CN101070351B - Polysubstituted radical cellulose composite ether and its preparing method - Google Patents
Polysubstituted radical cellulose composite ether and its preparing method Download PDFInfo
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Abstract
This invention relates to a polysubstituent group cellulose compound aether and preparation method. According to weight, he substituent group include methoxyl group 12 to 28%, hydroxyl propoxy 0.5 to 15% and hydroxyethyl 0.2 to 15%. This invention uses three kinds chemical substituent group to substitute cellulose molecule hydroxyl,by controlling the content of three group, make the ethylol hydroxypropyl methylcellulose cost low, gel temperature high, water retention good and property stable. It can completely substitute currently applied cellulose compound aether. The invention also discloses the preparation method of above polysubstitutent group cellulose compound ester.
Description
Technical field
The present invention relates to a kind of polysubstituted radical cellulose composite ether and preparation method thereof, relate in particular to substituting group and comprise polysubstituted radical cellulose composite ether of methoxyl group, propoxyl and hydroxyethyl and preparation method thereof.
Background technology
The product of cellulose complex ether representative now is mainly methylcellulose gum MC, methyl hydroxyl ethyl cellulose HEMC and methyl hydroxy propyl cellulose HPMC.These 3 kinds of cellulose complex ethers are widely used in each field, for example at mineral with disperse in the build material of construction system or be used as consistency modifiers and processing aid in the production of makeup and pharmaceutical preparation.About their chemical fundamentals of preparation and principle (production technique and processing step) and raw material enumerate with the description of product and various derivative possible be applied in the existing technical literature on the books.
Chinese invention patent application CN02126521.6 discloses in the presence of alkali metal hydroxide by Mierocrystalline cellulose and alkylating agent and hydroxyalkyl agent prepared in reaction methyl hydroxy propyl cellulose HPMC and the method for methyl hydroxyl ethyl cellulose HEMC in the dme solvent.
Chinese invention patent application CN02113771.4 discloses the preparation method of water soluble hydroxyethyl carboxymethyl cellulose thickener, be solvent and chloroethanol (or oxyethane), Mono Chloro Acetic Acid with the alcohol solution under the condition of 25-75 ± 2 ℃, make water soluble hydroxyethyl carboxymethyl cellulose thickener through hydroxyethylation, carboxymethylation reaction.
Chinese invention patent application CN02143167.1 discloses the method for a kind of industrial preparation methyl hydroxy alkyl cellulose (MHAC), described method comprises the reaction of Mierocrystalline cellulose and alkali metal hydroxide and subsequently and reaction alkylogen and hydroxyalkyl agent, and the described L/D of being reflected at is than carrying out less than 2.5 reactor discontinuous.
Above patent application is not all set forth the function of cellulose complex ether substituted radical, but the substituted radical of cellulose complex ether mainly acts on and can not be ignored, their content and combination are determining the performance of cellulose complex ether, hydroxyethylmethyl-cellulose or Vltra tears all have certain limitation in the application of building, coating, food, printing and dyeing, lagging material, as; Vltra tears, methylcellulose gum they have the high sensitivity of gelling temp to bring difficulty to using summer, reduces water retention property simultaneously.And the stability of solution of hydroxyethylmethyl-cellulose, water retention property is not good.
Summary of the invention
Above-mentioned cellulose complex ether gelling temp height, water retention property are low in order to solve, the technological deficiency of stability of solution difference.An object of the present invention is to provide a kind of polysubstituted radical cellulose composite ether, substituting group comprises: methoxyl group, propoxyl and hydroxyethyl, this cellulose complex ether full name hydroxyethyl Vltra tears, it is low that it has a production cost, the gelling temp height, the characteristics of the more superior and stable in properties of water retention property.
Another object of the present invention provides the preparation method of above-mentioned polysubstituted radical cellulose composite ether.
In order to realize first above-mentioned purpose, the present invention has adopted following technical scheme:
A kind of polysubstituted radical cellulose composite ether, its structural formula is as follows:
Wherein, described R comprises-CH
3,-CH
2CHOH or its etherate ,-CH
2CH (OH) CH
3Perhaps its etherate;
Wherein, the weight percent content of described methoxyl group is 12～28%, and the weight percent content of propoxyl is 0.5～15%, and the weight percent content of hydroxyethyl is 0.2～15%.
Above-mentioned-CH
2The CHOH etherate and-CH
2CH (OH) CH
3Etherate is respectively-CH
2CHOR ,-CH
2CH (OR) CH
3Its major cause be because-CH
2CHOH ,-CH
2CH (OH) CH
3Under etherification conditions, its-OH can also with further etherificate, formation-CH
2CHOR ,-CH
2CH (OR) CH
3Certainly, above-mentioned R also comprises-H.
As preferred scheme, the weight percent content of above-mentioned methoxyl group is 16～22%, and the weight percent content of propoxyl is 2.0～8.0%, and the weight percent content of hydroxyethyl is 0.2～5.0%.
As preferred scheme, the weight percent content of above-mentioned methoxyl group is 16～19%, and the weight percent content of propoxyl is 5.0～8.0%, and the weight percent content of hydroxyethyl is 0.4～2.0%.
The present invention utilizes the hydroxide radical on the cellulosic molecule to replace with three kinds of different chemical substituting groups, substituting group comprises: methoxyl group, propoxyl and hydroxyethyl, by three group contents of reasonable control, it is low to make polysubstituted radical cellulose composite ether of the present invention and former three compare production cost, the gelling temp height, the more superior and stable in properties of water retention property.Therefore, in industry widespread uses such as building, pottery, coating daily use chemicals, can replace Vltra tears, hydroxyethylmethyl-cellulose and the methylcellulose gum at most the most widely of present application fully.
In order to realize second above-mentioned purpose, the present invention has adopted following technical scheme:
The preparation method of the polysubstituted radical cellulose composite ether described in above-mentioned each technical scheme, this method comprises following technology:
(1) cellulose materials is pulverized, in solvent, activated with alkaline matter;
(2) use methyl chloride, propylene oxide and oxyethane at 15～85 ℃, etherificate under 0～3MPa;
(3) solvent is reclaimed in intensification, and adds hot water;
(4) add acid for adjusting pH, centrifugal then, washing, drying make described polysubstituted radical cellulose composite ether.
As preferred scheme, above-mentioned methyl chloride, propylene oxide and oxyethane consumption are respectively 30～120%, 5～50%, 8～60% of cellulose materials.
As preferred scheme, above-mentioned cellulose materials is selected from one or more in purified cotton, the cotton pulp dregs of rice, the wood pulps.
As preferred scheme, above-mentioned solvent is selected from water, toluene, in contract butanols and other alcohols, dme, the methyl chloride one or more.
As preferred scheme, above-mentioned alkaline matter is selected from oxyhydroxide, in (amine) based compound that contains ammonia or the alcoholization sodium one or more.As preferred again, alkaline matter is selected from sodium hydroxide, potassium hydroxide, methylamine, the diethylamine, sodium methylate, sodium ethylate one or more.
As preferred scheme, the condition of above-mentioned etherificate is: be warmed up to 50～70 ℃ earlier, reacted 1～2 hour, 70～85 ℃ of reactions 1～2 hour, reacting more than 85 ℃ 1～1.5 hour.
The yield that the present invention adopts above-mentioned method to prepare polysubstituted radical cellulose composite ether is 120%～140%, and yield improves about 5%.And preparation technology has lower production cost, is fit to the characteristics of suitability for industrialized production.
Embodiment
Embodiment 1
1. in 10 cubic metres of stainless steel reactors, add the mixed solvent that contains 520KG alkali of certain combination, stir and cool to 10～30 ℃, insulated and stirred.
2. below the cool to room temperature, add purified cotton 500KG, vacuumize 20～30 minutes after, keep temperature to stir 1～3 hour.
3. add propylene oxide, oxyethane and methyl chloride, be warmed up to 50～70 ℃, reacted 1～2 hour,, reacting more than 85 ℃ 1～1.5 hour 70～85 ℃ of reactions 1～2 hour.Observe pressure gauge reading, keep 0.3～0.5MPa reaction 1 hour, elevated temperature is to keep pressure in the time of necessary.
4. begin to reclaim solvent, add hot water more than 85 ℃ (amounting to 6000kg) simultaneously, be recovered to temperature in the kettle and reach more than 95 ℃, and kept 30 minutes.
5. be cooled to 60～80 ℃, add hydrochloric acid then and regulate pH to 4.0～8.0, stirred 20～40 minutes, centrifugal, dry.
6. pulverize the back and detect, the results are shown in " test statistics table ".
Composition of raw materials
The test statistics table
Annotate: HE represents hydroxyethyl content; ME representation methoxy content; HP represents hydroxypropyl content.
In the above-mentioned table, example 1～3, example 12 are Comparative Examples, it is good to have a water retention property from above-mentioned tabular analysis polysubstituted radical cellulose composite ether of the present invention as can be seen, while gelling temp height, by three group contents of reasonable control, yield improves about 5%, and it is more superior the application performance change of building, coating etc.
See from example 8,9,10,11, when hydroxyethyl content about 0.4～2.0%, methoxy content is more than 16%, hydroxypropyl content is 5.0% above the time, polysubstituted radical cellulose composite ether of the present invention has higher water-retentivity, product has lower production cost simultaneously, is fit to suitability for industrialized production.
Embodiment 2
1. in 2.5 cubic metres of stainless steel reactors, add purified cotton 200KG, vacuumize the back and add dme 650KG, stir and cool to 10～30 ℃.
2. spray into 50% sodium hydroxide solution 160KG, 10～15 ℃ keep stirring 1～3 hour.
3. add methyl chloride 120KG, propylene oxide 100KG, oxyethane 80KG is warmed up to 30～60 ℃ of reactions 1～3 hour, is reacting more than 60-85 ℃ 1～3 hour.
4. begin to reclaim solvent, add hot water more than 85 ℃ (amounting to 800kg) after finishing, mixed 30 minutes.
5. be cooled to 60～80 ℃, add hydrochloric acid then and regulate pH to 4.0～8.0, stirred 20～40 minutes, centrifugal, dry.
6. pulverize the back and detect hydroxyethyl content 2.1%; Representation methoxy content 18.6; Hydroxypropyl content 7.2%.
Claims (5)
1. polysubstituted radical cellulose composite ether is characterized in that structural formula is as follows:
Wherein, described R comprises and is selected from following group:
-H；
-CH
3；
-CH
2CH
2OH；
-CH
2CH(OH)CH
3；
-CH
2CH
2OH and-CH
3The etherate group that forms;
-CH
2CH
2OH and-CH
2CH
2The etherate group that OH forms;
-CH
2CH
2OH and-CH
2CH (OH) CH
3The etherate group that forms;
-CH
2CH (OH) CH
3With-CH
3The etherate group that forms;
-CH
2CH (OH) CH
3With-CH
2CH (OH) CH
3The etherate group that forms;
-CH
2CH
2OH and-CH
3, and-CH
2CH (OH) CH
3The etherate group that forms;
Weight by polysubstituted radical cellulose composite ether is 100%, the weight percent content of methoxyl group is 12～28% in the polysubstituted radical cellulose composite ether, the weight percent content of hydroxypropyl is 0.5～15%, and the weight percent content of hydroxyethyl is 0.2～15%.
2. a kind of polysubstituted radical cellulose composite ether according to claim 1, it is characterized in that the weight by polysubstituted radical cellulose composite ether is 100%, the weight percent content of methoxyl group is 16～22% in the polysubstituted radical cellulose composite ether, the weight percent content of hydroxypropyl is 2.0～8.0%, and the weight percent content of hydroxyethyl is 0.2～5.0%.
3. a kind of polysubstituted radical cellulose composite ether according to claim 2, it is characterized in that the weight by polysubstituted radical cellulose composite ether is 100%, the weight percent content of methoxyl group is 16～19% in the polysubstituted radical cellulose composite ether, the weight percent content of hydroxypropyl is 5.0～8.0%, and the weight percent content of hydroxyethyl is 0.4～2.0%.
4. the preparation method of a kind of polysubstituted radical cellulose composite ether according to claim 1 is characterized in that comprising following technology:
(1) cellulose materials is pulverized, in solvent, activate with alkaline matter, solvent is selected from water, toluene, in contract butanols and other alcohols, dme, the methyl chloride one or more, and alkaline matter is selected from one or more in sodium hydroxide, potassium hydroxide, methylamine, diethylamine, sodium methylate, the sodium ethylate;
(2) with methyl chloride, propylene oxide and oxyethane, etherificate under pressure 0～3MPa, the condition of etherificate is for being warmed up to 50～70 ℃ earlier, reacted 1～2 hour, 70～85 ℃ of reactions 1～2 hour, reacting more than 85 ℃ 1～1.5 hour, wherein, methyl chloride, propylene oxide and oxyethane consumption are respectively 30～120%, 5～50%, 8～60% of cellulose materials;
(3) solvent is reclaimed in intensification, and adds hot water more than 85 ℃;
(4) add acid for adjusting pH to 4.0～8.0, centrifugal then, washing, drying make described polysubstituted radical cellulose composite ether.
5. the preparation method of a kind of polysubstituted radical cellulose composite ether according to claim 4 is characterized in that described cellulose materials is selected from one or more in purified cotton, the cotton pulp dregs of rice, the wood pulps.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102311549A (en) * | 2011-07-13 | 2012-01-11 | 东北林业大学 | Preparation method of aldehyde lignin |
| CN102391380B (en) * | 2011-08-26 | 2013-05-22 | 大连工业大学 | Hemp stalk composite cellulose ether and preparation method thereof |
| CN102617741B (en) * | 2012-02-24 | 2014-05-07 | 刘传荣 | Process for producing hydroxy propyl cellulose with high substitution degree |
| CN102603899B (en) * | 2012-02-24 | 2013-09-25 | 邸勇 | Process for producing low-substituted hydroxypropyl cellulose |
| CN102690356A (en) * | 2012-05-11 | 2012-09-26 | 新疆光大山河化工科技有限公司 | Preparation method of hydroxyl-ethyl methyl cellulose |
| CN103880966B (en) * | 2014-04-11 | 2016-06-01 | 山东赫达股份有限公司 | The preparation method of special Vltra tears is released in slow control |
| CN104277123A (en) * | 2014-09-26 | 2015-01-14 | 广东东阳光药业有限公司 | Method for preparing low-substituted hydroxypropyl cellulose |
| JP6412853B2 (en) * | 2015-12-16 | 2018-10-24 | 信越化学工業株式会社 | Film molding composition |
| CN106188314B (en) * | 2016-08-12 | 2019-07-05 | 广东龙湖科技股份有限公司 | A kind of preparation method of modified mixed cellulose ethers and the product obtained by this method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1507453A (en) * | 2001-05-21 | 2004-06-23 | 陶氏环球技术公司 | Process for preparing alkyl hydroxyalkyl cellulose ethers |
| CN1745105A (en) * | 2003-01-31 | 2006-03-08 | 阿克佐诺贝尔股份有限公司 | A nonionic cellulose ether and its use |
| CN1789286A (en) * | 2005-12-19 | 2006-06-21 | 华南理工大学 | Modification method of cellulose ether product |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1507453A (en) * | 2001-05-21 | 2004-06-23 | 陶氏环球技术公司 | Process for preparing alkyl hydroxyalkyl cellulose ethers |
| CN1745105A (en) * | 2003-01-31 | 2006-03-08 | 阿克佐诺贝尔股份有限公司 | A nonionic cellulose ether and its use |
| CN1789286A (en) * | 2005-12-19 | 2006-06-21 | 华南理工大学 | Modification method of cellulose ether product |
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Effective date of registration: 20190829 Address after: 313000 Linghu Xizhuang Development Zone, Huzhou City, Zhejiang Province Patentee after: Huzhou Zhanwang Pharmaceutical Co., Ltd. Address before: 313000 No. 1921 Hongfeng West Road, Huzhou Economic and Technological Development Zone, Zhejiang Province Patentee before: Huzhou Hopetop Pharmaceutical Co., Ltd. |