CN1273684C - Application of chitosan of N-(2-hydroxy-3-dimethyl)propyl ammonium chloride - Google Patents
Application of chitosan of N-(2-hydroxy-3-dimethyl)propyl ammonium chloride Download PDFInfo
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- CN1273684C CN1273684C CN 200410012896 CN200410012896A CN1273684C CN 1273684 C CN1273684 C CN 1273684C CN 200410012896 CN200410012896 CN 200410012896 CN 200410012896 A CN200410012896 A CN 200410012896A CN 1273684 C CN1273684 C CN 1273684C
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- ammonium
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- shitosan
- propyl group
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Abstract
The present invention discloses an application by using N-(2-hydroxy-3-trimethyl) propyl ammonium chloride chitosan as an auxiliary papermaking retention and filtration agent. The molecular weight of the N-(2-hydroxy-3-trimethyl) propyl ammonium chloride chitosan is from 30, 000 to 300, 000, and the replacement degree is from 35% to 98%. Chitosan quaternary ammonium salt is used as the auxiliary papermaking retention and filtration agent which has the advantages of little dosage, good performance and convenient use, the running speed of a papermaking machine for neutral paper and alkali paper can be effectively enhanced, the concentration of white water can be decreased, and the sewage pollution is reduced. The chitosan quaternary ammonium salt is used as the auxiliary papermaking retention and filtration agent which has wide application range, can be used for acidic systems, and can be practical for neutral papermaking systems and alkali papermaking systems. Small fiber, soluble and colloidal carbohydrates and mineral filler particles in the non-wood slurry of reed pulp, straw pulp and the like can be well retained.
Description
Technical field
The invention belongs to chemical technology field, relate to of the application of N-(2-hydroxyl-3-chlorination front three ammonium) propyl group shitosan as paper retention and filter aid.
Background technology
Domestic papermaking straw pulp retention and drainage aid agent commonly used at present mainly contains cationic polyacrylamide, cationic starch etc.Shortcomings such as the former is a synthetic high polymer, although price is lower, performance is good, exists degraded difficult, and carrying capacity of environment is big, so the research of natural polymer will become first-selected from now on object with application.Native starch is used for the history of the existing more than one thousand years of paper industry, and its cation-modified thing is widely used in retention agent now, but also has some defectives, as consumption is big, operation is loaded down with trivial details, retention and drainage effect is not satisfactory, exists bigger expanding space.Shitosan compare with starch, and the active force between cellulosic substrate is bigger owing to chemical constitution, configuration and cellulose and similar, and the mechanical property and the paper machine running speed that cause into paper all have bigger improvement.Studies show that it in a large number under acid condition, use as paper making additive (as reinforcing agent, retention and drainage aid agent, sewage-treating agent etc.), but along with papermaking systems by acidity in, alkaline direction remodeling, placed restrictions on the use of shitosan.
Summary of the invention
The invention provides problem to be solved and provide of the application of N-(2-hydroxyl-3-chlorination front three ammonium) propyl group shitosan as paper retention and filter aid, this chitosan quaternary ammonium salt assitant is little as the use amount of paper retention and filter aid, easy to use, paper machine operation speed in effectively improving, in the alkaline paper-making, reduce white water consistency, alleviate sewage pollution.
Technical scheme provided by the invention is: N-(2-hydroxyl-3-chlorination front three ammonium) propyl group shitosan is as the application of paper retention and filter aid.
The molecular weight of described N-(2-hydroxyl-3-chlorination front three ammonium) propyl group shitosan is 30,000-300,000, and substitution value is 35%-98%.
N-(2-hydroxyl-3-chlorination front three ammonium) propyl group shitosan is made by laxative remedy: (1) cationic substituent: under pH=8.5-9.5 with trimethylamine hydrochloride and epoxychloropropane by 1: 1 to 1.3: 1 molar ratio hybrid reaction 1-3 hour, obtain cationic intermediates behind the reduction vaporization; (2) preparation of chitosan quaternary ammonium salt: by cationic intermediates and 4: 1 to 10: 1 molar ratio of shitosan, above-mentioned cationic intermediates is joined in the aqueous suspension of shitosan of 1-1.5wt%, in 60-85 ℃, reaction is 4-8 hour under the pH=9-10 condition, take out the crude product ultrafiltration, concentrate the back and after 80-120 ℃ of vacuumize, promptly obtain N-(2-hydroxyl-3-chlorination front three ammonium) propyl group shitosan.
The synthetic route of N-(2-hydroxyl-3-chlorination front three ammonium) propyl group shitosan:
The present invention also provides above-mentioned N-(2-hydroxyl-3-chlorination front three ammonium) propyl group shitosan to be used for the embodiment of paper making wet part additive: attach order and be slurry---auxiliary agent---filler grain.It promptly is the non-wood pulp material (beating degree: 35-75 of 7-9 at PH
0SR) (molecular weight is 30,000-300,000 to the propyl group shitosan to add relative quantity in and be the N-(2-hydroxyl-3-chlorination front three ammonium) of 1.8-12.6mg/g oven dry stock, substitution value is 35-98%) aqueous solution, after stirring, add the 1-6wt%CaCO that solid content is the 10-20wt% of oven dry stock
3Turbid liquid.The retention of fiber fines and hemicellulose can improve 15%-50%, CaCO when not adding this auxiliary agent
3Retention reach 30-80%,
0The SR value can improve 10-25%.
The present invention will introduce cation radical in the chitosan molecule, as trimethyl hydroxypropyl ammonium, can make shitosan in, water-soluble under the alkali condition, satisfy demand transition of paper industry.Simultaneously, chitosan quaternary ammonium salt has high positive electricity, can produce electrostatic interaction with the carboxyl negative charge on the cellulose, has further strengthened the active force of the two, improves the retention of fiber fines, filler grain greatly, reduces white water consistency.As paper retention and filter aid, its use amount is little with chitosan quaternary ammonium salt in the present invention, and performance is excellent, and is easy to use, and paper machine operation speed in effectively improving, in the alkaline paper-making reduces white water consistency, alleviates sewage pollution.Chitosan quaternary ammonium salt is suitable for face width as paper retention and filter aid, can be used for acid system, and especially centering, alkaline paper-making system more have practical value.Fiber fines in the non-wood pulp material such as reed pulp, straw pulp and dissolubility, colloid shape carbohydrate and inorganic filler particle had well keep.
The specific embodiment
Embodiment 1: at 4 ℃ 0.5mol hydrochloric acid is added drop-wise in the 0.5mol trimethylamine solution, is heated to 30 ℃ after mixing, add epoxychloropropane 0.42mol, stir, to the solution of 50 ℃ of Dropwise 5 0ml 40% in 1-1.5 hour, keep the pH=9 of mixed solution, continue reaction 2.5 hours.Afterwards this reactant mixture is moved in the decompression evaporator, evaporation 30min (40 ℃, vacuum is 0.09MPa) promptly gets cationic intermediates.Be that 200,000 shitosan, 12 grams join in the above-mentioned midbody solution then with molecular weight, regulating pH is 9, stir, keep reaction 6 hours at 75 ℃, promptly get thick product shitosan quaternary amine, with its ultrafiltration, concentrating in 100 ℃ of vacuumizes, to get molecular weight be that 190,000 substitution values are 90% N-(2-hydroxyl-3-chlorination front three ammonium) propyl group shitosan.
Embodiment 2: with molecular weight 11 * 10
4, substitution value is that 93% N-(2-hydroxyl-3-chlorination front three ammonium) propyl group shitosan is mixed with the aqueous solution, joining beating degree is 43
0In the reed pulp material of SR, after slight, of short duration stirring, add the CaCO of relative dry pulp 20%
3(average grain diameter: 2.69 μ m, specific area: 41684cm
2/ g) turbid liquid (3%) is copied sheet again after stirring.Through the analysis of dialogue water sample, CaCO when the metering of N-(2-hydroxyl-3-chlorination front three ammonium) propyl group shitosan is the 0.54mg/g dry pulp
3Retention is 51%.The retention of the carbon water thing of fiber fines and dissolubility colloid shape is 42%.
Embodiment 3: molecular weight is 11 * 10
4, substitution value is that 93% N-(2-hydroxyl-3-chlorination front three ammonium) propyl group shitosan is made the aqueous solution, joins beating degree 54-56
0In the reed pulp material of SR, when the propyl group chitosan dosage was the 6.7mg/g dry pulp, its water filtering performance improved 20-25% at N-(2-hydroxyl-3-chlorination front three ammonium).
Embodiment 4: with molecular weight is 4.8 * 10
4, substitution value is that 93% N-(2-hydroxyl-3-chlorination front three ammonium) propyl group shitosan is mixed with the aqueous solution, joining beating degree is 54-56
0SR, pH are in the reed pulp material of 7-8, and when the propyl ammonium chloride chitosan dosage was the 5.4mg/g dry pulp, water filtering performance improved 20-25% at N-(2 hydroxyl 3-trimethyl).
Embodiment 5: with molecular weight is 20 * 10
4, substitution value is that 63% N-(2-hydroxyl-3-chlorination front three ammonium) propyl group shitosan is water-soluble, joining pH is that 7-8, beating degree are 43
0In the straw slurry of SR, after slight, of short duration stirring, add the heavy CaCO of relative oven dry stock 20%
3(average grain diameter: 2.69 μ m, specific area: 41684cm
2/ g) turbid liquid (3%) is copied sheet then.When N-(2-hydroxyl-3-chlorination front three ammonium) propyl group chitosan dosage be oven dry stock 0.54% the time, the retention of calcium carbonate improves 61%, the retention of the carbon water thing of fiber fines and dissolubility colloid shape improves 45%.
Embodiment 6: with molecular weight 20 * 10
4, substitution value is that 43% N-(2-hydroxyl-3-chlorination front three ammonium) propyl group shitosan is water-soluble, joining pH is that 7-8, beating degree are 43
0In the reed pulp material of SR, after slight, of short duration stirring, add the heavy CaCO of relative oven dry stock 20%
3(average grain diameter: 2.69 μ m, specific area: 41684cm
2/ g) turbid liquid (3%) is copied sheet then.When N-(2-hydroxyl-3-chlorination front three ammonium) propyl group chitosan dosage be oven dry stock 1% the time, the retention of calcium carbonate improves 50.5%, the retention of the carbon water thing of fiber fines and dissolubility colloid shape improves 31%.
Claims (4)
1.N-(2-hydroxyl-3-chlorination front three ammonium) propyl group shitosan is as the application of paper retention and filter aid.
2. application according to claim 1 is characterized in that: the molecular weight of described N-(2-hydroxyl-3-chlorination front three ammonium) propyl group shitosan is 30,000-300,000, and substitution value is 35%--98%.
3. application according to claim 2, it is characterized in that: N-(2-hydroxyl-3-chlorination front three ammonium) propyl group shitosan is made by laxative remedy: (1) cationic substituent: under pH=8.5-9.5 with trimethylamine hydrochloride and epoxychloropropane by 1: 1 to 1.3: 1 molar ratio hybrid reaction 1-3 hour, obtain cationic intermediates behind the reduction vaporization; (2) preparation of chitosan quaternary ammonium salt: by cationic intermediates and 4: 1 to 10: 1 molar ratio of shitosan, above-mentioned cationic intermediates is joined in the aqueous suspension of shitosan of 1-1.5wt%, in 60--85 ℃, reaction is 4-8 hour under the pH=9-10 condition, take out the crude product ultrafiltration, concentrate the back and after 80-120 ℃ of vacuumize, promptly obtain N-(2-hydroxyl-3-chlorination front three ammonium) propyl group shitosan.
4. according to claim 1 or 2 or 3 described application, it is characterized in that: at PH is that 7-9, beating degree are that to add relative quantity in the wheat slurry of 35-75 ° of SR or the reed pulp slurry be N-(2-hydroxyl-3-chlorination front three ammonium) the propyl group chitosan aqueous solution of 1.8-12.6mg/g oven dry stock, adds the 1-6wt%CaCO that solid content is the 10-20wt% of oven dry stock after stirring
3Turbid liquid; The molecular weight of used N-(2-hydroxyl-3-chlorination front three ammonium) propyl group shitosan is 30,000-300,000, and substitution value is 35-98%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410012896 CN1273684C (en) | 2004-03-25 | 2004-03-25 | Application of chitosan of N-(2-hydroxy-3-dimethyl)propyl ammonium chloride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410012896 CN1273684C (en) | 2004-03-25 | 2004-03-25 | Application of chitosan of N-(2-hydroxy-3-dimethyl)propyl ammonium chloride |
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| Publication Number | Publication Date |
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| CN1563573A CN1563573A (en) | 2005-01-12 |
| CN1273684C true CN1273684C (en) | 2006-09-06 |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101857734B (en) * | 2010-06-23 | 2012-09-05 | 牡丹江恒丰纸业股份有限公司 | Composition and method for preparing modified calcium carbonate |
| CN103510428B (en) * | 2013-10-22 | 2015-10-28 | 大连工业大学 | The application of a kind of chitosan quaternary ammonium salt in regenerated papermaking |
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