CN1286265A - High-substituted hydroxypropylcellulose ether and its preparing process - Google Patents
High-substituted hydroxypropylcellulose ether and its preparing process Download PDFInfo
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- CN1286265A CN1286265A CN 00111228 CN00111228A CN1286265A CN 1286265 A CN1286265 A CN 1286265A CN 00111228 CN00111228 CN 00111228 CN 00111228 A CN00111228 A CN 00111228A CN 1286265 A CN1286265 A CN 1286265A
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Abstract
An "One-step slurry method" is used to prepare high-substituted hydroxypropyl cellulose ether containing hydroxypropoxy (50-80%) includes alkalizing, etherifying and neutralizing. It can be dissolved in both water and polar organic solvent and has high biodegradation resistance. Its advantages are simple process, high safety, low cost and high etherifying effect.
Description
The present invention relates to a kind of ether of cellulose of non-ionic type, main as thickening material, caking agent, membrane-forming agent, vehicle, water-holding agent and protective colloid etc. in food, medicine, makeup etc.; In industrial aspect, be mainly used in PVC suspension polymerization and make dispersion agent and be used for industries such as printing ink, paint remover: also can be squeezed into goods such as plastics in addition.
At present, the ether of cellulose of domestic production mainly contains ionic and non-ionic type two big classifications.The anti-salt error of ionic Mierocrystalline cellulose is subjected to electrolytical influence the in the solution easily, and is insoluble to organic solvent, is just gradually substituted by non-ionic celluloses ether.The non-ionic celluloses ether kind mainly contains: HPMC, MC, L-HPC, and they exist following shortcoming, and over-all properties is reduced:
1, MC and the HPMC water-soluble organic solvent that is dissolved in again of can not holding concurrently;
2, L-HPC was both water insoluble, also was insoluble to organic solvent;
3, substitution value low (DS≤2);
4, the antibiont degradation property is poor.
Domestic existing production technique generally adopts the dipping milling process simultaneously, contaminate environment, and the product instability, the production cost height, etherificate efficient is low, and reaction pressure is higher, is unfavorable for safety.
For overcoming above-mentioned shortcoming, the purpose of this invention is to provide a kind of substitution value height (molar substitution MS 〉=3, mol substitution value DS 〉=2), germ resistance is strong, can water-solublely can be dissolved in multifunctional macromolecule novel material-high-substituted hydroxypropylcelluloether ether (H-HPC) of various polarity organic solvent and preparation method thereof again.
The present invention utilizes the substituting group propoxyl can replace hydroxyl on the glucose unit, and has side chain to generate, can be water-soluble, can be dissolved in the characteristic of various polarity organic solvent again; With purified cotton and propylene oxide reaction, adopt " a step slurry process " production technique, be about to purified cotton is made substituting group propoxyl content height (50～80%) after alkalization, etherificate, neutralization high-substituted hydroxypropylcelluloether ether (H-HPC).Its basic craft course is: through alkalinisation treatment, secondary adds etherifying agent then in the presence of inert solvent for purified cotton after will pulverizing and alkali, and entire reaction is one step of slurry state and finishes in reactor.React the end back and use in the acid and lixiviating, desalt and impurity with hot wash, last drying, pulverizing.
High-substituted hydroxypropylcelluloether ether (H-HPC) (hereinafter to be referred as H-HPC), its chemical formula:
The molar substitution MS of H-HPC is 3～4.5 (n), and promptly propoxyl content 50～80%; Mol substitution value DS is 2.2～2.8, poly-degree of containing x=150～3000, and molecular weight is 60000～1200000.
H-HPC dissolves in cold water, the aqueous solution is heated to 40～45 ℃ and cloud point occurs, polymkeric substance begins to be precipitated out from solution, soltion viscosity descends rapidly up near pure water, there is other composition existence can influence its cloud point in the solution, when having dissolve polymer and easy and solution blended organic solvent, cloud point raises; Some ionogenic surfactant such as sodium lauryl sulphate also can make cloud point raise, and temperature can be up to more than 95 ℃.Because the difference of substituent characteristic and distribution, the H-HPC hydrophobicity is strong than HEC, obtain the flow characteristics organic solution identical with the aqueous solution so H-HPC also dissolves in multiple organic solvent, but viscosity is lower than the aqueous solution slightly.The organic solvent of H-HPC mostly is polar organic liquid, comprise methyl alcohol, ethanol, propylene glycol, diox and cellosolve (ethylene glycol monoethyl ether) etc., unless nonpolar aliphatic hydrocarbon or aromatic hydrocarbons are mixed use with methyl alcohol or ethanol, otherwise do not dissolve H-HPC, H-HPC solution has the pseudoplastic fluid dynamic characteristic, and viscosity increases rapidly with the increase of concentration.When strength of solution was very high, H-HPC showed liquid crystal characteristic.Below cloud point temperature, the H-HPC soltion viscosity is with the rising of temperature or reduce and reduce uniformly respectively or increase.The same with other non-ionic celluloses ether, H-HPC soltion viscosity stability is subjected to the pH value variable effect little, and pH value is in 2～12 scopes, and its viscosity and pH value are irrelevant.It is a thermoplastic material, does not need softening agent to push under 160 ℃～180 ℃.The water regain difference, H-HPC is no more than 12% when relative temperature 90%, and therefore film or the material that is made by H-HPC has moistureproofness, though be water miscible, is not clamminess.In addition, H-HPC is because replacement is more abundant, and is responsive unlike HEC to microbial attack, so the antibiont degradation property is good.
H-HPC has technical grade and two kinds of specifications of food grade; food grade also is used for medicine and makeup; its outstanding feature is a water-soluble and multiple organic solvent simultaneously; and have the surface of good activity, therefore can be used for polycomponent water-oil dispersion system and make thickening material, binding agent, membrane-forming agent, water-holding agent and protective colloid.Major part is used in food, medicine and makeup aspect in the market, in medicine, make auxiliary materials such as the binding agent of tablet and dressing, main as thickening material, binding agent and vehicle in makeup and food, in PVC makes, be used for suspension polymerization of VC and be used for industries such as printing ink, paint remover as dispersion agent.
The production method of product of the present invention adopts " a step slurry process " production technique.
Product of the present invention is to be raw material with purified cotton, etherifying agent.1, reaction principle:
That is: the hydroxyl on the Mierocrystalline cellulose glucose unit is replaced by propoxyl under alkaline condition.
The also available wood pulp of purified cotton replaces.
2, technical process:
Purified cotton → opener → alkalization → etherificate → neutralization → separation → washing → separation → drying → pulverizing → packing → finished product
Opener:, pulverize then with purified cotton shredding deironing.Purified cotton after the pulverizing is powdery, and its granularity is 80 order transmitances 100%, otherwise coalesces together easily in reaction process, reduces etherificate efficient.
Alkalization: the powdery purified cotton behind the opener is joined in the inert solvent, carry out activation treatment, make the lattice swelling of purified cotton and be beneficial to the infiltration of etherifying agent molecule, the homogeneity of raising etherification reaction with alkali and soft water.The used alkali that alkalizes is metal hydroxides, also can be organic bases.The add-on of alkali (by mass, down together) is 0.1-0.6 a times of purified cotton, and the soft add-on is 0.3-1.0 a times of purified cotton; Inert solvent is the mixture of pure and mild hydrocarbon, and the add-on of inert solvent is 7-15 a times of purified cotton; Inert solvent also can be alcohol (as alcohol, propyl alcohol), the acetone of 3-5 carbon atom, also can be aliphatic hydrocarbon, aromatic hydrocarbon; Temperature should be controlled in 0-35 ℃ and carry out during alkalization; Alkalization time is about 1hr.The adjusting of temperature and time can be decided according to back material and product requirement.
Etherificate: after the alkalinisation treatment, under vacuum condition, add etherifying agent and carry out etherificate, etherifying agent is a propylene oxide.In order to reduce the consumption of etherifying agent, in etherification procedure, etherifying agent adds at twice, and primary add-on is 1-3.5 a times of purified cotton, and the total amount of twice adding is 1.5-4 a times of purified cotton.After for the first time adding etherifying agent, stir under≤30 ℃ of temperature earlier, churning time is 45min-90min, be warming up to 50-100 ℃ then, carry out etherificate, the time is 1-5hr, be cooled to again≤30 ℃, add for the second time etherifying agent and stir, churning time is 30-120min, is warming up to 50-110 ℃ again and carries out etherificate, time is 1-4hr, at this moment, purified cotton and etherifying agent fully react, and generate H-HPC.Etherifying agent is propylene chlorohydrin also.
In whole etherification procedure, the add-on of etherifying agent, churning time, etherification temperature, etherificate time, can determine according to the content of the substituting group propoxyl of concrete working condition and user's needs.When the substituting group content height that the user needs, etherifying agent suitably more, etherification temperature suitably height a bit, the etherificate time can suitably be grown a bit.When propoxyl content hanged down, etherification temperature, etherificate time etc. then can suitably reduce.
Neutralization: after etherificate finished, binder went into to reclaim still, is cooled to normal temperature, added acetic acid and neutralized, and the time is 10-60min, and the control pH value is between 5-8.5, and neutralization goes out inert solvent after finishing through fractionation by distillation, sent the recycling of alkalization operation.
Separation, washing, drying: the material of the present invention after will neutralizing, carry out the solid-liquid separation first time with supercentrifuge earlier, remaining waste liquid is got rid of; Material after the separation is sent to laundry and is washed still, wash with hot water, in the flush away and the time salt and the impurity that generate, wash temperature can be controlled in 50-100 ℃, washing time can be controlled in 0.5-2hr; Material after washing carries out the secondary solid-liquid separation again, and bath water and remaining waste liquid are further got rid of; Material after separating for the second time carries out drying with moisture eliminator, and drying temperature is 80-140 ℃, and the moisture content of dried product of the present invention is controlled at≤and 5%.
Pulverize, pack: dried product of the present invention is pulverized, sieved, and the granularity of the product of the present invention after pulverizing, sieving is that 40 order transmitances are 100%, or according to user's needs.Packing is dispatched from the factory then.
Below be one embodiment of the present of invention:
When preparing the H-HPC of propoxyl content 58%, 1 part purified cotton powder can be fed into and fill 0.4 part of alkali, 0.8 part water, alkalized 1 hour in 30 ℃ in 14 parts of reaction of toluene stills, vacuumize the back and add 1 part of propylene oxide, stir, be warming up to 60 ± 1 ℃ after stirring, react after 3 hours, be cooled to below 30 ℃, add for the second time propylene oxide, add-on is 2.5 parts, is warming up to 85 ± 1 ℃ of reactions 4 hours, is cooled to add acetic acid below 60 ℃ and be neutralized to about PH7, the distillation of carrying out inert solvent that heats up is then reclaimed, after the end, with 70-90 ℃ hot wash, separate, be dried to water content again below 5%, through pulverizing, promptly get product of the presently claimed invention.
The present invention is owing to be the characteristic of utilizing the substituting group propoxyl, developed the high-substituted hydroxypropylcelluloether ether of propoxyl content at 50-80%, its preparation method adopts " a step slurry process " production technique, entire reaction is to finish at slurry state next time, the maximum characteristics of production technique of the present invention are that various parameter regulation leeway is big, can adjust at any time according to raw material, working condition, and are strong to the adaptability of working condition, easy to operate, easy, and carry out at normal pressure and vacuum condition.Therefore, product of the present invention has the substitution value height, can water-solublely can be dissolved in polar organic solvent again, characteristics such as the antibiont degradation property is good, the convenient production process operation of its preparation can be according to raw material, the working condition setting range is big, easy to control, characteristics such as the production technique scope of application is big, and is safe, pollution-free.
Claims (5)
1, a kind of is substituent high-substituted hydroxypropylcelluloether ether with propoxyl, and the propoxyl content that it is characterized in that product of the present invention is 50～80%.
2, according to the said high-substituted hydroxypropylcelluloether ether of claim 1, it is characterized in that said Hydroxypropylcelliloxe is is raw material with purified cotton, etherifying agent, adopt " a step slurry process " the production technique preparation, its technical process is: purified cotton → opener → alkalization → etherificate → neutralization → separation → washing → separation → drying → pulverizing → packing → finished product; The also available wood pulp of purified cotton replaces.
3, according to the said high-substituted hydroxypropylcelluloether ether of claim 2, it is characterized in that the alkalization in the said technical process: the powdery purified cotton behind the opener is joined in the inert solvent, carry out activation treatment with alkali and soft water; The used alkali that alkalizes is metal hydroxides, also can be organic bases; The add-on of alkali (by mass, down together) is 0.1～0.6 times of purified cotton, and the soft add-on is 0.3～1.0 times of purified cotton; Inert solvent is the mixture of pure and mild hydrocarbon, and the add-on of inert solvent is 7～15 times of purified cotton; Inert solvent also can be alcohol, the acetone of 3～5 carbon atoms, also can be aliphatic hydrocarbon, aromatic hydrocarbon.
4, according to the said high-substituted hydroxypropylcelluloether ether of claim 2, it is characterized in that said etherificate in the said technical process: after the alkalinisation treatment, under vacuum condition, add etherifying agent and carry out etherificate, etherifying agent is a propylene oxide; In etherification procedure, etherifying agent adds at twice, and primary add-on is 1～3.5 times of purified cotton, and the total amount of twice adding is 1.5～4 times of purified cotton; After for the first time adding etherifying agent, under≤30 ℃ of temperature, stir earlier, be warming up to 50～100 ℃ then, carry out etherificate, be cooled to again≤30 ℃, add etherifying agent for the second time and stir, be warming up to 50～110 ℃ again and carry out etherificate; Etherifying agent is propylene chlorohydrin also.
5, according to the said high-substituted hydroxypropylcelluloether ether of claim 2, it is characterized in that the neutralization in the said technical process: after etherificate finishes, be cooled to normal temperature, adding acetic acid neutralizes, the control pH value is between 5～8.5, neutralization goes out inert solvent after finishing through fractionation by distillation, send the recycling of alkalization operation.
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| CN 00111228 CN1286265A (en) | 2000-07-20 | 2000-07-20 | High-substituted hydroxypropylcellulose ether and its preparing process |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101830990A (en) * | 2010-05-08 | 2010-09-15 | 山东一滕化工有限公司 | Instant hydroxypropyl methyl cellulose ether and preparation method thereof |
| CN101891827A (en) * | 2010-07-29 | 2010-11-24 | 安徽山河药用辅料股份有限公司 | Method for preparing hydroxypropyl cellulose |
| CN101280023B (en) * | 2008-01-31 | 2010-12-01 | 重庆力宏精细化工有限公司 | Preparation of acid-resistant sodium carboxymethylcellulose |
| CN101003577B (en) * | 2006-01-20 | 2010-12-22 | 上海长光企业发展有限公司 | Technique for producing polyanionic cellulose with high degree of substitution |
| CN102127170A (en) * | 2011-03-23 | 2011-07-20 | 山东一滕化工有限公司 | Method for preparing cellulose ether by utilizing wood pulp |
| CN104151436A (en) * | 2014-08-20 | 2014-11-19 | 安徽山河药用辅料股份有限公司 | Preparation method of high content hydroxypropylcellulose |
| CN104327190A (en) * | 2014-10-15 | 2015-02-04 | 泸州北方化学工业有限公司 | Method for refining ethyl cellulose ether |
| CN104892773A (en) * | 2015-07-10 | 2015-09-09 | 泸州北方化学工业有限公司 | Preparation method of high-substitution-degree sodium carboxymethylcellulose |
| CN105862388A (en) * | 2015-01-21 | 2016-08-17 | 重庆联佰博超医疗器械有限公司 | Preparation method of hydroxy propyl cellulose used for haemostasis |
| CN107602708A (en) * | 2017-11-09 | 2018-01-19 | 安徽山河药用辅料股份有限公司 | A kind of preparation method of high substitution hydroxypropylcellulose |
| CN109021118A (en) * | 2018-07-24 | 2018-12-18 | 河南正弘药用辅料有限公司 | A kind of production method of hydroxypropyl cellulose |
| TWI668232B (en) * | 2014-09-22 | 2019-08-11 | 日商信越化學工業股份有限公司 | Method for continuously producing cellulose ether |
| CN113201075A (en) * | 2021-06-07 | 2021-08-03 | 浙江中维药业股份有限公司 | Preparation method of special hydroxypropyl methylcellulose for sustained-release tablets |
-
2000
- 2000-07-20 CN CN 00111228 patent/CN1286265A/en active Pending
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101003577B (en) * | 2006-01-20 | 2010-12-22 | 上海长光企业发展有限公司 | Technique for producing polyanionic cellulose with high degree of substitution |
| CN101280023B (en) * | 2008-01-31 | 2010-12-01 | 重庆力宏精细化工有限公司 | Preparation of acid-resistant sodium carboxymethylcellulose |
| CN101830990A (en) * | 2010-05-08 | 2010-09-15 | 山东一滕化工有限公司 | Instant hydroxypropyl methyl cellulose ether and preparation method thereof |
| CN101891827A (en) * | 2010-07-29 | 2010-11-24 | 安徽山河药用辅料股份有限公司 | Method for preparing hydroxypropyl cellulose |
| CN101891827B (en) * | 2010-07-29 | 2012-05-09 | 安徽山河药用辅料股份有限公司 | Method for preparing hydroxypropyl cellulose |
| CN102127170A (en) * | 2011-03-23 | 2011-07-20 | 山东一滕化工有限公司 | Method for preparing cellulose ether by utilizing wood pulp |
| CN104151436A (en) * | 2014-08-20 | 2014-11-19 | 安徽山河药用辅料股份有限公司 | Preparation method of high content hydroxypropylcellulose |
| TWI668232B (en) * | 2014-09-22 | 2019-08-11 | 日商信越化學工業股份有限公司 | Method for continuously producing cellulose ether |
| CN104327190A (en) * | 2014-10-15 | 2015-02-04 | 泸州北方化学工业有限公司 | Method for refining ethyl cellulose ether |
| CN105862388A (en) * | 2015-01-21 | 2016-08-17 | 重庆联佰博超医疗器械有限公司 | Preparation method of hydroxy propyl cellulose used for haemostasis |
| CN104892773A (en) * | 2015-07-10 | 2015-09-09 | 泸州北方化学工业有限公司 | Preparation method of high-substitution-degree sodium carboxymethylcellulose |
| CN107602708A (en) * | 2017-11-09 | 2018-01-19 | 安徽山河药用辅料股份有限公司 | A kind of preparation method of high substitution hydroxypropylcellulose |
| CN109021118A (en) * | 2018-07-24 | 2018-12-18 | 河南正弘药用辅料有限公司 | A kind of production method of hydroxypropyl cellulose |
| CN113201075A (en) * | 2021-06-07 | 2021-08-03 | 浙江中维药业股份有限公司 | Preparation method of special hydroxypropyl methylcellulose for sustained-release tablets |
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