CN107298720A - The preparation method of the polyanion cellulose of the viscous heatproof low filtration loss of height - Google Patents
The preparation method of the polyanion cellulose of the viscous heatproof low filtration loss of height Download PDFInfo
- Publication number
- CN107298720A CN107298720A CN201610229800.XA CN201610229800A CN107298720A CN 107298720 A CN107298720 A CN 107298720A CN 201610229800 A CN201610229800 A CN 201610229800A CN 107298720 A CN107298720 A CN 107298720A
- Authority
- CN
- China
- Prior art keywords
- cellulose
- preparation
- micro
- cross
- linking reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
- C08B15/005—Crosslinking of cellulose derivatives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B1/00—Preparatory treatment of cellulose for making derivatives thereof, e.g. pre-treatment, pre-soaking, activation
- C08B1/08—Alkali cellulose
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B11/00—Preparation of cellulose ethers
- C08B11/02—Alkyl or cycloalkyl ethers
- C08B11/04—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals
- C08B11/10—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals substituted with acid radicals
- C08B11/12—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals substituted with acid radicals substituted with carboxylic radicals, e.g. carboxymethylcellulose [CMC]
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/02—Well-drilling compositions
- C09K8/03—Specific additives for general use in well-drilling compositions
- C09K8/035—Organic additives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
- C09K2208/08—Fiber-containing well treatment fluids
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Biochemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention discloses a kind of preparation method of the polyanion cellulose of high viscous heatproof low filtration loss.The preparation method is comprised the step of using purified cotton as cellulosic material：（a）The alkalization of cellulose；（b）The etherificate of cellulose；（c）Neutralize washing；（d）The post processing of product.The preparation method also includes micro- cross-linking reaction step, and the step exists（b）Carried out after the etherificate of cellulose, micro- cross-linking reaction is that N DMAAs, which are added in cellulose, carries out cross-linking reaction by crosslinking agent N.The characteristics of polyanion cellulose prepared by this method has high viscosity, substitution value height, low filter loss and good temperature tolerance, with certain prospects for commercial application.
Description
Technical field
The present invention relates to a kind of preparation method of polyanion cellulose, more particularly to a kind of high viscosity polyanion fiber
The preparation method of element.
Background technology
Polyanion cellulose（Abbreviation PAC）, it is one obtained by chemical modification using native cellulose as base stock
The plain enzyme of water miscible ionic cellulose is planted, is a kind of important mud conditioner in oil drilling, for drilling well, completion and state
In terms of well, play thickening, filtrate reducing, suspension etc..Continuous expansion and the drilling depth that is averaged due to petroleum exploration field
Increasingly increase, PAC quality requirement is improved constantly, it is desirable to which PAC has higher viscosity, salt tolerance and temperature resistance.
, can be using cellulose crushing, nitrogen-sealed, increasing solvent liquor ratio, addition antioxidant etc. in terms of PAC mass is improved
Method, to reach the purpose for improving PAC viscosity, substitution value and substituted pattern homogeneity.Scientific research Main way is at present
PAC performance is improved by the way of micro- crosslinking.The country is for using borate, and aluminium salt, epoxychloropropane etc. is used as crosslinking
Agent is used for oneself report many through having in terms of micro- crosslinking of polyanion cellulose, but these crosslinking agents improve it is poly- it is cloudy from
Subbundle quality amount aspect and application performance method have respective defect, it is impossible to meet matter of the people to polyanion cellulose
The high request of amount.
Aluminium salt and organic titanium [oilfield chemistry, 1988,5 (3) are used in the prior art：171-176] it is fine to polyanion
Dimension element carries out micro- crosslinking, but polyanion cellulose is not only formed Polymer Solution by the technology, and to add aluminium salt chela
Mixture, so the technology not enough facilitates；Epoxychloropropane [Textile Research Journal, 1974,44:946-
952] as crosslinking agent, its cross-linking reaction need to be carried out at relatively high temperatures, and the reaction time is long, and the extent of reaction is difficult to control；
Using esterification, polybasic carboxylic acid and cellulose crosslinked [Textile Research Joumal, 1965,35:260-277],
Representative is 1,2,3,4- butyl tetrabasic carboxylic acids, maleic acid, malonic acid etc., because the production of carboxymethyl cellulose
Cheng Bixu could be crosslinked acids crosslinking agent in strong alkaline condition, finished product polyanion cellulose that can only be after washing.To sum up, this
A little crosslinking agents have respective defect in terms of the quality of polyanion cellulose is improved.
The content of the invention
It is an object of the invention to propose a kind of preparation method of high viscous heatproof polyanion cellulose, to solve existing system
The problem of polyanion cellulose viscosity that Preparation Method is obtained is low, filter loss is high, temperature tolerance is inadequate.
The present invention solves the above problems by the following technical programs, reaches the purpose of the present invention.
A kind of preparation method of the polyanion cellulose of high viscous heatproof low filtration loss, the preparation method is using purified cotton as fibre
The plain raw material of dimension, including the step of have：（a）The alkalization of cellulose；（b）The etherificate of cellulose；（c）Neutralize washing；（d）Product
Post processing.
The preparation method also includes connecing micro- cross-linking reaction step, and micro- cross-linking reaction step is in the step（b）With
Step（c）Between carry out, micro- cross-linking reaction step is that crosslinking agent N,N-DMAA is added in cellulose
Carry out micro- cross-linking reaction.
Purified cotton of the present invention is made up of carbon, hydrogen, 3 kinds of elements of oxygen, its mass ratio constituted:Carbon 44.4%%, hydrogen
6.17%th, oxygen 49.39%, its chemical composition is cellulose, lignin and hemicellulose.
The purified cotton that present invention selection reaction raw materials are degree of polymerization DP >=2400, M1000, and in reactions steps（a）, step
Suddenly（b）And during micro- cross-linking reaction, lead to N2Protect cellulose.
15-40 DEG C of the temperature of quaternization in preparation method of the present invention, alkalization time is 1.5h, and sodium hydroxide is water-soluble
The concentration of liquid is 40-50%.Etherifying agent monoxone consumption and the mass ratio of purified cotton are 1.1-1.3 during etherification reaction：1；Ether
The progress of two steps is divided into, the first step maintains 1h at 50 DEG C, and second step maintains 1-2h at 75 DEG C.
The initiator of micro- cross-linking reaction of the present invention is potassium peroxydisulfate or ammonium persulfate one kind therein, and its micro- crosslinking is anti-
Temperature control is answered at 65-75 DEG C, the time control of micro- cross-linking reaction is in 3-4h, and the dosage of crosslinking agent is purified cotton quality
0.75-1.5%.
The present invention have selected N, and N- DMAAs carry out micro- friendship as the crosslinking agent of polyanion cellulose to it
Connection is modified.N,N-DMAA is as a kind of temperature-resistant anti-salt monomer, with compared with high reaction activity, the hydroxyl with cellulose
After reaction, polyanion cellulose substitution value and its viscosity can be improved, and effectively increase polyanion cellulose
Application performance, the particularly filter loss and temperature tolerance in polyanion cellulose.
Change it is an advantage of the current invention that carrying out micro- crosslinking to cellulose as crosslinking agent from N,N-DMAA
Property, method of modifying is simple and easy to apply, with certain prospects for commercial application.Modified polyanion cellulose function admirable, relatively changes
There is more apparent raising in solution viscosity, filter loss and heat resistance before property.
Embodiment
Below by embodiment, the present invention is further illustrated, its purpose be only that be better understood from the present invention rather than
Limit the scope of protection of the invention.
The raw material that following examples are used is at M1000, the purified cotton of degree of polymerization DP=2650, and process preliminary crushing
Reason.
The substitution value of polyanion cellulose is used《Drilling fluid materialses specification ISO 13500：2006》Middle method is surveyed
Examination；Apparent viscosity and filter loss are used《Drilling fluid materialses specification GB/T 5005-2010》Middle method is tested.
Temperature tolerance method of testing is as follows：The sample solution of 3% concentration is prepared, in 150 DEG C of heat rolling 16h, with six fast rotary viscosities
With the solution apparent viscosity after heat rolling before measurement examination heat rolling, viscosity retention ratio is calculated with below equation.Viscosity retention ratio is higher, sample
The heat resistance of product is better.
Apparent viscosity after apparent viscosity/heat rolling before viscosity retention ratio=heat rolling
Comparative example
A kind of preparation method of the polyanion cellulose of high viscous heatproof low filtration loss, concrete operation method is as follows：
（1）The alkalization of cellulose：In kneader by 1500g concentration be 40%（w/w）Sodium hydrate aqueous solution, 1800g concentration
For 92%（v/v）Ethanol water, kneader mixing 20min is put into together, is cooled to 15 DEG C, will be through preliminary crushing at
In the 1000g purified cotton fibres element input kneader of reason, alkali cellulose is obtained after carrying out quaternization 1.5h.
（2）The etherificate of cellulose：By 1100g monoxones by way of spray in 20-30min（Being configured to concentration is
50% aqueous solution）Mixed with alkali cellulose, the etherification reaction 1h at 50 DEG C, then be warming up to 75 DEG C of etherification reaction 1h.React full mistake
N is carried out in journey2Protection.
（3）The post processing of product：Less than 50 DEG C are cooled to after the completion of reaction, is 70% by product and concentration（v/v）Ethanol
The aqueous solution is mixed, and is added glacial acetic acid and is adjusted pH value to neutrality, the operation washed and centrifuged 3 times, used during washing concentration for
80%（v/v）Ethanol water as detergent, and using horizontal spiral discharge sedimentation centrifuge centrifuged, dried, powder
It is broken, obtain final products.
Embodiment 1
A kind of preparation method of the polyanion cellulose of high viscous heatproof low filtration loss, concrete operation method is as follows：
（1）The alkalization of cellulose：In kneader by 1500g concentration be 40%（w/w）Sodium hydrate aqueous solution, 1800g concentration
For 92%（v/v）Ethanol water, kneader mixing 20min is put into together, is cooled to 15 DEG C, will be through preliminary crushing at
In the 1000g purified cotton fibres element input kneader of reason, alkali cellulose is obtained after carrying out quaternization 1.5h.
（2）The etherificate of cellulose：By 1100g monoxones by way of spray in 20-30min（Being configured to concentration is
50% aqueous solution）Mixed with alkali cellulose, the etherification reaction 1h at 50 DEG C, then be warming up to 75 DEG C of etherification reaction 1h.
（3）The crosslinking of cellulose：By 7.5g N, N- DMAAs are dissolved in 95% with 0.0075g potassium peroxydisulfates（v/
v）Ethanol water, added by way of spray in kneader, by temperature control 65 DEG C react 3h.React in overall process
Carry out N2Protection.
（4）The post processing of product：Less than 50 DEG C are cooled to after the completion of reaction, is 70% by product and concentration（v/v）Ethanol
The aqueous solution is mixed, and is added glacial acetic acid and is adjusted pH value to neutrality, the operation washed and centrifuged 3 times, used during washing concentration for
80%（v/v）Ethanol water as detergent, and using horizontal spiral discharge sedimentation centrifuge centrifuged, dried, powder
It is broken, obtain final products.
Embodiment 2
A kind of preparation method of the polyanion cellulose of high viscous heatproof low filtration loss, concrete operation method is as follows：
（1）The alkalization of cellulose：In kneader by 1500g concentration be 50%（w/w）Sodium hydrate aqueous solution, 1800g concentration
For 92%（v/v）Ethanol water, kneader mixing 20min is put into together, is cooled to 40 DEG C, will be through preliminary crushing at
In the 1000g purified cotton fibres element input kneader of reason, alkali cellulose is obtained after carrying out quaternization 1.5h.
（2）The etherificate of cellulose：By 1300g monoxones by way of spray in 20-30min（Being configured to concentration is
50% aqueous solution）Mixed with alkali cellulose, the etherification reaction 1h at 50 DEG C, then be warming up to 75 DEG C of etherification reaction 2h.
（3）The crosslinking of cellulose：By 15g N, N- DMAAs are dissolved in 95% with 0.03g ammonium persulfates（v/v）'s
Ethanol water, is added in kneader by way of spray, and temperature control is reacted into 4h at 75 DEG C.React in overall process and carry out
N2Protection.
（4）The post processing of product：Less than 50 DEG C are cooled to after the completion of reaction, is 70% by product and concentration（v/v）Ethanol
The aqueous solution is mixed, and is added glacial acetic acid and is adjusted pH value to neutrality, the operation washed and centrifuged 3 times, used during washing concentration for
80%（v/v）Ethanol water as detergent, and using horizontal spiral discharge sedimentation centrifuge centrifuged, dried, powder
It is broken, obtain final products.
Embodiment 3
A kind of preparation method of the polyanion cellulose of high viscous heatproof low filtration loss, concrete operation method is as follows：
（1）The alkalization of cellulose：In kneader by 1500g concentration be 45%（w/w）Sodium hydrate aqueous solution, 1800g concentration
For 92%（v/v）Ethanol water, kneader mixing 20min is put into together, is cooled to 30 DEG C, will be through preliminary crushing at
In the 1000g purified cotton fibres element input kneader of reason, alkali cellulose is obtained after carrying out quaternization 1.5h.
（2）The etherificate of cellulose：By 1200g monoxones by way of spray in 20-30min（Being configured to concentration is
50% aqueous solution）Mixed with alkali cellulose, the etherification reaction 1h at 50 DEG C, then be warming up to 75 DEG C of etherification reaction 1.5h.
（3）The crosslinking of cellulose：10g N, N- DMAAs are dissolved in 95% with 0.015g potassium peroxydisulfates（v/v）'s
Ethanol water, is added in kneader by way of spray, and temperature control is reacted into 3.5h at 70 DEG C.Enter in reaction overall process
Row N2Protection.
（4）The post processing of product：Less than 50 DEG C are cooled to after the completion of reaction, is 70% by product and concentration（v/v）Ethanol
The aqueous solution is mixed, and is added glacial acetic acid and is adjusted pH value to neutrality, the operation washed and centrifuged 3 times, used during washing concentration for
80%（v/v）Ethanol water as detergent, and using horizontal spiral discharge sedimentation centrifuge centrifuged, dried, powder
It is broken, obtain final products.
Embodiment 4
A kind of preparation method of the polyanion cellulose of high viscous heatproof low filtration loss, concrete operation method is as follows：
（1）The alkalization of cellulose：In kneader by 1500g concentration be 47%（w/w）Sodium hydrate aqueous solution, 1800g concentration
For 92%（v/v）Ethanol water, kneader mixing 20min is put into together, is cooled to 20 DEG C, will be through preliminary crushing at
In the 1000g purified cotton fibres element input kneader of reason, alkali cellulose is obtained after carrying out quaternization 1.5h.
（2）The etherificate of cellulose：By 1150g monoxones by way of spray in 20-30min（Being configured to concentration is
50% aqueous solution）Mixed with alkali cellulose, the etherification reaction 1h at 50 DEG C, then be warming up to 75 DEG C of etherification reaction 2h.
（3）The crosslinking of cellulose：By 12g N, N- DMAAs are dissolved in 95% with 0.024g ammonium persulfates（v/v）
Ethanol water, added by way of spray in kneader, by temperature control 75 DEG C react 3h.Enter in reaction overall process
Row N2Protection.
（4）The post processing of product：Less than 50 DEG C are cooled to after the completion of reaction, is 70% by product and concentration（v/v）Ethanol
The aqueous solution is mixed, and is added glacial acetic acid and is adjusted pH value to neutrality, the operation washed and centrifuged 3 times, used during washing concentration for
80%（v/v）Ethanol water as detergent, and using horizontal spiral discharge sedimentation centrifuge centrifuged, dried, powder
It is broken, obtain final products.
The polyanion cellulose performance of table 1
| Substitution value | Apparent viscosity/mPa.s | Filter loss/ml | Viscosity retention ratio/% | |
| Comparative example | 1.12 | 48 | 16.2 | 53 |
| Embodiment 1 | 1.34 | 56 | 10.6 | 65 |
| Embodiment 2 | 1.36 | 55 | 9.2 | 76 |
| Embodiment 3 | 1.43 | 58 | 8.4 | 82 |
| Embodiment 4 | 1.46 | 52 | 11.0 | 63 |
Claims (8)
1. a kind of preparation method of the polyanion cellulose of high viscous heatproof low filtration loss, it is characterised in that the preparation method is with essence
Cotton processed is cellulosic material, and preparation process is：（a）The alkalization of cellulose；（b）The etherificate of cellulose；（c）Micro- cross-linking reaction；（d）
Neutralize washing；（e）The post processing of product；Wherein micro- cross-linking reaction step is that, by crosslinking agent N, N- DMAAs are added to
Micro- cross-linking reaction is carried out in cellulose.
2. a kind of preparation method of the polyanion cellulose of high viscous heatproof low filtration loss according to claim 1, it is special
Levy and be：In reactions steps（a）, step（b）And during micro- cross-linking reaction, lead to N2Protect cellulose.
3. a kind of preparation method of the polyanion cellulose of high viscous heatproof low filtration loss according to claim 1, it is special
Levy and be：Micro- cross-linking reaction temperature control is at 65-75 DEG C, and the time control of micro- cross-linking reaction is in 3-4h, the friendship
Join the 0.75-1.5% that agent N, N- DMAA consumption is purified cotton quality.
4. a kind of preparation method of the polyanion cellulose of high viscous heatproof low filtration loss according to claim 1, it is special
Levy and be：The initiator of micro- cross-linking reaction is potassium peroxydisulfate or ammonium persulfate one kind therein, and consumption is crosslinking agent quality
0.1-0.2%.
5. a kind of preparation method of the polyanion cellulose of high viscous heatproof low filtration loss according to claim 1, it is special
Levy and be：Alkalization temperature is 15-40 DEG C in the preparation method, and alkalization time is 1.5h, and etherification procedure is divided into two steps, the first step
1h is maintained at 50 DEG C, second step maintains 1-2h at 75 DEG C.
6. a kind of preparation method of the polyanion cellulose of high viscous heatproof low filtration loss according to claim 1, it is special
Levy and be：Step in the preparation method（b）In etherification procedure, etherifying agent is monoxone, the mass ratio of its consumption and purified cotton
For 1.1-1.3：1.
7. a kind of preparation side of the polyanion cellulose of high viscous heatproof low filtration loss according to claim any one of 1-6
Method, it is characterised in that：Described purified cotton is made up of carbon, hydrogen, 3 kinds of elements of oxygen, its mass ratio constituted:Carbon 44.4%%, hydrogen
6.17%th, oxygen 49.39%, its chemical composition is cellulose, lignin and hemicellulose.
8. a kind of preparation side of the polyanion cellulose of high viscous heatproof low filtration loss according to claim any one of 1-6
Method, it is characterised in that：The purified cotton is degree of polymerization DP >=2400, M1000 purified cottons.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610229800.XA CN107298720A (en) | 2016-04-14 | 2016-04-14 | The preparation method of the polyanion cellulose of the viscous heatproof low filtration loss of height |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610229800.XA CN107298720A (en) | 2016-04-14 | 2016-04-14 | The preparation method of the polyanion cellulose of the viscous heatproof low filtration loss of height |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107298720A true CN107298720A (en) | 2017-10-27 |
Family
ID=60137198
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610229800.XA Pending CN107298720A (en) | 2016-04-14 | 2016-04-14 | The preparation method of the polyanion cellulose of the viscous heatproof low filtration loss of height |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107298720A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111363526A (en) * | 2020-04-23 | 2020-07-03 | 中国海洋石油集团有限公司 | Application of modified apricot kernel powder as environment-friendly drilling fluid flow pattern regulator |
| CN117164728A (en) * | 2023-09-06 | 2023-12-05 | 山东扬子生物科技有限公司 | Production process for preparing CMC (CMC) for lithium battery by slurry method |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101838334A (en) * | 2009-03-19 | 2010-09-22 | 上海长光企业发展有限公司 | Preparation method of high viscosity polyanion cellulose |
-
2016
- 2016-04-14 CN CN201610229800.XA patent/CN107298720A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101838334A (en) * | 2009-03-19 | 2010-09-22 | 上海长光企业发展有限公司 | Preparation method of high viscosity polyanion cellulose |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111363526A (en) * | 2020-04-23 | 2020-07-03 | 中国海洋石油集团有限公司 | Application of modified apricot kernel powder as environment-friendly drilling fluid flow pattern regulator |
| CN117164728A (en) * | 2023-09-06 | 2023-12-05 | 山东扬子生物科技有限公司 | Production process for preparing CMC (CMC) for lithium battery by slurry method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104448010B (en) | A kind of instant polyanion cellulose and preparation method thereof | |
| CN103087202B (en) | Preparation method of polyanionic cellulose with ultrahigh viscosity for water-based drilling fluid | |
| CN104558640B (en) | A kind of preparation method of cellulose diacetate microgranule | |
| CN103936930B (en) | The preparation method of the netted quaternary ammonium salt cationic Mierocrystalline cellulose of sugarcane marrow thin-walled cell | |
| CN104558217A (en) | Cross-linked starch for drilling fluid and preparation method thereof | |
| CN102344495A (en) | Cyanoethyl cellulose glycerin ether and preparation method thereof | |
| CN103319611B (en) | Production process of 2000s/v nitrocotton | |
| Köpcke et al. | Optimization of treatment sequences for the production of dissolving pulp from birch kraft pulp | |
| CN107298720A (en) | The preparation method of the polyanion cellulose of the viscous heatproof low filtration loss of height | |
| CN102603903A (en) | Method for preparing double-crosslinking amphoteric tapioca starch | |
| CN104878454A (en) | High-water-content ionic liquid/cellulose spinning solution preparation method | |
| CN105566500B (en) | A kind of preparation method of granular pattern polyanion cellulose | |
| CN102093481A (en) | Method for preparing instant carboxymethylcellulose | |
| CN108589405B (en) | Paper reinforcing agent, paper and preparation method thereof | |
| CN101838334A (en) | Preparation method of high viscosity polyanion cellulose | |
| CN101161684B (en) | Infra-red synthesis of crosslinked carboxymethyl fecula | |
| CN104497154A (en) | Preparation method of hydroxy butyl starch ether or hydroxy butyl modified starch ether | |
| CN101838331A (en) | Preparation method of poly anionic cellulose with low viscosity and filtration | |
| CN103290503B (en) | Cellulosic chemical modification and continuous low-temperature dissolving spinning technology and equipment | |
| CN103992435B (en) | A kind of synthetic method of Vltra tears graft acrylic acid methyl esters/vinyl acetate sand-fixation agent | |
| CN101357994B (en) | Carboxymethyl wood flour with high degree of substitution and preparation method thereof | |
| CN104086658B (en) | A kind of preparation method of food grade sodium carboxymethylcellulose | |
| CN106084069B (en) | Sodium carboxymethylcellulose and preparation method thereof | |
| CN107955189A (en) | A kind of preparation method of hydrogel | |
| CN103554291A (en) | Modification method and application of saponin gum for oil field production |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20171027 |
|
| WD01 | Invention patent application deemed withdrawn after publication |