is carried out time variable control by computingmachine;
4) neutralization: be under 40 ℃ the situation in temperature, the pH value that uses the acetum of 500 mass parts to adjust above-mentioned gained solution is 5.5, in the time be 1 hour;
5) flash liberation: gained solution in the aforesaid reaction vessel is carried out flash liberation, use the spiral pump convey materials, separate with the horizontal spiral separating machine, solid materials gets into the washing still, and evaporation gets into reaction kettle to liquid solvent through the solvent evaporation device, recycles;
6) washing: in the washing still, the fixedly material in the step 5) is washing 2 hours under 20 ℃ the situation in temperature;
7) secondary separation: the solution that will wash in the still carries out secondary separation, uses the spiral pump convey materials, separates with the horizontal spiral separating machine, and solid materials gets into the washing still, and evaporation gets into the washing still to liquid solvent through the solvent evaporation device, recycles.
8) drying, packing.
Embodiment 2:
1) pulverize: the natural refined cellulose that will become bag is got 1000 mass parts through opening bag, pulverizes with rotating knife formula kibbler, separates through cyclonic separator, reaches 0.03-0.15mm (about 80 orders), and tail gas is through bag-type dusting;
2) alkalization: in reaction kettle, add the n-propyl alcohol solution of 10000 mass parts, stir, add the sheet alkali of 250 mass parts, be warmed up to 60 ℃ of cholines, choline cools to normal temperature after finishing, and adds above-mentioned refined cellulose, is alkalization 1 hour under 20 ℃ the situation in temperature;
3) reaction: the lauryl bromide that in reaction kettle, adds 30 mass parts; Stirred 40 minutes; The oxyethane that adds 1000 mass parts then, reaction process divide two stages, and the fs is to be reaction 1 hour under 55 ℃ the situation in temperature; Subordinate phase is to be reaction 2.5 hours under 70 ℃ the situation in temperature, and reaction process is carried out time variable control by computingmachine;
4) neutralization: be under 50 ℃ the situation in temperature, the pH value that uses the acetum of 400 mass parts to adjust above-mentioned gained solution is 7, in the time be 0.6 hour;
5) flash liberation: gained solution in the aforesaid reaction vessel is carried out flash liberation, use the spiral pump convey materials, separate with the horizontal spiral separating machine, solid materials gets into the washing still, and evaporation gets into reaction kettle to liquid solvent through the solvent evaporation device, recycles;
6) washing: in the washing still, the fixedly material in the step 5) is washing 1.5 hours under 30 ℃ the situation in temperature;
7) secondary separation: the solution that will wash in the still carries out secondary separation, uses the spiral pump convey materials, separates with the horizontal spiral separating machine, and solid materials gets into the washing still, and evaporation gets into the washing still to liquid solvent through the solvent evaporation device, recycles.
8) drying, packing.
Embodiment 3:
1) pulverize: the natural refined cellulose that will become bag is got 1000 mass parts through opening bag, pulverizes with rotating knife formula kibbler, separates through cyclonic separator, reaches 0.03-0.15mm (about 80 orders), and tail gas is through bag-type dusting;
2) alkalization: in reaction kettle, add the butanol solution of 6000 mass parts, stir, add the sheet alkali of 240 mass parts, be warmed up to 65 ℃ of cholines, choline cools to normal temperature after finishing, and adds above-mentioned refined cellulose, is alkalization 0.8 hour under 25 ℃ the situation in temperature;
3) reaction: the tetradecyl bromine that in reaction kettle, adds 20 mass parts; Stirred 50 minutes; The oxyethane that adds 1200 mass parts then, reaction process divide two stages, and the fs is to be reaction 0.6 hour under 60 ℃ the situation in temperature; Subordinate phase is to be reaction 0.6 hour under 75 ℃ the situation in temperature, and reaction process is carried out time variable control by computingmachine;
4) neutralization: be under 45 ℃ the situation in temperature, the pH value that uses the oxalic acid solution of 450 mass parts to adjust above-mentioned gained solution is 7.5, in the time be 0.8 hour;
5) flash liberation: gained solution in the aforesaid reaction vessel is carried out flash liberation, use the spiral pump convey materials, separate with the horizontal spiral separating machine, solid materials gets into the washing still, and evaporation gets into reaction kettle to liquid solvent through the solvent evaporation device, recycles;
6) washing: in the washing still, the fixedly material in the step 5) is washing 1.2 hours under 25 ℃ the situation in temperature;
7) secondary separation: the solution that will wash in the still carries out secondary separation, uses the spiral pump convey materials, separates with the horizontal spiral separating machine, and solid materials gets into the washing still, and evaporation gets into the washing still to liquid solvent through the solvent evaporation device, recycles.
8) drying, packing.
Embodiment 4:
1) pulverize: the natural refined cellulose that will become bag is got 1000 mass parts through opening bag, pulverizes with rotating knife formula kibbler, separates through cyclonic separator, reaches 0.03-0.15mm (about 80 orders), and tail gas is through bag-type dusting;
2) alkalization: in reaction kettle, add the aqueous isopropanol of 12000 mass parts, stir, add the sheet alkali of 200 mass parts; Be warmed up to 70 ℃ of cholines; Cooling to normal temperature after choline finishes, add above-mentioned refined cellulose, is alkalization 1.5 hours under 15 ℃ the situation in temperature;
3) reaction: the tetradecyl bromine that in reaction kettle, adds 10 mass parts; Stirred 60 minutes; The oxyethane that adds 900 mass parts then, reaction process divide two stages, and the fs is to be reaction 0.5 hour under 60 ℃ the situation in temperature; Subordinate phase is to be reaction 0.5 hour under 80 ℃ the situation in temperature, and reaction process is carried out time variable control by computingmachine;
4) neutralization: be under 60 ℃ the situation in temperature, the pH value that uses the phosphoric acid solution of 300 mass parts to adjust above-mentioned gained solution is 8.5, in the time be 0.5 hour;
5) flash liberation: gained solution in the aforesaid reaction vessel is carried out flash liberation, use the spiral pump convey materials, separate with the horizontal spiral separating machine, solid materials gets into the washing still, and evaporation gets into reaction kettle to liquid solvent through the solvent evaporation device, recycles;
6) washing: in the washing still, the fixedly material in the step 5) is washing 1 hour under 35 ℃ the situation in temperature;
7) secondary separation: the solution that will wash in the still carries out secondary separation, uses the spiral pump convey materials, separates with the horizontal spiral separating machine, and solid materials gets into the washing still, and evaporation gets into the washing still to liquid solvent through the solvent evaporation device, recycles.
8) drying, packing.
Embodiment 5:
1) pulverize: the natural refined cellulose that will become bag is got 1000 mass parts through opening bag, pulverizes with rotating knife formula kibbler, separates through cyclonic separator, reaches 0.03-0.15mm (about 80 orders), and tail gas is through bag-type dusting;
2) alkalization: in reaction kettle, add the isobutanol solution of 10000 mass parts, stir, add the sheet alkali of 250 mass parts, be warmed up to 70 ℃ of cholines, choline cools to normal temperature after finishing, and adds above-mentioned refined cellulose, is alkalization 1 hour under 35 ℃ the situation in temperature;
3) reaction: the hexadecyl bromine that in reaction kettle, adds 40 mass parts; Stirred 35 minutes; The oxyethane that adds 1000 mass parts then, reaction process divide two stages, and the fs is to be reaction 1 hour under 55 ℃ the situation in temperature; Subordinate phase is to be reaction 2.5 hours under 70 ℃ the situation in temperature, and reaction process is carried out time variable control by computingmachine;
4) neutralization: be under 50 ℃ the situation in temperature, the pH value that uses the acetum of 400 mass parts to adjust above-mentioned gained solution is 7, in the time be 0.6 hour;
5) flash liberation: gained solution in the aforesaid reaction vessel is carried out flash liberation, use the spiral pump convey materials, separate with the horizontal spiral separating machine, solid materials gets into the washing still, and evaporation gets into reaction kettle to liquid solvent through the solvent evaporation device, recycles;
6) washing: in the washing still, the fixedly material in the step 5) is washing 1.5 hours under 30 ℃ the situation in temperature;
7) secondary separation: the solution that will wash in the still carries out secondary separation, uses the spiral pump convey materials, separates with the horizontal spiral separating machine, and solid materials gets into the washing still, and evaporation gets into the washing still to liquid solvent through the solvent evaporation device, recycles.
8) drying, packing.
Embodiment 6:
1) pulverize: the natural refined cellulose that will become bag is got 1000 mass parts through opening bag, pulverizes with rotating knife formula kibbler, separates through cyclonic separator, reaches 0.03-0.15mm (about 80 orders), and tail gas is through bag-type dusting;
2) alkalization: in reaction kettle, add the aqueous isopropanol of 8000 mass parts, stir, add the sheet alkali of 260 mass parts, be warmed up to 55 ℃ of cholines, choline cools to normal temperature after finishing, and adds above-mentioned refined cellulose, is alkalization 0.6 hour under 30 ℃ the situation in temperature;
3) reaction: the tetradecyl bromine that in reaction kettle, adds 35 mass parts; Stirred 45 minutes; The oxyethane that adds 1000 mass parts then, reaction process divide two stages, and the fs is to be reaction 1.5 hours under 50 ℃ the situation in temperature; Subordinate phase is under the situation of 80 ℃ of temperature, to react 2.0 hours, and reaction process is carried out time variable control by computingmachine;
4) neutralization: be under 50 ℃ the situation in temperature, the pH value that uses the hydrochloric acid soln of 350 mass parts to adjust above-mentioned gained solution is 8, in the time be 0.8 hour;
5) flash liberation: gained solution in the aforesaid reaction vessel is carried out flash liberation, use the spiral pump convey materials, separate with the horizontal spiral separating machine, solid materials gets into the washing still, and evaporation gets into reaction kettle to liquid solvent through the solvent evaporation device, recycles;
6) washing: in the washing still, the fixedly material in the step 5) is washing 1 hour under 35 ℃ the situation in temperature;
7) secondary separation: the solution that will wash in the still carries out secondary separation, uses the spiral pump convey materials, separates with the horizontal spiral separating machine, and solid materials gets into the washing still, and evaporation gets into the washing still to liquid solvent through the solvent evaporation device, recycles.
8) drying, packing.
Embodiment 7:
1) pulverize: the natural refined cellulose that will become bag is got 1000 mass parts through opening bag, pulverizes with rotating knife formula kibbler, separates through cyclonic separator, reaches 0.03-0.15mm (about 80 orders), and tail gas is through bag-type dusting;
2) alkalization: in reaction kettle, add the n-propyl alcohol solution of 9000 mass parts, stir, add the sheet alkali of 280 mass parts, be warmed up to 60 ℃ of cholines, choline cools to normal temperature after finishing, and adds above-mentioned refined cellulose, is alkalization 0.8 hour under 25 ℃ the situation in temperature;
3) reaction: the hexadecyl bromine that in reaction kettle, adds 20 mass parts; Stirred 60 minutes; The oxyethane that adds 1000 mass parts then, reaction process divide two stages, and the fs is to be reaction 1.2 hours under 60 ℃ the situation in temperature; Subordinate phase is to be reaction 1.5 hours under 70 ℃ the situation in temperature, and reaction process is carried out time variable control by computingmachine;
4) neutralization: be under 60 ℃ the situation in temperature, the pH value that uses the acetum of 400 mass parts to adjust above-mentioned gained solution is 8.5, in the time be 1 hour;
5) flash liberation: gained solution in the aforesaid reaction vessel is carried out flash liberation, use the spiral pump convey materials, separate with the horizontal spiral separating machine, solid materials gets into the washing still, and evaporation gets into reaction kettle to liquid solvent through the solvent evaporation device, recycles;
6) washing: in the washing still, the fixedly material in the step 5) is washing 2 hours under 20 ℃ the situation in temperature;
7) secondary separation: the solution that will wash in the still carries out secondary separation, uses the spiral pump convey materials, separates with the horizontal spiral separating machine, and solid materials gets into the washing still, and evaporation gets into the washing still to liquid solvent through the solvent evaporation device, recycles.
8) drying, packing.
Embodiment 8:
1) pulverize: the natural refined cellulose that will become bag is got 1000 mass parts through opening bag, pulverizes with rotating knife formula kibbler, separates through cyclonic separator, reaches 0.03-0.15mm (about 80 orders), and tail gas is through bag-type dusting;
2) alkalization: in reaction kettle, add the aqueous isopropanol of 5000 mass parts, stir, add the sheet alkali of 250 mass parts, be warmed up to 60 ℃ of cholines, choline cools to normal temperature after finishing, and adds above-mentioned refined cellulose, is alkalization 1 hour under 30 ℃ the situation in temperature;
3) reaction: the tetradecyl bromine that in reaction kettle, adds 40 mass parts; Stirred 40 minutes; The oxyethane that adds 1000 mass parts then, reaction process divide two stages, and the fs is to be reaction 1 hour under 55 ℃ the situation in temperature; Subordinate phase is to be reaction 4 hours under 70 ℃ the situation in temperature, and reaction process is carried out time variable control by computingmachine;
4) neutralization: be under 40 ℃ the situation in temperature, the pH value that uses the oxalic acid solution of 400 mass parts to adjust above-mentioned gained solution is 6, in the time be 0.8 hour;
5) flash liberation: gained solution in the aforesaid reaction vessel is carried out flash liberation, use the spiral pump convey materials, separate with the horizontal spiral separating machine, solid materials gets into the washing still, and evaporation gets into reaction kettle to liquid solvent through the solvent evaporation device, recycles;
6) washing: in the washing still, the fixedly material in the step 5) is washing 1.5 hours under 30 ℃ the situation in temperature;
7) secondary separation: the solution that will wash in the still carries out secondary separation, uses the spiral pump convey materials, separates with the horizontal spiral separating machine, and solid materials gets into the washing still, and evaporation gets into the washing still to liquid solvent through the solvent evaporation device, recycles.
8) drying, packing.
Embodiment 9:
1) pulverize: the natural refined cellulose that will become bag is got 1000 mass parts through opening bag, pulverizes with rotating knife formula kibbler, separates through cyclonic separator, reaches 0.03-0.15mm (about 80 orders), and tail gas is through bag-type dusting;
2) alkalization: in reaction kettle, add the isobutanol solution of 10000 mass parts, stir, add the sheet alkali of 280 mass parts; Be warmed up to 70 ℃ of cholines; Cooling to normal temperature after choline finishes, add above-mentioned refined cellulose, is alkalization 0.5 hour under 15 ℃ the situation in temperature;
3) reaction: the lauryl bromide that in reaction kettle, adds 50 mass parts; Stirred 30 minutes; The oxyethane that adds 1000 mass parts then, reaction process divide two stages, and the fs is to be reaction 3.5 hours under 50 ℃ the situation in temperature; Subordinate phase is to be reaction 0.8 hour under 65 ℃ the situation in temperature, and reaction process is carried out time variable control by computingmachine;
4) neutralization: be under 50 ℃ the situation in temperature, the pH value that uses the phosphoric acid solution of 400 mass parts to adjust above-mentioned gained solution is 7, in the time be 0.6 hour;
5) flash liberation: gained solution in the aforesaid reaction vessel is carried out flash liberation, use the spiral pump convey materials, separate with the horizontal spiral separating machine, solid materials gets into the washing still, and evaporation gets into reaction kettle to liquid solvent through the solvent evaporation device, recycles;
6) washing: in the washing still, the fixedly material in the step 5) is washing 1.5 hours under 30 ℃ the situation in temperature;
7) secondary separation: the solution that will wash in the still carries out secondary separation, uses the spiral pump convey materials, separates with the horizontal spiral separating machine, and solid materials gets into the washing still, and evaporation gets into the washing still to liquid solvent through the solvent evaporation device, recycles.
8) drying, packing.
Embodiment 10:
1) pulverize: the natural refined cellulose that will become bag is got 1000 mass parts through opening bag, pulverizes with rotating knife formula kibbler, separates through cyclonic separator, reaches 0.03-0.15mm (about 80 orders), and tail gas is through bag-type dusting;
2) alkalization: in reaction kettle, add the aqueous isopropanol of 10000 mass parts, stir, add the sheet alkali of 200 mass parts, be warmed up to 65 ℃ of cholines, choline cools to normal temperature after finishing, and adds above-mentioned refined cellulose, is alkalization 1 hour under 20 ℃ the situation in temperature;
3) reaction: the hexadecyl bromine that in reaction kettle, adds 40 mass parts; Stirred 40 minutes; The oxyethane that adds 1200 mass parts then, reaction process divide two stages, and the fs is to be reaction 1 hour under 50 ℃ the situation in temperature; Subordinate phase is to be reaction 0.8 hour under 70 ℃ the situation in temperature, and reaction process is carried out time variable control by computingmachine;
4) neutralization: be under 45 ℃ the situation in temperature, the pH value that uses the acetum of 450 mass parts to adjust above-mentioned gained solution is 7, in the time be 0.6 hour;
5) flash liberation: gained solution in the aforesaid reaction vessel is carried out flash liberation, use the spiral pump convey materials, separate with the horizontal spiral separating machine, solid materials gets into the washing still, and evaporation gets into reaction kettle to liquid solvent through the solvent evaporation device, recycles;
6) washing: in the washing still, the fixedly material in the step 5) is washing 1.5 hours under 30 ℃ the situation in temperature;
7) secondary separation: the solution that will wash in the still carries out secondary separation, uses the spiral pump convey materials, separates with the horizontal spiral separating machine, and solid materials gets into the washing still, and evaporation gets into the washing still to liquid solvent through the solvent evaporation device, recycles.
8) drying, packing.
The leading indicator that product reaches:
Total substitution value: 1.8-2.5 improves 10-20% than present common process, reaches external equal quality level.
Transmittance: 85-90% improves 5-15% than present common process, reaches international best level.
Viscosity: NDJ-1 viscosity (2% aqueous solution) 10000-100000mPa.s.
Claims (3)
1. the technology of a high-carbon alkylation modification Natvosol is characterized in that, is realized by following step:
1) pulverize: the refined cellulose of getting 1000 mass parts is pulverized, is separated, and the refined cellulose length after the pulverizing reaches 0.03-0.15mm, tails dedusting;
2) alkalization: in reaction kettle, add the alcoholic solution of 5000-12000 mass parts, stir, add the sheet alkali of 200-280 mass parts; Be warmed up to 50-70 ℃ of choline; Cooling to normal temperature after choline finishes, add above-mentioned refined cellulose, is alkalization 0.5-1.5 hour under 15-35 ℃ the situation in temperature;
3) reaction: the high-carbon alkyl bromide that in reaction kettle, adds the 10-50 mass parts; Described high-carbon alkyl bromide is lauryl bromide, tetradecyl bromine or hexadecyl bromine, stirs 30-60 minute, adds the oxyethane of 900-1300 mass parts then; Reaction process is divided two stages; Fs is to be reaction 0.5-3.5 hour under 50-60 ℃ the situation in temperature, and subordinate phase is to be reaction 0.5-4 hour under 65-80 ℃ the situation in temperature, and reaction process is carried out time variable control by computingmachine;
4) neutralization: be under 40-60 ℃ the situation in temperature, the pH value that uses the acid solution of 300-500 mass parts to adjust above-mentioned gained solution is 5.5-8.5, in and the time be 0.5-1 hour;
5) flash liberation: the outstanding liquid that mixes of gained in the aforesaid reaction vessel is carried out flash liberation, and solid materials Natvosol product gets into the washing still, and evaporation gets into reaction kettle to liquid solvent through the solvent evaporation device, recycles;
6) washing: in the washing still, the solid materials Natvosol product in the step 5) is washing 1-2 hour under 20-35 ℃ the situation in temperature;
7) secondary separation: the outstanding liquid that mixes that will wash in the still carries out secondary separation, and solid materials Natvosol product gets into the washing still, and evaporation gets into the washing still to liquid solvent through the solvent evaporation device, recycles;
8) drying, packing.
2. the technology of high-carbon alkylation modification Natvosol according to claim 1 is characterized in that, described alcoholic solution is aqueous isopropanol, n-propyl alcohol solution, isobutanol solution or butanol solution.
3. the technology of high-carbon alkylation modification Natvosol according to claim 1 is characterized in that, described acid solution is hydrochloric acid soln, oxalic acid solution, acetum or phosphoric acid solution.
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| CN107266703B (en) * | 2017-05-25 | 2020-08-18 | 华南理工大学 | Method for synthesizing micro-diplopore HKUST-1 material in lamella at normal temperature by using neutral template agent |
| CN107964048A (en) * | 2018-01-04 | 2018-04-27 | 泸州北方化学工业有限公司 | A kind of coating process of hydrophobic associated ethoxyl cellulose |
| CN115716881A (en) * | 2022-11-28 | 2023-02-28 | 泸州北方纤维素有限公司 | Hydrophobically modified hydroxyethyl cellulose and its preparation method |
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| CN1032796A (en) * | 1987-09-17 | 1989-05-10 | 阿奎龙公司 | Natvosol of carboxymethyl hydrophobically modified (CMHMHEC) and the application in protective coating compositions thereof |
| EP0566911A1 (en) * | 1992-04-20 | 1993-10-27 | Aqualon Company | Improved leveling aqueous coating compositions |
| CN101177261A (en) * | 2007-11-08 | 2008-05-14 | 上海交通大学 | Preparation method of biocompatible cellulose functionalized carbon nanotubes |
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| CN1032796A (en) * | 1987-09-17 | 1989-05-10 | 阿奎龙公司 | Natvosol of carboxymethyl hydrophobically modified (CMHMHEC) and the application in protective coating compositions thereof |
| EP0566911A1 (en) * | 1992-04-20 | 1993-10-27 | Aqualon Company | Improved leveling aqueous coating compositions |
| CN101177261A (en) * | 2007-11-08 | 2008-05-14 | 上海交通大学 | Preparation method of biocompatible cellulose functionalized carbon nanotubes |
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