CN104888227B - Capsules hydroxypropul starch copolymer and using the hydroxypropul starch copolymer as the preparation method of the capsule of raw material - Google Patents
Capsules hydroxypropul starch copolymer and using the hydroxypropul starch copolymer as the preparation method of the capsule of raw material Download PDFInfo
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Abstract
The invention discloses a kind of hydroxypropul starch copolymer Capsules and preparation method thereof, belong to pharmaceutic adjuvant technical field, a kind of preparation method of hydroxypropul starch copolymer, it in turn includes the following steps: hydroxypropul starch, esterifying agent, catalyst is added in reaction vessel, pH value is adjusted, agitating and heating carries out polymerization reaction；Cellulose ether, condensing agent and reaction medium are added in reaction vessel, agitating and heating carries out polymerization reaction；After reaction, it is cooled to room temperature, precipitating reagent is added after reaction solution concentration, be filtered, washed and dry sediment after obtain hydroxypropul starch copolymer, using dipping method, using hydroxypropul starch copolymer as the preparation method of the plant capsule of primary raw material, the problems such as production cost generally existing in current plant hollow capsule manufacture is excessively high, complicated for operation, matter mark is unstable and quality is uncontrollable can be solved.
Description
Technical field:
The present invention relates to the preparation method of hydroxypropyl methyl cellulose copolymer and its plant capsule, belong to chemical synthesis and
Medical auxiliary materials technical field.
Background technique:
Capsule (Capsules) has many advantages, such as covering flavour of a drug, high-drug-effect, control sustained release and is widely used in drug, health care
In product and functional food.Currently, Capsules product in the market is substantially prepared with gelatin (Gelatin) for material.
Gelatin is to be made by the bone of animal, skin through hydrolyzing, and the unique structure feature of molecule, which makes it in the application, has be difficult to overcome to lack
Point makes gelatin shell water solubility be deteriorated, leads for example, being easy to be crosslinked with containing drugs such as aldehyde, reduced sugar base class compound and vitamin Cs
Cause the delay of capsule shells disintegration and capsule 's content dissolution；Gelatin can produce build-up of electrostatic charges in dry conditions, to subsequent
Processing has an impact；It is stored in the environment of low humidity for a long time, easily become fragile and cause capsule broken etc..Further, since faith and religion
The factor of aspect does not receive animal source capsule in Islam and minority name race, China area.In recent years, due to medicinal bright
Glue short supply agent holds at high price, and then causes toxic capsule event caused by domestic illegal enterprise's abuse industrial gelatine,
Cause social greatly fear, the exploitation of traditional gelatine capsule and production is even more allowed to make the matter worse.Therefore, there is an urgent need to research and develop to be used for
The virgin rubber capsule material of replacing gelatin.
In capsule pharmaceutic adjuvant market, plant capsule is one of fastest-rising product, and industry is generally believed and only used
Plant-based capsule replacing gelatin capsule is only the fundamental way for solving capsule persistent ailment.Some hydrophilic macromolecule foodstuff glues are such as tied
Cold glue, carragheen, xanthan gum, cellulose ether etc. are already used to the substitute that research prepares gelatine capsule.Wherein starch conduct
A kind of renewable natural resources has many advantages, such as abundance, cheap, easily biological-degradable, is that most potential capsule is former
Expect substitute.But there is also many defects for starch: do not dissolved in cold water, gelatinized corn starch viscosity it is unstable etc., make its application by
Greatly limitation.To make full use of starch resource and improving the economic value of starch, need to be modified starch to improve its property
Energy.Hydroxypropul starch is a kind of important etherificate converted starch, and there is gelatinization to stablize low, the paste transparency is high, filming performance is good etc.
Advantage is included by Capsules auxiliary material catalogue by version Chinese Pharmacopoeia in 2015.But single hydroxypropul starch Capsules are deposited
Brittle in film, the disadvantages of breakage rate is high, limits its large-scale application in preparing Capsules.Hydroxypropyl methylcellulose, ethoxy
The cellulose ethers such as cellulose are that have good in food and the common water soluble polyhydroxy high-molecular compound of field of pharmaceutical excipients
Film forming and flexibility, be also used for Capsules manufacture, such as " be used to prepare the phyteral glue and its hollow glue of Capsules
Capsule " (CN103933011), the inventions such as " a kind of production method of starch hollow capsule " (CN103830736) all employ fiber
Plain ether and starch blending system, but cellulose ether and hydroxypropul starch solution belong to thermodynamics Immiscible Polymer Blends, simple blend pole
The wild effects such as glue layering are easily caused, product quality is seriously affected.
Summary of the invention:
It is total to the object of the present invention is to provide a kind of hydroxypropul starch copolymer of replacing gelatin and using the hydroxypropul starch
Polymers is the preparation method of the plant capsule of primary raw material.
For achieving the above object, technical solution provided by the invention is as follows.
A kind of preparation method of Capsules hydroxypropul starch copolymer, it is characterised in that: it includes following parts by weight
The raw material of meter reacts, 100 parts of hydroxypropul starch, 1-30 parts of esterifying agent, 1-50 parts of cellulose ether, 0.1-1 parts of condensing agent；Its
Preparation method includes the following steps:
(1) it is esterified: hydroxypropul starch, esterifying agent and catalyst being added in reaction vessel, agitating and heating is reacted；
(2) it polymerize: cellulose ether, condensing agent and reaction medium is added in reaction vessel, agitating and heating is polymerize
Reaction；
(3) product extracts: after reaction, being cooled to room temperature, precipitating reagent is added after reaction solution concentration, is filtered, washed and does
Hydroxypropul starch copolymer is obtained after dry sediment.
Further, the preparation method of a kind of Capsules hydroxypropul starch copolymer, it includes following parts by weight meter
Raw material react, 100 parts of hydroxypropul starch, 5-30 parts of esterifying agent, 15-30 parts of cellulose ether, 0.1-1 parts of condensing agent.
Esterifying agent described in above-mentioned steps (1) be disodium hydrogen phosphate, sodium dihydrogen phosphate, sodium trimetaphosphate, sodium tripolyphosphate,
Chlorethoxyfos, acetic anhydride, vinylacetate, glacial acetic acid, ketenes, octenyl succinic acid anhydride, last of the ten Heavenly stems enetutanedioic acid anhydride, laurylene base
One of succinic anhydride, octadecylene base succinic anhydride are several, and preferred esterifying agent is disodium hydrogen phosphate, biphosphate
Sodium, acetic anhydride and octenyl succinic acid anhydride, charged material weight are the 1-30% of hydroxypropul starch dry weight.
Catalyst described in above-mentioned steps (1) is sodium hydroxide, sodium carbonate, tertiary sodium phosphate, magnesium hydroxide, sulfuric acid, acetic acid
One of ammonium is several, and preferred catalyst is sodium hydroxide, sodium carbonate.
Esterifying agent charged material weight described in above-mentioned steps (1) is the 1-30% of hydroxypropul starch dry weight.Preferred charged material weight
5-10%
Cellulose ether described in above-mentioned steps (2) is hydroxypropyl methylcellulose, hydroxypropyl cellulose, hydroxyethyl cellulose, carboxylic
One of methylcellulose is several.Preferred cellulose ether is hydroxypropyl methylcellulose, hydroxypropyl cellulose.
Cellulose ether charged material weight described in above-mentioned steps (2) is the 0.1-50% of hydroxypropul starch dry weight.Preferably feed intake
Weight is 15-30%
Condensing agent described in above-mentioned steps (2) is sodium trimetaphosphate, in sodium hexametaphosphate, phosphorus oxychloride, epoxychloropropane
One or several kinds.Preferred condensing agent sodium trimetaphosphate, sodium hexametaphosphate.
The buffer solution that reaction medium is deionized water or pH value is 3-12 described in above-mentioned steps (2).It is preferred anti-
Answering medium is the buffer solution that pH value is 5.5-9.
Reaction temperature described in above-mentioned steps (2) is room temperature to 30-80 DEG C, and the reaction time is 0.5-24 h.It is preferred anti-
Answering temperature is 40-70 DEG C, and the reaction time is 2-12 h.
Precipitating reagent described in above-mentioned steps (3) is one of ether, methanol, ethyl alcohol, isopropanol, acetone, dioxane
Or it is several.Preferred precipitating reagent is ethyl alcohol, acetone, and deal is 2-3 times of liquid weight after step (3) concentration.
Catalyst action mentioned in above-mentioned steps is to adjust the pH value of reaction environment.
More than one state the preparation method for the Capsules that hydroxypropul starch copolymer is primary raw material, including walk as follows
It is rapid:
It (1) is the increasing of the hydroxypropul starch copolymer of 10-35%, the flocculation aid of 0.05-5%, 0.1-20% by weight percent
Modeling agent is added to the water, and is heated with stirring to 35-90 DEG C system is made to be completely dissolved clarification and obtain glue；
(2) it by solvent under reduced pressure or evacuation and centrifugal degassing, is maintained in 35-60 DEG C, the template for preparing capsule is immersed into feed liquid, is used
It dips in embrane method and dips in film and form to obtain capsule；
(3) capsule cut after 25-45 DEG C of dry 0.5-5 h, pull out shell and obtains capsule finished product.
Further, above-mentioned using hydroxypropul starch copolymer as the preparation method step (1) of the Capsules of primary raw material
In, weight percent is the hydroxypropul starch copolymer of 15-30%, the plasticizer of the flocculation aid of 0.8-1%, 2-6% are added to the water,
It is heated with stirring to 45-50 DEG C system is made to be completely dissolved clarification and obtain glue.
It is above-mentioned solidifying using hydroxypropul starch copolymer to be helped described in the preparation method step (1) of the Capsules of primary raw material
Agent is one of pectin, xanthan gum, locust bean gum, carragheen, agar or several, and preferred flocculation aid is xanthan gum, card
Draw glue.
It is above-mentioned using hydroxypropul starch copolymer as plasticising described in the preparation method step (1) of the Capsules of primary raw material
Agent is one of glycerol, polyethylene glycol, ethylene glycol, glycerin diacetate, monoacetin, polypropylene glycol or several.
Preferred plasticizer is glycerol, polyethylene glycol, glycerin diacetate.
The invention has the benefit that existing capsule, it is incompatible that cellulose ether with hydroxypropul starch solution belongs to thermodynamics
System, simple blend easily cause the wild effects such as glue layering, seriously affect product quality, the invention patent scheme passes through
Lot of experiments finds that hydroxypropul starch has excellent compatibility after appropriate esterification modification with cellulose ether, and can be by dividing
The copolymer that activity hydroxy reaction in subchain generates is used to prepare plant hollow capsule, can effective integration both natural former materials
The excellent performance of material significantly improves the quality of hydroxypropul starch copolymerization composite capsule and can operate at Capsule technologies (dipping method)
Property, and plant capsule preparation cost is greatly lowered, which produces suitable for hydroxypropul starch plant capsule, can solve at present
The problems such as generally existing production cost is excessively high, complicated for operation, matter mark is unstable and quality is uncontrollable in plant capsule manufacture.
Specific embodiment:
Following example will be explained in detail the contents of the present invention, but the contents of the present invention are not limited solely to following implementation
Example.
Embodiment 1
A kind of hydroxypropul starch copolymer Capsules and preparation method thereof, preparation step is as follows: first by 50kg hydroxyl
Propyl starch, which is added in the 120kg water containing 5kg disodium hydrogen phosphate and 20kg sodium dihydrogen phosphate, adjusts 5.5,55 DEG C of pH value stirrings to add
10kg hydroxypropyl methylcellulose, 0.1kg sodium hexametaphosphate was added to reaction 1 hour in heat, adjusted pH to 9,55 DEG C are stirred to react 3 hours.
After reaction, it is cooled to room temperature, is concentrated into 90kg, 180kg ethyl alcohol is added, is sufficiently stirred, precipitates copolymer, be filtered, washed
And hydroxypropul starch copolymer 58kg is obtained after dry sediment.By weight percent be 15% hydroxypropul starch copolymer, 1%
Xanthan gum, 5% glycerol be added to the water, 50 DEG C agitating and heating 2 hours, so that system is completely dissolved clarification and obtain glue；Solvent subtracts
Pressure or evacuation and centrifugal degassing, are maintained in 45 DEG C, and the template that will prepare capsule immerses feed liquid, form to obtain glue with dipping in embrane method and dipping in film
Capsule；Capsule is cut after 40 DEG C of dry 1 h, fitting obtains capsule finished product.When using official method detection Capsules disintegration
It is limited to 6-13 minutes, takes 50 test friabilities, none is damaged.
Embodiment 2
A kind of hydroxypropul starch copolymer Capsules and preparation method thereof, preparation step is as follows: first by 10kg hydroxyl
Propyl starch is added in 40kg water, is slowly added to containing 0.8kg acetic anhydride, it is small that 8,35 DEG C of pH value of maintenance is stirred and heated to reaction 2
When, 3kg hydroxypropyl methylcellulose, 0.1kg epoxychloropropane is added, adjusts pH to 10,50 DEG C are stirred to react 2 hours.After reaction,
It is cooled to room temperature, is concentrated into 30kg, 60kg ethyl alcohol is added, is sufficiently stirred, precipitates copolymer, is filtered, washed and dry sediment
After obtain hydroxypropul starch copolymer 1 2.5kg.By weight percent be 15% hydroxypropul starch copolymer, 1% carragheen,
4% glycerol is added to the water, 50 DEG C agitating and heating 2 hours, so that system is completely dissolved clarification and obtain glue；Solvent under reduced pressure or from
Heart deaeration is maintained in 50 DEG C, and the template that will prepare capsule immerses feed liquid, forms to obtain capsule with dipping in embrane method and dipping in film；By capsule
Cutting, fitting obtain capsule finished product after 50 DEG C of dry 1 h.Use official method detection Capsules disintegration time limited for 7-15 points
Clock takes 50 test friabilities, none is damaged.
Embodiment 3
A kind of hydroxypropul starch copolymer Capsules and preparation method thereof, preparation step is as follows: first by 30kg hydroxyl
Propyl starch is added in the 90kg water containing 3kg octenyl succinic acid anhydride, and 35 DEG C are stirred and heated to reaction 10 hours, and 6kg is added
Hydroxyethyl cellulose, 0.1kg sodium hexametaphosphate adjust pH to 9, and 55 DEG C are stirred to react 3 hours.After reaction, it is cooled to room temperature, mistake
Filter, concentrated supernatant to 90kg are added 200kg methanol, are sufficiently stirred, precipitate copolymer, be filtered, washed and dry sediment
After obtain hydroxypropul starch copolymer 35kg.It is 25% hydroxypropul starch copolymer, 1% carragheen, 5% by weight percent
Ethylene glycol be added to the water, 55 DEG C agitating and heating 2 hours, so that system is completely dissolved clarification and obtain glue；Solvent under reduced pressure or from
Heart deaeration is maintained in 45 DEG C, and the template that will prepare capsule immerses feed liquid, forms to obtain capsule with dipping in embrane method and dipping in film；By capsule
Cutting, fitting obtain capsule finished product after 40 DEG C of dry 2 h.Use official method detection Capsules disintegration time limited for 5-10 points
Clock takes 50 test friabilities, none is damaged.
Embodiment 4
A kind of hydroxypropul starch copolymer Capsules and preparation method thereof, preparation step is as follows: first by 50kg hydroxyl
It is small to be stirred and heated to reaction 8 for 5.5,35 DEG C of pH value of tune in 120kg water of the propyl starch addition containing 5kg octadecylene base succinic anhydride
When, 10kg hydroxypropyl methylcellulose, 0.1kg sodium hexametaphosphate is added, adjusts pH to 9,55 DEG C are stirred to react 3 hours.After reaction,
It is cooled to room temperature, filters, concentrated supernatant to 90kg, 180kg methanol is added, is sufficiently stirred, precipitates copolymer, be filtered, washed
And hydroxypropul starch copolymer 58kg is obtained after dry sediment.By weight percent be 25% hydroxypropul starch copolymer,
0.8% carragheen, 6% polyethylene glycol are added to the water, 50 DEG C agitating and heating 2 hours, so that system is completely dissolved clarification and obtain glue
Liquid；Solvent under reduced pressure or evacuation and centrifugal degassing are maintained in 50 DEG C, will prepare capsule template immerse feed liquid, with dip in embrane method dip in film at
Type obtains capsule；Capsule is cut after 40 DEG C of dry 3h, fitting obtains capsule finished product.Capsules are detected using official method
Disintegration time limited is 6-11 minutes, takes 50 test friabilities, none is damaged.
Embodiment 5
A kind of hydroxypropul starch copolymer Capsules and preparation method thereof, preparation step is as follows: first by 20kg hydroxyl
Propyl starch, which is added in the 60kg water containing 1kg phosphorus oxychloride, adjusts 8,55 DEG C of pH value to be stirred and heated to reaction 1 hour, and 3kg is added
Hydroxypropyl methylcellulose, 0.2kg sodium hexametaphosphate adjust pH to 9, and 55 DEG C are stirred to react 5 hours.After reaction, it is cooled to room temperature, mistake
Filter, concentrated supernatant to 50kg are added 100kg acetone, are sufficiently stirred, precipitate copolymer, be filtered, washed and dry sediment
After obtain hydroxypropul starch copolymer 21kg.It is 18% hydroxypropul starch copolymer, 1% carragheen, 4% by weight percent
Glycerol be added to the water, 50 DEG C agitating and heating 2 hours, so that system is completely dissolved clarification and obtain glue；Solvent under reduced pressure or centrifugation
Deaeration is maintained in 50 DEG C, and the template that will prepare capsule immerses feed liquid, forms to obtain capsule with dipping in embrane method and dipping in film；Capsule is existed
Cutting, fitting obtain capsule finished product after 45 DEG C of 1 h of drying.Use official method detection Capsules disintegration time limited for 9-18 points
Clock takes 50 test friabilities, none is damaged.
Embodiment 6
A kind of hydroxypropul starch copolymer Capsules and preparation method thereof, preparation step is as follows: first by 100kg hydroxyl
Propyl starch is added in 60kg glacial acetic acid, and 80 DEG C are stirred to react 10 hours, and recycling removes remaining glacial acetic acid, and 100kg water is added,
20kg hydroxypropyl cellulose, 0.1kg sodium hexametaphosphate adjust pH to 9, and 55 DEG C are stirred to react 4 hours.After reaction, it is cooled to room
Temperature, filtering, concentrated supernatant to 150kg are added 300kg ethyl alcohol, are sufficiently stirred, precipitate copolymer, be filtered, washed and dry
Hydroxypropul starch copolymer 1 15kg is obtained after sediment.It is 15% hydroxypropul starch copolymer, 1% card by weight percent
Draw glue, 4% glycerol be added to the water, 50 DEG C agitating and heating 2 hours, so that system is completely dissolved clarification and obtain glue；Solvent under reduced pressure or
Person's evacuation and centrifugal degassing is maintained in 50 DEG C, and the template that will prepare capsule immerses feed liquid, forms to obtain capsule with dipping in embrane method and dipping in film；It will
Capsule is cut after 45 DEG C of dry 1.5h, fitting obtains capsule finished product.Use official method detection Capsules disintegration time limited for
5-13 minutes, 50 test friabilities are taken, none is damaged.
Embodiment 7
A kind of hydroxypropul starch copolymer Capsules and preparation method thereof, preparation step is as follows: first by 50kg hydroxyl
Propyl starch is added in the 120kg water containing 5kg last of the ten Heavenly stems enetutanedioic acid anhydride, and 25 DEG C are stirred to react 18 hours, and 15kg hydroxypropyl is added
Methylcellulose, 0.2kg sodium hexametaphosphate adjust pH to 9, and 55 DEG C are stirred to react 5 hours.After reaction, it is cooled to room temperature, filters,
Concentrated supernatant is added 200kg ethyl alcohol, is sufficiently stirred, precipitates copolymer to 90kg, be filtered, washed and dry sediment after
Obtain hydroxypropul starch copolymer 58kg.It is 30% hydroxypropul starch copolymer, 1% carragheen, 2% by weight percent
Glycerin diacetate is added to the water, 50 DEG C agitating and heating 2 hours, so that system is completely dissolved clarification and obtain glue；Solvent under reduced pressure or
Person's evacuation and centrifugal degassing is maintained in 50 DEG C, and the template that will prepare capsule immerses feed liquid, forms to obtain capsule with dipping in embrane method and dipping in film；It will
Capsule is cut after 35 DEG C of dry 1 h, fitting obtains capsule finished product.Use official method detection Capsules disintegration time limited for 4-
9 minutes, 50 test friabilities are taken, none is damaged.
Embodiment 8
A kind of hydroxypropul starch copolymer Capsules and preparation method thereof, preparation step is as follows: first by 25kg hydroxyl
Propyl starch is added in the 60kg water containing 2kg disodium hydrogen phosphate and 3kg sodium dihydrogen phosphate, adjusts 5,45 DEG C of pH value and is stirred and heated to
4kg carboxymethyl cellulose, 0.1kg Sodium metaphosphate is added in reaction 3 hours, adjusts pH to 9,55 DEG C are stirred to react 5 hours.Reaction
After, it is cooled to room temperature, filters, concentrated supernatant to 60kg, 180kg ethyl alcohol is added, is sufficiently stirred, precipitates copolymer, mistake
Hydroxypropul starch copolymer 27kg is obtained after filter, washing and dry sediment.The hydroxypropul starch that weight percent is 15% is total to
Polymers, 1% locust bean gum, 0.1% potassium citrate, 4% polypropylene glycol be added to the water, 50 DEG C agitating and heating 2 hours, make body
System is completely dissolved clarification and obtains glue；Solvent under reduced pressure or evacuation and centrifugal degassing are maintained in 50 DEG C, and the template for preparing capsule is immersed
Feed liquid forms to obtain capsule with dipping in embrane method and dipping in film；Capsule is cut after 35 DEG C of dry 1 h, fitting obtains capsule finished product.Using
Official method detection Capsules disintegration time limited is 5-12 minutes, takes 50 test friabilities, none is damaged.
Claims (3)
1. the Capsules preparation method of hydroxypropul starch copolymer, it is characterised in that: it includes the original of following parts by weight meter
Material reacts, 100 parts of hydroxypropul starch, 1-30 parts of esterifying agent, 15-30 parts of cellulose ether, 0.1-1 parts of condensing agent；It is prepared
Method includes the following steps:
(1) it is esterified: hydroxypropul starch, esterifying agent and catalyst being added in reaction vessel, agitating and heating is reacted, described
Esterifying agent be disodium hydrogen phosphate, sodium dihydrogen phosphate, sodium trimetaphosphate, sodium tripolyphosphate, phosphorus oxychloride, acetic anhydride, acetic acid second
Enester, glacial acetic acid, ketenes, octenyl succinic acid anhydride, last of the ten Heavenly stems enetutanedioic acid anhydride, dodecenylsuccinic anhydride, octadecylene base fourth
One of dicarboxylic anhydride is several, and charged material weight is the 1-30% of hydroxypropul starch dry weight；The catalyst is hydroxide
One of sodium, sodium carbonate, tertiary sodium phosphate, magnesium hydroxide, sulfuric acid, ammonium acetate are several；
(2) it polymerize: cellulose ether, condensing agent and reaction medium is added in reaction vessel, agitating and heating carries out polymerization reaction,
The cellulose ether is one of hydroxypropyl methylcellulose, hydroxypropyl cellulose, carboxymethyl cellulose, and cellulose ether feeds intake again
Amount is the 15-30% of hydroxypropul starch dry weight；The condensing agent is one of sodium trimetaphosphate, calgon or several
Kind；
(3) product extracts: after reaction, being cooled to room temperature, precipitating reagent is added after reaction solution concentration, it is heavy to be filtered, washed and dry
Hydroxypropul starch copolymer is obtained after starch.
2. the Capsules according to claim 1 preparation method of hydroxypropul starch copolymer, it is characterised in that: step
(2) reaction temperature described in is 40-70 DEG C, reaction time 2-12h.
3. the Capsules according to claim 1 preparation method of hydroxypropul starch copolymer, it is characterised in that: step
(2) buffer solution that the reaction medium described in is deionized water or pH value is 5.5-9.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102952280A (en) * | 2012-08-23 | 2013-03-06 | 安徽大学 | Hydroxypropyl methylcellulose copolymer for preparing plant capsules and preparation method thereof |
| CN103087264A (en) * | 2013-01-27 | 2013-05-08 | 桂林理工大学 | Preparation method of amphipathic acrylic acid/maleic anhydride (AA/MA) grafted esterified hydroxypropyl cassava starch |
| CN103638001A (en) * | 2013-12-10 | 2014-03-19 | 中国科学院长春应用化学研究所 | Vegetable hard capsules and preparation method thereof |
| CN103830736A (en) * | 2014-03-05 | 2014-06-04 | 中国科学院青岛生物能源与过程研究所 | Production method of starch empty capsule |
| CN104530491A (en) * | 2014-12-15 | 2015-04-22 | 浙江中同科技有限公司 | Preparation method of amylocellulose composite material |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102952280A (en) * | 2012-08-23 | 2013-03-06 | 安徽大学 | Hydroxypropyl methylcellulose copolymer for preparing plant capsules and preparation method thereof |
| CN103087264A (en) * | 2013-01-27 | 2013-05-08 | 桂林理工大学 | Preparation method of amphipathic acrylic acid/maleic anhydride (AA/MA) grafted esterified hydroxypropyl cassava starch |
| CN103638001A (en) * | 2013-12-10 | 2014-03-19 | 中国科学院长春应用化学研究所 | Vegetable hard capsules and preparation method thereof |
| CN103830736A (en) * | 2014-03-05 | 2014-06-04 | 中国科学院青岛生物能源与过程研究所 | Production method of starch empty capsule |
| CN104530491A (en) * | 2014-12-15 | 2015-04-22 | 浙江中同科技有限公司 | Preparation method of amylocellulose composite material |
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