CN115716881A - Hydrophobically modified hydroxyethyl cellulose and preparation method thereof - Google Patents
Hydrophobically modified hydroxyethyl cellulose and preparation method thereof Download PDFInfo
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- CN115716881A CN115716881A CN202211498830.2A CN202211498830A CN115716881A CN 115716881 A CN115716881 A CN 115716881A CN 202211498830 A CN202211498830 A CN 202211498830A CN 115716881 A CN115716881 A CN 115716881A
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Abstract
The invention discloses hydrophobically modified hydroxyethyl cellulose and a preparation method thereof, belonging to the field of polymer chemistry. The preparation method of the hydrophobically modified hydroxyethyl cellulose comprises the following steps: a. mixing sodium hydroxide with a mixed solvent, fully dissolving alkali, and cooling; b. mixing the solution treated in the step a with refined cotton powder, and alkalizing under the protection of inert gas; c. c, adding a hydrophobic modifier into the solution treated in the step b, carrying out hydrophobic modification reaction, and cooling; d. and d, adding ethylene oxide into the solution treated in the step c for etherification reaction, cooling to obtain a crude product, and neutralizing, separating, washing and drying the crude product to obtain the hydrophobically modified hydroxyethyl cellulose. According to the technical scheme, the hydrophobically modified hydroxyethyl cellulose with unique properties of hydroxyethyl cellulose and hydrophobically associating polymer can be prepared, and the substitution degree and substitution uniformity of the hydrophobically modified group can be effectively improved, so that the application performance of the product in the water-based multicolor paint is improved.
Description
Technical Field
The invention belongs to the field of polymer chemistry, and particularly relates to hydrophobically modified hydroxyethyl cellulose and a preparation method thereof.
Background
The water-based multicolor paint replaces the traditional emulsion paint with excellent water resistance, color adjustability, cracking resistance, weather resistance and other properties. However, the waterborne multicolor coatings have a relatively high technical content due to their relatively late development. The existing water-based colorful paint on the market still faces many problems, such as poor storage stability, and the traditional construction process is generally coated with common real stone paint, texture paint or common exterior wall emulsion paint, which causes the constructed paint surface to have poor water resistance, poor alkali resistance, poor scrubbing resistance, poor crack covering capability and poor artificial weather aging resistance. The multicolor paint has a plurality of systems, and the currently widely used system is a hydroxyethyl cellulose special viscosity system. Hydroxyethyl cellulose as an important component of the system has important influence on the properties of the colorful coating, such as color particles, storage and the like. However, in the prior art, hydroxyethyl cellulose is applied to a multicolor paint, which is prone to problems of bleeding, viscosity reduction, whitening and the like, so that the hydroxyethyl cellulose needs to be modified.
The hydrophobically modified hydroxyethyl cellulose (HMHEC) has the properties of hydroxyethyl cellulose (HEC) and the unique performance of hydrophobic groups, and the related documents of the preparation method of the hydrophobic association hydroxyethyl cellulose are few at present, for example, patent CN102219863A discloses a process for high carbon alkylation modified hydroxyethyl cellulose; CN102140337A discloses a hydrophobic association hydroxyethyl cellulose oil displacement agent; CN1560083 discloses a preparation method of hydrophobic association hydroxyethyl cellulose and the like. At present, the main flow is to prepare the hydrophobic association hydroxyethyl cellulose by a method of dripping alkali liquor into hydroxyethyl cellulose for swelling and then adding hydrophobic monomers for hydrophobic association reaction, and the swelling time is longer by the method and is about 24 hours generally; the hydrophobic association reaction time is relatively long, generally about 5-10 h; secondly, the hydrophobic modifier and ethylene oxide are added after refined cotton is alkalized, the temperature is increased to 55 ℃ for reaction for about 1 hour, and then the temperature is increased to 75 ℃ for reaction for about 2.5 hours, so that a hydrophobic modified product is obtained, but the reaction temperature is low, and the reaction activity of long-chain hydrophobic macromolecules is poor under the condition of low temperature, so that the hydrophobic modification reaction effect is influenced.
Disclosure of Invention
The invention aims to solve the technical problem that the existing hydroxyethyl cellulose is easy to cause color bleeding, viscosity reduction and whitening when applied to a multicolor paint.
The technical scheme adopted by the invention for solving the technical problem is as follows: the preparation method of the hydrophobically modified hydroxyethyl cellulose comprises the following steps:
a. mixing sodium hydroxide with the mixed solvent A, controlling the alkali concentration in the mixed solution to be 35-40%, fully dissolving alkali and cooling;
b. mixing the solution treated in the step a with refined cotton powder, and alkalizing at 15-25 ℃ under the protection of inert gas;
c. c, adding a hydrophobic modifier into the solution treated in the step b, carrying out hydrophobic modification reaction at high temperature, and cooling after the reaction is finished;
d. and c, adding ethylene oxide into the solution treated in the step c for etherification reaction, cooling to obtain a hydrophobic modified hydroxyethyl cellulose crude product, and neutralizing, separating, washing and drying the crude product to obtain the hydrophobic modified hydroxyethyl cellulose.
In the step a, the mixed solvent A is composed of water and an organic solvent.
Furthermore, the mass fraction of water in the mixed solvent A is 10-15%, and the organic solvent is at least one of C3-C4 alcohols.
Further, the organic solvent is at least one of isopropyl alcohol and t-butyl alcohol.
In the step a, the alkali concentration is a mass concentration.
In the step a, the alkali is dissolved at the temperature of 50-70 ℃ for 0.5-1h under the stirring state, and is cooled to 15-25 ℃ after the alkali dissolution is finished.
In the step b, the mass ratio of the sodium hydroxide to the refined cotton powder is 0.54-1: 1, and the mass ratio of the refined cotton powder to the organic mixed solvent is 1: 10.
Further, the grain size of the refined cotton powder is 20-100 meshes.
In the step b, the alkalization time is 1-1.5h.
In the step c, the mole ratio of the hydrophobic modifier to the cellulose glucose unit is 0.02-0.1: 1, and the hydrophobic modifier is a hexadecyl substance.
Further, the hydrophobic modifier is bromohexadecane or epoxyhexadecane.
In the step c, the hydrophobic modification reaction is carried out by uniformly heating to 90-110 ℃, keeping the temperature and reacting for 2-3h, and cooling to below 40 ℃ after the reaction is finished.
In the step d, the mass ratio of the ethylene oxide to the refined cotton is 0.8-1.2: 1, the etherification reaction is carried out at the temperature of 70-85 ℃ for 1-2.5h, and the temperature is cooled to 20-45 ℃ after the reaction is finished.
In the step d, the specific modes of neutralization, separation, washing and drying are as follows: adding acid to adjust the pH value of the system to be neutral, then separating, washing the separated solid phase material for 3-5 times by using a mixed solvent B, and drying for 8-16h at 50-80 ℃ after separating to obtain solid.
Further, the mixed solvent B consists of water and an organic solvent, wherein the water content is 10-25%, and the organic solvent is a low molecular weight alcohol organic solvent with carbon atoms of C3-C4.
The hydrophobically modified hydroxyethyl cellulose is prepared by the preparation method of the hydrophobically modified hydroxyethyl cellulose.
The beneficial effects of the invention are: the hexadecyl group is a high-carbon low-polarity group, the hydrophobicity is obvious, the product performance can be obviously improved by introducing the hexadecyl group into a hydroxyethyl cellulose molecular chain, and the application effect of the product in water-based paint, especially colorful paint, is improved. According to the characteristics of reactivity of hydroxyl groups under different alkali concentrations and the characteristic of difficult macromolecule modification reaction, the invention adopts the method of firstly carrying out hydrophobic modification under the high temperature condition and then adding ethylene oxide for etherification reaction to obtain the hydrophobic modified hydroxyethyl cellulose.
According to the technical scheme, the hydrophobically modified hydroxyethyl cellulose with unique properties of hydroxyethyl cellulose and hydrophobically associating polymer can be prepared, and the substitution degree and substitution uniformity of the hydrophobically modified group can be effectively improved, so that the application performance of the product in the water-based multicolor paint is improved. When the hydrophobically modified hydroxyethyl cellulose prepared by the invention is used in the water-based multicolor paint, the problems of easy color bleeding, viscosity reduction, whitening and the like of hydroxyethyl cellulose in the multicolor paint can be effectively solved, and the performances of water resistance, oil resistance, washing resistance, high weather resistance, stain resistance and the like of the water-based multicolor paint are improved.
Drawings
FIG. 1 is a schematic process flow diagram of a technical solution according to an embodiment of the present invention;
FIG. 2 is a graph of the effect of HEC in application to an aqueous multicolor paint;
FIG. 3 is a graph showing the effect of HMHEC prepared according to an embodiment of the present invention on a container in an aqueous multicolor paint;
FIG. 4 is a graph showing the effect of HMHEC prepared according to an embodiment of the present invention on a container used in an aqueous multicolor paint;
FIG. 5 is a diagram illustrating the spraying effect of HMHEC prepared according to the embodiment of the present invention applied to an aqueous multicolor paint;
FIG. 6 is a state diagram of the HMHEC aqueous solution prepared by the embodiment of the invention after being mixed with oil and water and standing for 48 hours;
FIG. 7 is a state diagram of the HEC aqueous solution after mixing with oil and water and standing for 48 h.
Detailed Description
The technical solution of the present invention can be specifically implemented as follows.
The preparation method of the hydrophobically modified hydroxyethyl cellulose comprises the following steps:
a. mixing sodium hydroxide with a mixed solvent A, controlling the alkali concentration in the mixed solution to be 35-40%, fully dissolving alkali, and cooling;
b. b, mixing the solution treated in the step a with refined cotton powder, and alkalizing at 15-25 ℃ under the protection of inert gas;
c. c, adding a hydrophobic modifier into the solution treated in the step b, carrying out hydrophobic modification reaction at high temperature, and cooling after the reaction is finished;
d. and d, adding ethylene oxide into the solution treated in the step c for etherification reaction, cooling to obtain a hydrophobic modified hydroxyethyl cellulose crude product, and neutralizing, separating, washing and drying the crude product to obtain the hydrophobic modified hydroxyethyl cellulose.
In order to ensure the sufficient activation and swelling of the cellulose, the alkali concentration must meet the requirement to ensure the alkali adsorption of the cellulose. Therefore, in the step a of the invention, the alkali concentration (mass concentration) in the mixed solution is 35-40%; the mixed solvent A consists of water and an organic solvent, the mass fraction of the water in the mixed solvent A is 10-15%, and the organic solvent is at least one of C3-C4 alcohols; preferably, the organic solvent is at least one of isopropanol and tert-butanol; the alkali dissolving is carried out under the stirring state and the heat preservation at 50-70 ℃ for 0.5-1h, and the temperature is cooled to 15-25 ℃ after the alkali dissolving is finished.
The purpose of controlling the alkalization temperature and the alkali concentration is to ensure the sufficient swelling of the cellulose and ensure that the hydroxyl functional groups on the cellulose have good reaction activity, so in the step b, the alkalization reaction condition is alkalization for 1 to 1.5 hours at 15 to 25 ℃; the mass ratio of the sodium hydroxide to the refined cotton powder is 0.54-1: 1, and the mass ratio of the refined cotton powder to the organic mixed solvent is 1: 10; preferably, the refined cotton powder has a particle size of 20-100 meshes; in the step b, the alkalization time is 1-1.5h.
In the step c, the mole ratio of the hydrophobic modifier to the cellulose glucose unit is 0.02-0.1: 1, and the hydrophobic modifier is a hexadecyl substance; preferably, the hydrophobic modifier is bromohexadecane or epoxyhexadecane; the hydrophobic modification reaction is that the temperature is uniformly increased to 90-110 ℃ and the reaction is carried out for 2-3h under heat preservation, and the reaction is cooled to below 40 ℃ after the reaction is finished.
In the step d, the mass ratio of the ethylene oxide to the refined cotton is 0.8-1.2: 1, the etherification reaction is carried out for 1-2.5h at the temperature of 70-85 ℃, and the mixture is cooled to 20-45 ℃ after the reaction is finished; in the step d, the specific modes of neutralization, separation, washing and drying are as follows: adding acid to adjust the pH value of the system to be neutral, then separating, washing the separated solid-phase material for 3-5 times by using a mixed solvent B, and drying for 8-16h at 50-80 ℃ after the solid is obtained by separation; preferably, the mixed solvent B consists of water and an organic solvent, wherein the water content is 10-25%, and the organic solvent is a low molecular weight alcohol organic solvent with carbon atoms of C3-C4.
The hydrophobically modified hydroxyethyl cellulose is prepared by the preparation method of the hydrophobically modified hydroxyethyl cellulose.
The technical solution and effects of the present invention will be further described below by way of practical examples.
Examples
The present invention is further illustrated below with reference to examples, which are intended to be illustrative only and not to limit the scope of the invention.
1. Preparation of hydrophobically modified hydroxyethyl cellulose
The technical scheme of the embodiment of the invention is schematically shown in figure 1, and the raw materials adopted in the embodiments 1-3 are as follows: isopropanol (99.9%), tert-butanol (99.9%), flake caustic soda (technical grade), refined cotton (1000 #), hydrochloric acid (30%), acetic acid (95%), sulfuric acid (60%), ethylene oxide (technical grade), bromohexadecane (reagent), and epoxyhexadecane (reagent).
Example 1
20kg of mixed solvent (2 kg of water and 18kg of isopropanol) and 1.08kg of caustic soda flakes are added into a 50L reaction kettle, stirred and heated to 55 ℃, and the heat is preserved to dissolve the caustic soda for 40min. Cooling to 15 deg.C, adding 2.0kg cotton powder, vacuum-pumping for 5 times, filling nitrogen gas at 0.20MPa, and alkalifying at 15-20 deg.C for 1h. And after the alkalization is finished, 188.27g of hydrophobic modifier bromohexadecane is added, the temperature is raised to 100 ℃, and the reaction is carried out for 2.5 hours under the condition of heat preservation. Cooling to below 40 ℃, adding 1.8kg of ethylene oxide, heating to 75 ℃, preserving heat and reacting for 1.5h. Cooling to below 40 deg.C, adding acetic acid to neutralize to neutrality, discharging, and centrifuging. Washing with 25% water content isopropanol-water mixed solvent at washing bath ratio of 1: 15 for 3 times, centrifuging to obtain solid phase, and drying to obtain hydrophobically modified hydroxyethyl cellulose product.
Example 2
20kg of mixed solvent (3 kg of water and 17kg of tert-butyl alcohol) and 2.0kg of caustic soda flakes are added into a 50L reaction kettle, stirred and heated to 65 ℃, and the heat is preserved to dissolve the caustic soda for 50min. Cooling to 20 deg.C, adding 2.0kg cotton powder, vacuum-pumping for 5 times, filling nitrogen gas at 0.15MPa, and alkalifying at 20-25 deg.C for 1h. And after the alkalization is finished, adding 301.23g of hydrophobic modifier bromohexadecane, heating to 95 ℃, and carrying out heat preservation reaction for 3 hours. Cooling to below 40 ℃, adding 2.2kg of ethylene oxide, heating to 80 ℃, and reacting for 2.0h under the condition of heat preservation. Cooling to below 40 deg.C, adding sulfuric acid to neutralize to neutrality, discharging, and centrifuging. Washing with 15% water content tert-butanol-water mixed solvent at a bath ratio of 1: 15 for 4 times, centrifuging to obtain solid phase, and drying the solid phase to obtain hydrophobically modified hydroxyethyl cellulose product.
Example 3
20kg of mixed solvent (2.4 kg of water, 8.3kg of isopropanol and 8.3kg of tert-butyl alcohol) and 1.41kg of caustic soda flakes are added into a 50L reaction kettle, stirred and heated to 60 ℃, and the caustic soda is dissolved for 60min under the condition of heat preservation. Cooling to 15 deg.C, adding 2.0kg cotton powder, vacuum-pumping for 5 times, filling nitrogen gas at 0.20MPa, and alkalifying at 15-20 deg.C for 1.5h. After the alkalization is finished, 376.54g of hydrophobic modifier bromohexadecane is added, the temperature is raised to 105 ℃, and the reaction is kept for 2 hours. Cooling to below 40 ℃, adding 2.0kg of ethylene oxide, heating to 85 ℃, and reacting for 2.5 hours with heat preservation. Cooling to below 40 deg.C, adding acetic acid to neutralize to neutrality, discharging, and centrifuging. Washing with 20% water content tert-butanol-water mixed solvent at a washing bath ratio of 1: 15 for 4 times, centrifuging to obtain solid phase, and drying the solid phase to obtain hydrophobically modified hydroxyethyl cellulose product.
2. Performance detection
The present invention employs conventional hydroxyethyl cellulose (HEC) as a comparative example, and the results of the physical and chemical properties of the hydrophobically modified hydroxyethyl cellulose (HMHEC) and the conventional hydroxyethyl cellulose (HEC) prepared in examples 1 to 3 were respectively measured, and are shown in table 1.
TABLE 1 results of physical and chemical analyses
When the hydrophobically modified hydroxyethyl cellulose (HMHEC) and the conventional hydroxyethyl cellulose (HEC) prepared by the invention are applied to the water-based multicolor paint for detection respectively, the results are as follows:
(1) The performance test results are shown in Table 2.
TABLE 2 waterborne multicolor coatings application Properties
(2) The results of the application are shown in FIGS. 2-5.
FIG. 2 shows the application of HEC in an aqueous multicolor paint, and it can be seen from FIGS. 2 (a) and (b) that bleeding and viscosity reduction of the HEC aqueous multicolor paint occur in a container; as can be seen from fig. 2 (c), the HEC waterborne multicolor paint exhibited a blush problem after spray application.
FIGS. 3 to 5 show the application of HMHEC in an aqueous multicolor paint under the same conditions, and it can be seen from FIGS. 3 to 4 that the HMHEC aqueous multicolor paint is uniformly mixed in a container without the problems of bleeding and viscosity reduction; as can be seen from fig. 5, the HMHEC waterborne multicolor paint developed good color after spray application, with no blush problem.
(3) The results of oil-water mixing are shown in FIGS. 6-7.
FIG. 6 shows that the HMHEC aqueous solution is mixed with oil and water, and is in a uniform state after standing for 48 hours.
FIG. 7 shows the layering state of HEC aqueous solution after mixing with oil and water and standing for 48 h.
As can be seen from examples 1-3 and comparative examples, when the hydrophobically modified hydroxyethyl cellulose prepared by the invention is applied to the aqueous multicolor paint, the problems of easy color bleeding, viscosity reduction and whitening of the conventional hydroxyethyl cellulose in the multicolor paint can be effectively improved, and the water resistance, oil resistance, washing resistance, high weather resistance, stain resistance and the like of the aqueous multicolor paint are improved.
Claims (10)
1. The preparation method of the hydrophobically modified hydroxyethyl cellulose is characterized by comprising the following steps:
a. mixing sodium hydroxide with the mixed solvent A, controlling the alkali concentration in the mixed solution to be 35-40%, fully dissolving alkali and cooling;
b. mixing the solution treated in the step a with refined cotton powder, and alkalizing at 15-25 ℃ under the protection of inert gas;
c. c, adding a hydrophobic modifier into the solution treated in the step b, carrying out hydrophobic modification reaction at high temperature, and cooling after the reaction is finished;
d. and c, adding ethylene oxide into the solution treated in the step c for etherification reaction, cooling to obtain a hydrophobic modified hydroxyethyl cellulose crude product, and neutralizing, separating, washing and drying the crude product to obtain the hydrophobic modified hydroxyethyl cellulose.
2. The method for producing hydrophobically modified hydroxyethyl cellulose according to claim 1, wherein: in the step a, the mixed solvent A consists of water and an organic solvent, wherein the mass fraction of the water is 10-15%, and the organic solvent is at least one of C3-C4 alcohols.
3. The method for producing hydrophobically modified hydroxyethyl cellulose according to claim 1, wherein: in the step a, the alkali is dissolved by keeping the temperature of 50-70 ℃ for 0.5-1h under the stirring state, and is cooled to 15-25 ℃ after the alkali dissolution is finished.
4. The method for producing hydrophobically modified hydroxyethyl cellulose according to claim 1, wherein: in the step b, the mass ratio of the sodium hydroxide to the refined cotton powder is 0.54-1: 1, the mass ratio of the refined cotton powder to the organic mixed solvent is 1: 10, and the granularity of the refined cotton powder is 20-100 meshes; the alkalization time is 1-1.5h.
5. The method for producing hydrophobically modified hydroxyethyl cellulose according to claim 1, wherein: in the step c, the mole ratio of the hydrophobic modifier to the cellulose glucose unit is 0.02-0.1: 1, and the hydrophobic modifier is a hexadecyl substance.
6. The method for producing hydrophobically modified hydroxyethyl cellulose according to claim 1, characterized in that: in the step c, the hydrophobic modification reaction is carried out by uniformly heating to 90-110 ℃, carrying out heat preservation reaction for 2-3h, and cooling to below 40 ℃ after the reaction is finished.
7. The method for producing hydrophobically modified hydroxyethyl cellulose according to claim 1, characterized in that: in the step d, the mass ratio of the ethylene oxide to the refined cotton is 0.8-1.2: 1, the etherification reaction is carried out for 1-2.5h at the temperature of 70-85 ℃, and the temperature is cooled to 20-45 ℃ after the reaction is finished.
8. The method for producing hydrophobically modified hydroxyethyl cellulose according to claim 1, characterized in that: in the step d, the specific modes of neutralization, separation, washing and drying are as follows: adding acid to adjust the pH value of the system to be neutral, then separating, washing the separated solid phase material for 3-5 times by using a mixed solvent B, and drying for 8-16h at 50-80 ℃ after separating to obtain solid.
9. The method for producing hydrophobically modified hydroxyethyl cellulose according to claim 8, wherein: the mixed solvent B consists of water and an organic solvent, wherein the water content is 10-25%, and the organic solvent is a low molecular weight alcohol organic solvent with carbon atoms of C3-C4.
10. A hydrophobically modified hydroxyethyl cellulose prepared by the method of preparing the hydrophobically modified hydroxyethyl cellulose of claims 1 to 9.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102140337A (en) * | 2011-01-04 | 2011-08-03 | 中国石油大学(华东) | Hydrophobically associating hydroxyethylcellulose oil displacement agent |
| CN102219863A (en) * | 2011-05-06 | 2011-10-19 | 邸勇 | Process for modifying hydroxyethylcellulose (HEC) by high-carbon alkylation |
| 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 |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102140337A (en) * | 2011-01-04 | 2011-08-03 | 中国石油大学(华东) | Hydrophobically associating hydroxyethylcellulose oil displacement agent |
| CN102219863A (en) * | 2011-05-06 | 2011-10-19 | 邸勇 | Process for modifying hydroxyethylcellulose (HEC) by high-carbon alkylation |
| 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 |
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