CN100543037C - The preparation method of hydrophobic modified cation cellulose ether - Google Patents
The preparation method of hydrophobic modified cation cellulose ether Download PDFInfo
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- CN100543037C CN100543037C CNB2006101225722A CN200610122572A CN100543037C CN 100543037 C CN100543037 C CN 100543037C CN B2006101225722 A CNB2006101225722 A CN B2006101225722A CN 200610122572 A CN200610122572 A CN 200610122572A CN 100543037 C CN100543037 C CN 100543037C
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Abstract
The present invention relates to the preparation method of hydrophobic modified cation cellulose ether, be a kind of preparation method of ether of cellulose of high-cation substitution value of modification, it discloses ether of cellulose at first under stirring condition, carry out dry process reaction with dewatered modified cation reagent after, the gained mixture adds organic solvent and carries out Wet Method Reaction with dewatered modified cation reagent again, solvent wash after filtration,, filter, drying obtains the method for the hydrophobic modified cation cellulose ether of high substitution value after the screening.This method can improve the positively charged ion substitution value, makes the product of making have good flexibility, conditioning property, and moisture-keeping functions is easy to functions such as rinsing, and synthesis technique is simple, and raw material consumption is reasonable, and cost reduces relatively, save energy.
Description
Technical field
The present invention relates to a kind of method of water-soluble high-molecular compound modification, the preparation method of the ether of cellulose of the high-cation substitution value of a kind of modification specifically.
Background technology
Hydrophobic modified cation cellulose ether is a kind of cation type water-soluble polymer compound, it has flexibility, conditioning property, moisture-keeping functions, and rinsing easily, can on hair, not produce accumulative effect, it has the dual-use function of ether of cellulose and cats product concurrently, be a kind of raw material that has characteristic in the cosmetics production, be widely used in the production of producing hair conditioner, shampoo and makeup.Use the synthetic method of cation cellulose ether in the past, the positively charged ion substitution value of product only has 0.3, and the water-soluble polymer polyquaternium that WO 98/18434 uses in producing, its cationization degree is too high, and adsorptivity is too strong, and rinsing performance is poor, storage effect is serious, life-time service can remain in hair surface in a large number, causes hair heavy, has influenced the effect of hairdressing hair washing.Hydrophobic modified cation cellulose ether in the past is dewatered modified cation group substitution value low (US 4228277) in the preparation, cause product hydrophobically modified DeGrain, influence the use of product, also have also same as above similar of the CN200510102381.5 effect of Wet Method Reaction.Use wet method secondary reaction method, the reaction process complexity, raw material consumption amount height is not suitable for production operation (WO 01/48021).
Summary of the invention
The preparation method who the purpose of this invention is to provide hydrophobic modified cation cellulose ether, it carries out Wet Method Reaction after adopting dry process reaction again, can improve the positively charged ion substitution value, makes the product of making have good flexibility, conditioning property, moisture-keeping functions is easy to functions such as rinsing, and synthesis technique is simple, raw material consumption is reasonable, cost reduces relatively, and save energy is convenient to promote and use.
Technical solution of the present invention is:
A, under the agitation condition of normal temperature and pressure and inert gas environment, with the ether of cellulose add-on is 1, ether of cellulose is added alkali metal hydroxide or metal oxide 0.005～0.08, dewatered modified cation reagent 0.1～1.2,30～80 ℃ of down reactions 80～100 minutes, obtain mixing solutions through the hydrophobic modified cation cellulose ether of the part substitution value of dried preparation;
B, A is reacted products therefrom under whipped state, add solvent 3～8, alkali metal hydroxide or metal oxide 0.01～0.10, temperature is controlled at 50～120 ℃, add dewatered modified cation reagent 0.1～1.2 again, reacted 80～100 minutes, and obtained mixing solutions through the hydrophobic modified cation cellulose ether of the high substitution value of wet method preparation;
C, the B reaction product removed after filtration desolvate, after the dissolved dose of washing, filter again, drying, screening promptly gets hydrophobic modified cation cellulose ether.
The above employed ether of cellulose of the present invention is to be a kind of moulding high molecular polymer that narrows that raw material makes through chemical modification with the natural fiber, it has a kind of structure of saccharan, in the structure of this saccharan, have more oh group with reactive behavior, it is selected from TYLOSE 30000, hydroxyethyl ether cellulose, carboxymethyl hydroxyethyl cellulose ether, hydroxypropylcelluloether ether, carboxymethyl hydroxypropyl cellulose ether, hydroxybutyl cellulose ether, or carboxymethyl hydroxybutyl cellulose ether.
Temperature in the A reaction of the present invention is 40～60 ℃, and the temperature in the B reaction is 60～80 ℃.
More than A of the present invention reaction add dewatered modified cation reagent 0.3～0.8, the B reaction adds dewatered modified cation reagent 0.3～0.8, dewatered modified cation reagent is that alkyl replaces nitrogen compound, has following structure:
R wherein
1Be C
8-C
14Alkyl, epoxy group(ing);
R
2Be H or C
1-C
14Alkyl;
R
3Be C
1-C
14Alkyl, aryl;
R
4Be H or C
1-C
14Alkyl, epoxide group.
The above B reaction adds solvent 4～6, and employed solvent is ethanol, Virahol, n-propyl alcohol, butanols, octanol, acetone, butanone, methylethylketone, pimelinketone or methyl iso-butyl ketone (MIBK).
Add alkali metal hydroxide or metal oxide 0.01～0.05 in the A reaction of the present invention, add alkali metal hydroxide or metal oxide 0.04～0.06, the magnesium oxide of the lithium hydroxide of employed alkali metal hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, hydrated barta or metal oxide, stannic oxide, zinc oxide, cupric oxide, zirconium white, nickel oxide in the B reaction.
More than step C of the present invention at normal temperatures behind the solvent wash, add stablizer 0.005～0.13.
More than the stablizer 0.015～0.09 of adding of the present invention, employed stablizer be formic acid, acetate, propionic acid, butyric acid, succsinic acid, formic acid, phenylformic acid, formaldehyde, acetaldehyde, oxalic dialdehyde, glutaraldehyde or phenyl aldehyde.
The particle diameter of the hydrophobic modified cation cellulose ether that finally obtains of the present invention is 5～100 μ m, and the positively charged ion substitution value of hydrophobic modified cation cellulose ether is 0.7～0.9.
Principle of work of the present invention is that preparation high-cation substitution value hydrophobic modified cation cellulose ether is to be raw material with dewatered modified cation reagent, the first step is even with ether of cellulose and dewatered modified cation reagent mix, under alkali metal hydroxide or metal oxide effect, react, obtain mixing solutions through the hydrophobic modified cation cellulose ether of the part substitution value of dried preparation, the reaction back adds organic solvent, add dewatered modified cation reagent again, under alkali metal hydroxide or metal oxide effect, carry out the reaction of second step, obtain mixing solutions after the reaction through the hydrophobic modified cation cellulose ether of the high substitution value of wet method preparation, mixing solutions after filtration, the viscosity stability that adds stablizer maintenance product, water dissolution stability, stability in storage, washing then, drying obtains finished product.
Advantage of the present invention is to carry out Wet Method Reaction again after adopting dry process reaction, and can improve the positively charged ion substitution value, makes the product of making have good flexibility, conditioning property, moisture-keeping functions is easy to functions such as rinsing, and synthesis technique is simple, raw material consumption is reasonable, and cost reduces relatively, save energy.
Embodiment
Embodiment 1
Having the 1000ml four-hole glass reaction flask internal reaction of stirring, thermometer, nitrogen tube, heating unit:
A, adding 100g hydroxyethyl ether cellulose (H300YP2, Clariate), open and stir, lead to nitrogen, slowly drip the sodium hydroxide solution (sky sky, Guangzhou) of 26.6g25%, stirred 30 minutes, add the dewatered modified cation reagent of 47g70%, stirred 30 minutes, be warmed up to 50 ℃, reacted 90 minutes, and obtained hydrophobic modified cation cellulose ether through dried preparation;
B, A reaction product add 85% solvent Virahol 500g, add 15.5g 25% sodium hydroxide solution, stirred 30 minutes, be warmed up to 60 ℃, the dewatered modified cation reagent that adds 52.8g 70%, reacted 90 minutes, and obtained mixing solutions through the hydrophobic modified cation cellulose ether of wet method preparation;
After C, the B reaction, vacuum filtration removes and desolvates, use each 500g of solvent Virahol of 88～99% respectively, 45 ℃ of washings four times, after the 4th washing, add 2.3g stablizer oxalic dialdehyde, continue to stir 30 minutes, be cooled to 30 ℃, vacuum filtration, vacuum-drying then, screening, obtain 155g high substitution value dewatered modified cation hydroxyethyl ether cellulose, this product positively charged ion substitution value is 0.81, and viscosity is 435cps.
Employed dewatered modified cation reagent is in above A reaction and the B reaction:
R
1Be epoxypropyl, R
2Be methyl, R
3Be dodecyl, R
4Be methyl.
The preparation method of above dodecyl-dimethyl-epoxypropyl ammonium chloride is: add 213 gram dodecyl-dimethyl tertiary amines in the glass reaction bottle, add 130 gram Virahols, stir, be warmed up to 60 ℃, in 2 hours, be added drop-wise to 96.6 gram epoxy chloropropane in the glass reaction bottle, reacted 3 hours at 60 ℃ after dripping epoxy chloropropane, the unreacted epoxy chloropropane of vacuum removal obtains dodecyl-dimethyl-epoxypropyl ammonium chloride.
Detection method: viscosity: take by weighing 4 gram samples, add 196 gram deionized waters, use the Brookfield-RVT rotational viscosimeter, 3# rotor, 20 rev/mins of rotating speeds 25 ℃ of stirring and dissolving 2 hours.
Substitution value: use Kjeldahl determination testing product nitrogen content, be calculated as follows substitution value by nitrogen content:
A: the nitrogen content that uses the product of Kjeldahl determination detection.
Hydrophobic modified cation cellulose ether detects after making product with following raw material:
Get gained hydrophobic modified cation cellulose ether 0.3g, add EDTA-disodium (Guangzhou chemical reagent work) 0.05g, alcohol ether sodium sulfate (Zhejiang is lucky to be reached) 16g, alkylolamide (German section is peaceful) 2g, sultaine (being bestowed by heaven in Guangzhou) 5g, dihydroxymethyl dimethyl Hai Yin (being bestowed by heaven in Guangzhou) 0.3g, citric acid (Shantou Xi Long) is an amount of, sodium-chlor (Guangdong salt industry) is an amount of, and deionized water is to 100g.Products obtained therefrom carries out viscosity, foam power, and transparence detects, and carries out human body evaluation contrast.
Embodiment 2-7
With embodiment 1, just embodiment 1 each reactive material add-on is adjusted, as shown in table 1 below, and carry out embodiment 1 described various detections with regard to the hydrophobic modified cation cellulose ether of gained:
Embodiment 9
With embodiment 1, just the hydroxyethyl ether cellulose with ether of cellulose changes TYLOSE 30000 into, change the sodium hydroxide of alkali metal hydroxide into lithium hydroxide, the Virahol of solvent changes n-propyl alcohol into, the A temperature of reaction is 40 ℃, the A reaction times is 80 minutes, and the B reaction times is 100 minutes, and carries out the various detections of embodiment 1 with regard to the hydrophobic modified cation cellulose ether of gained.
Embodiment 10
With embodiment 1, just the hydroxyethyl ether cellulose with ether of cellulose changes carboxymethyl hydroxyethyl cellulose ether into, change the sodium hydroxide of alkali metal hydroxide into potassium hydroxide, change the Virahol of solvent into ethanol, the A temperature of reaction is 60 ℃, and the A reaction times is 100 minutes, and the B reaction times is 80 minutes, the oxalic dialdehyde of stablizer changes formic acid into, and carries out the various detections of embodiment 1 with regard to the hydrophobic modified cation cellulose ether of gained.
Embodiment 11
With embodiment 1, just the sodium hydroxide of alkali metal hydroxide is changed into the magnesium oxide of metal oxide, the Virahol of solvent changes acetone into, the A temperature of reaction is 30 ℃, the B temperature of reaction is 120 ℃, do not add the stablizer oxalic dialdehyde, and carry out the various detections of embodiment 1 with regard to the hydrophobic modified cation cellulose ether of gained.
Embodiment 12
With embodiment 1, just employed dewatered modified cation reagent is reacted in the reaction of A portion and B portion and changes into:
R
1, R
2Be methyl, R
3Be benzyl, R
4Be epoxypropyl;
The preparation method of above epoxypropyl-benzyl-dimethyl-ammonium chloride is: add 135 gram benzyl-dimethyl tertiary amines in the glass reaction bottle, add 97 gram Virahols, stir, be warmed up to 60 ℃, in 2 hours, be added drop-wise to 96.6 gram epoxy chloropropane in the glass reaction bottle, reacted 3 hours at 60 ℃ after dripping epoxy chloropropane, the unreacted epoxy chloropropane of vacuum removal obtains epoxypropyl-benzyl-alkyl dimethyl ammonium chloride.
Change the sodium hydroxide of alkali metal hydroxide the stannic oxide of metal oxide into, the Virahol of solvent changes butanone into, and the A temperature of reaction is 80 ℃, and the B temperature of reaction is 80 ℃, and carries out the various detections of embodiment 1 with regard to the hydrophobic modified cation cellulose ether of gained.
Embodiment 13
With embodiment 1, just A reaction and B are reacted employed dewatered modified cation reagent and change into:
R
1, R
2Be ethyl, R
3Be octadecyl, R
4Be epoxypropyl.
The preparation method of above octadecyl-diethyl-epoxypropyl ammonium chloride is: add 325 gram octadecyl-diethyl tertiary amines in the glass reaction bottle, add 178.7 gram Virahols, stir, be warmed up to 60 ℃, in 2 hours, be added drop-wise to 96.6 gram epoxy chloropropane in the glass reaction bottle, reacted 3 hours at 60 ℃ after dripping epoxy chloropropane, the unreacted epoxy chloropropane of vacuum removal obtains octadecyl-diethyl-epoxypropyl ammonium chloride.
The sodium hydroxide of alkali metal hydroxide changes the nickel oxide of metal oxide into, and the Virahol of solvent changes pimelinketone into, and the A temperature of reaction is 50 ℃, and the B temperature of reaction is 60 ℃, and carries out the various detections of embodiment 1 with regard to the hydrophobic modified cation cellulose ether of gained.
Comparative Examples 1
Use one time Wet Method Reaction, reaction unit is identical with embodiment 1.85% isopropanol solvent 500 grams, feed nitrogen, stirred 30 minutes, (H300YP2 Clariate), adds 24.3 grams, 25% sodium hydroxide solution (vast and boundless day of Guangzhou) to add 100 gram hydroxyethyl ether celluloses, stirred 30 minutes, be warmed up to 60 ℃, add the epoxypropyl-dodecyl-alkyl dimethyl ammonium chloride solution of 55.7 grams 70%, reacted 90 minutes.After the reaction, vacuum filtration removes and desolvates.Use each 500 gram of isopropanol solvent of 88-99% respectively, 45 ℃ of washings four times.After the 4th washing, add 2.3 gram oxalic dialdehydes, continue to stir 30 minutes, be cooled to 30 ℃, vacuum filtration, vacuum-drying then, screening obtain 123 gram dewatered modified cation hydroxyethyl ether celluloses, and products therefrom carries out the various detections of embodiment 1.
Table 2 carries out nitrogen content for each hydrophobic surname cation cellulose ether that changes of various embodiments of the present invention and Comparative Examples, viscosity, and weight, the analytical results that particle diameter etc. detect:
| Embodiment | Weight loss on drying (%) | Nitrogen content (%) | The positively charged ion substitution value | Viscosity (2% aqueous solution, cps) | The cation cellulose ether particle diameter, μ m |
| 1 | 3.6 | 1.97 | 0.87 | 412 | 60 |
| 2 | 3.7 | 1.88 | 0.83 | 410 | 5 |
| 3 | 3.5 | 1.93 | 0.85 | 411 | 100 |
| 4 | 3.4 | 1.84 | 0.81 | 413 | 53 |
| 5 | 3.8 | 1.77 | 0.78 | 414 | 80 |
| 6 | 3.6 | 1.81 | 0.80 | 415 | 10 |
| 7 | 3.7 | 1.70 | 0.75 | 411 | 20 |
| 8 | 3.6 | 1.93 | 0.85 | 414 | 50 |
| 9 | 3.4 | 1.59 | 0.70 | 412 | 70 |
| 10 | 3.4 | 1.75 | 0.77 | 413 | 75 |
| 11 | 3.6 | 2.02 | 0.89 | 414 | 65 |
| 12 | 3.5 | 1.63 | 0.72 | 415 | 45 |
| 13 | 3.7 | 1.59 | 0.70 | 413 | 36 |
| Comparative Examples 1 | 2.3 | 0.84 | 0.37 | 450 | 50 |
Table 3 is the viscosity behind the product made of various embodiments of the present invention and Comparative Examples gained ether of cellulose, foam power, and performance detection contrast tables such as transparence:
| Product | Viscosity (cps) | Foam power (mm) | Transparence (%) |
| Embodiment 1 | 6850 | 165 | 93 |
| Embodiment 2 | 6840 | 166 | 94 |
| Embodiment 3 | 6850 | 167 | 93 |
| Embodiment 4 | 6860 | 165 | 94 |
| Embodiment 5 | 6870 | 164 | 95 |
| Embodiment 6 | 6820 | 168 | 92 |
| Embodiment 7 | 6830 | 168 | 93 |
| Embodiment 8 | 6850 | 165 | 94 |
| Embodiment 9 | 6850 | 165 | 95 |
| Embodiment 10 | 6860 | 167 | 96 |
| Embodiment 11 | 6840 | 164 | 93 |
| Embodiment 12 | 6870 | 166 | 92 |
| Embodiment 13 | 6900 | 169 | 93 |
| Comparative Examples 1 | 6620 | 155 | 81 |
Use above each embodiment to make product, product is carried out the following tabulation 4 of contrast of sensory evaluation with aspiration trier 10 people 1 male 9 woman, shown in the table 5, table 6:
Show that by above comparative test result the hydrophobic modified cation cellulose ether that the inventive method prepares gained has good flexibility, conditioning property, moisture-keeping functions is easy to the rinsing function.
Claims (6)
1, the preparation method of hydrophobic modified cation cellulose ether is characterized in that:
A, under the agitation condition of normal temperature and pressure and inert gas environment, with the ether of cellulose add-on is 1, add alkali metal hydroxide or metal oxide 0.005～0.08, dewatered modified cation reagent 0.1～1.2, reacted 80～100 minutes down at 30～80 ℃, obtain the mixing solutions through the hydrophobic modified cation cellulose ether of the part substitution value of dried preparation, dewatered modified cation reagent is that alkyl replaces nitrogen compound, has following structure:
R wherein
1Be C
8-C
14Alkyl, epoxy group(ing);
R
2Be H or C
1-C
14Alkyl;
R
3Be C
1-C
14Alkyl, aryl;
R
4Be H or C
1-C
14Alkyl, epoxide group;
B, A is reacted products therefrom under whipped state, add solvent 3～8, alkali metal hydroxide or metal oxide 0.01～0.10, temperature is controlled at 50～120 ℃, add dewatered modified cation reagent 0.1～1.2 again, reacted 80～100 minutes, and obtained mixing solutions through the hydrophobic modified cation cellulose ether of the high substitution value of wet method preparation;
C, the B reaction product removed after filtration desolvate, after the dissolved dose of washing, filter again, drying, screening promptly gets hydrophobic modified cation cellulose ether.
2, the preparation method of hydrophobic modified cation cellulose ether according to claim 1, it is characterized in that employed ether of cellulose is a TYLOSE 30000, hydroxyethyl ether cellulose, carboxymethyl hydroxyethyl cellulose ether, hydroxypropylcelluloether ether, carboxymethyl hydroxypropyl cellulose ether, hydroxybutyl cellulose ether, or carboxymethyl hydroxybutyl cellulose ether.
3, the preparation method of hydrophobic modified cation cellulose ether according to claim 1 is characterized in that the temperature in the A reaction is 40～60 ℃, and the temperature in the B reaction is 60～80 ℃.
4, the preparation method of hydrophobic modified cation cellulose ether according to claim 1 is characterized in that adding dewatered modified cation reagent 0.3～0.8 in the A reaction, and the B reaction adds dewatered modified cation reagent 0.3～0.8.
5, the preparation method of hydrophobic modified cation cellulose ether according to claim 1, it is characterized in that the B reaction adds solvent 4～6, employed solvent is ethanol, Virahol, n-propyl alcohol, butanols, octanol, acetone, butanone, methylethylketone, pimelinketone or methyl iso-butyl ketone (MIBK).
6, the preparation method of hydrophobic modified cation cellulose ether according to claim 1, it is characterized in that adding alkali metal hydroxide or metal oxide 0.01～0.05 in the A reaction, add alkali metal hydroxide or metal oxide 0.04～0.06 in the B reaction, employed alkali metal hydroxide is lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide or hydrated barta, and employed metal oxide is magnesium oxide, stannic oxide, zinc oxide, cupric oxide, zirconium white or nickel oxide.
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| CN108864811B (en) * | 2018-08-01 | 2021-05-07 | 佛山市高明绿色德化工有限公司 | Mirror glass ink with good weather resistance and preparation method thereof |
| CN110724205A (en) * | 2019-11-25 | 2020-01-24 | 重庆东寰科技开发有限公司 | Cationic hydroxypropyl methyl cellulose ether and preparation method thereof |
| CN116535528A (en) * | 2022-01-25 | 2023-08-04 | 中国科学院理化技术研究所 | Cationic nanocellulose and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998018434A1 (en) * | 1996-10-25 | 1998-05-07 | The Procter & Gamble Company | Conditioning shampoo compositions containing emulsion polymerized polymers |
| WO2001048021A1 (en) * | 1999-12-29 | 2001-07-05 | Union Carbide Chemicals & Plastics | Highly charged cationic cellulose ethers |
| WO2005058970A1 (en) * | 2003-12-16 | 2005-06-30 | Samsung Fine Chemicals, Co., Ltd. | Method for preparation of fine powdered cellulose ethers |
| CN1789286A (en) * | 2005-12-19 | 2006-06-21 | 华南理工大学 | Modification method of cellulose ether product |
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2006
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998018434A1 (en) * | 1996-10-25 | 1998-05-07 | The Procter & Gamble Company | Conditioning shampoo compositions containing emulsion polymerized polymers |
| WO2001048021A1 (en) * | 1999-12-29 | 2001-07-05 | Union Carbide Chemicals & Plastics | Highly charged cationic cellulose ethers |
| WO2005058970A1 (en) * | 2003-12-16 | 2005-06-30 | Samsung Fine Chemicals, Co., Ltd. | Method for preparation of fine powdered cellulose ethers |
| CN1789286A (en) * | 2005-12-19 | 2006-06-21 | 华南理工大学 | Modification method of cellulose ether product |
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