CN101870755B - Glutinous rice starch/acrylic ester interpolymer and composite and application thereof - Google Patents
Glutinous rice starch/acrylic ester interpolymer and composite and application thereof Download PDFInfo
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- CN101870755B CN101870755B CN 200910068583 CN200910068583A CN101870755B CN 101870755 B CN101870755 B CN 101870755B CN 200910068583 CN200910068583 CN 200910068583 CN 200910068583 A CN200910068583 A CN 200910068583A CN 101870755 B CN101870755 B CN 101870755B
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Abstract
The invention relates to a glutinous rice starch/acrylic ester interpolymer and a composite and an application thereof. The glutinous rice starch/acrylic ester interpolymer is a product by adopting crylic acid and esters monomer thereof to be copolymerized with the glutinous rice starch, wherein the glutinous rice starch comprises one or a mixture of a plurality of starch of sticky rice, glutinous rice, glutinous corn, millet, glutinous broom corn and glutinous husked kaoliang and modified starch thereof, wherein the glutinous rice starch/acrylic ester interpolymer and the composite forming by the glutinous rice starch/acrylic ester interpolymer and starch or modified starch as well as cross-linking agent are used as water absorbent, tackifier, adhesive, thickener and solubilizer, and are used as medicinal preparation auxiliary materials in medicine tablet, capsule, gels, emulsion, electuary, film agent, poultice and patch.
Description
Technical field
The present invention relates to glutinous rice starch/Yodo Sol GH 28 and compsn thereof and application.This multipolymer has good viscosity, water-absorbent, ventilation property, and therefore, the present invention is suitable for pharmaceutical tamanori, pressure sensitive adhesive component, medicine sustained and controlled release carrier material application.
Background technology
The pressure sensitive adhesive of rubber-like mainly is to be main raw material and to add tackifier, tenderizer and oxidation inhibitor, stablizer etc. with natural or viton as the main pressure sensitive adhesive kind of using on the skin.Pressure sensitive adhesive with these feedstock production is hydrophobic, can not effectively absorb moisture, therefore can cause pasting position ponding, causes the skin whiting.The low-molecular-weight component of being added in addition, can be infiltrated skin and caused untoward reactions such as allergy.The appearance of polyacrylate(s) pressure sensitive adhesive is that one of traditional pressure sensitive adhesive is improved greatly, and it has overcome some shortcomings of rubber-like pressure sensitive adhesive.Because this type tackiness agent has autohension, low-molecular-weight materials such as the modifier that therefore needn't interpolation in the preparation process can cause allergic reaction, tackifier.But problem is that present polyacrylate(s) pressure sensitive adhesive is solvent-borne type, aqueous emulsion type basically, need volatilize in the use and desolvate or water, causes the waste of the environmental pollution and the energy, is particularly useful for the percutaneous administration patch complex manufacturing, poor practicability.The cataplasma that is cross-linked to form based on ZX-I and metal-salt that development in recent years is got up; Owing to wetting ability, need not organic solvent and be beneficial to characteristics such as drug release; Receive the concern of medical field, but that the shortcoming of this type pressure sensitive adhesive matrix is a viscosity is relatively poor, it is complicated to form, production technique is wayward.
Though rice flour such as polyacrylic acid modified starch, sticky rice flour as a kind of natural glutinous rice material, have been applied in the tamanori field of fluting board, label, coating etc., use also rare report as pressure sensitive adhesive and medicine controlled release carrier.Chinese patent CN02100464.1 has reported a kind of carrier of exterior-applied medicines and preparation method thereof; Be by having strongly adherent farm crop glutinous rice pulvis, halogen powder, water three by ratio of weight and the number of copies 6 after cooking: 4-7: 1.8-2.3 and the soft cheese carrier processed with viscosity; Processing and the equal non-pollutant discharge of use have environment friendly.But easy dehydration when this material is placed or attached and hardening, the attaching time is short, also exists ripe glutinous rice pudding to return living problem, therefore, is not applied.
Summary of the invention
The purpose of this invention is to provide a kind of glutinous rice starch/Yodo Sol GH 28 and compsn and application.Utilize the characteristics that have viscosity after natural product glutinous rice starch and the water mixing slaking; Carry out modification through the acrylic ester monomer copolymerization; Prepare polymeric articles water-soluble, that viscosity good and intensity is high, for percutaneous dosing matrix, wound dressings and oral drug preparation provide one type to have renewable resources property, energy-saving and emission-reduction, environment friendly and pharmaceutical pressure-sensitive adhesive and water-absorbent film easy to use.It is cheap and easy to get to have starting material, synthetic and application art is simple, easy handling, advantage such as aftertreatment technology is easy.
The present invention provides a kind of glutinous rice starch/Yodo Sol GH 28, is the multipolymer of glutinous rice starch and vinylformic acid and esters monomer thereof.
Described glutinous rice starch is glutinous rice, glutinous rice, glutinous corn, Radix Et Rhizoma Rhei rice, small Semen setariae, glutinous sorghum rice, the starch of milled glutinous broomcorn millet and one or more mixtures of treated starch thereof; Described vinylformic acid and esters monomer thereof are selected from vinylformic acid, methylacrylic acid and (methyl) acrylic ester monomer, and ester group wherein contains 1～18 carbon atom.
Described vinylformic acid and esters monomer thereof are selected from vinylformic acid; Methylacrylic acid; Hydroxyethyl acrylate; Rocryl 400; Methyl acrylate; Ethyl propenoate; The vinylformic acid n-propyl; Isopropyl acrylate; N-butyl acrylate; NSC 20949; The vinylformic acid n-pentyl ester; The vinylformic acid isopentyl ester; The just own ester of vinylformic acid; Isooctyl acrylate monomer; The vinylformic acid n-octyl; Isodecyl acrylate; Vinylformic acid ester in the positive last of the ten Heavenly stems; Vinylformic acid ester in the different ninth of the ten Heavenly Stems; TEB 3K; Jia Jibingxisuanyizhi; N propyl methacrylate; Isopropyl methacrylate; N-BMA; Propenoic acid, 2-methyl, isobutyl ester; The methylacrylic acid n-pentyl ester; The methacrylic isoamyl valerate; The just own ester of methylacrylic acid; Isooctyl methacrylate; N octyl methacrylate; Isodecyl methacrylate; Methylacrylic acid ester in the positive last of the ten Heavenly stems; In the methylacrylic acid ester in the different ninth of the ten Heavenly Stems one or more.
The mass ratio of described glutinous rice starch and vinylformic acid and esters monomer thereof is 0.05-20: 1; Water-soluble monomer accounts for the 10-100% of monomer total mass.
The present invention provides a kind of step that comprises with the preparation method of glutinous rice starch/Yodo Sol GH 28: under nitrogen protection, with the aqueous dispersion of starch gelatinization, adding alkali, to regulate pH be alkaline (8～11), to increase its gelatinization degree under 80～100 ℃; Cool to then below 60 ℃, slowly add vinylformic acid and esters monomer thereof after the adding water soluble starter, 60～80 ℃ were reacted 3～24 hours down; The pH value that adds the alkali regulation system then is extremely neutral, steams and removes moisture content, and dry, pulverizing obtains the powder of glutinous rice starch/Yodo Sol GH 28.The preferred Potassium Persulphate of initiator, H
2O
2, ammonium persulphate, cerous ammonium nitrate, 2,2-azo [2-(2-tetrahydroglyoxaline-2-yl) propane] dihydrochloride, consumption is monomeric 0.01%～5%.
The present invention provides a kind of compsn of glutinous rice starch/Yodo Sol GH 28, and quality is formed and comprised:
Glutinous rice starch/Yodo Sol GH 28 0.01%～99.98%
Starch or treated starch 0～99.98%
Linking agent 0.01%～10%
Described starch is W-Gum, wheat starch, sweet potato starch, yam starch, glutinous rice starch etc., and treated starch is cationic starch, CMS, Sumstar 190, phosphate ester starch, acetate starch, toxilic acid esterification starch and the alkyl esterification starch that contains 5～18 carbon atoms etc.
Described linking agent is selected from one or more in tripoly phosphate sodium STPP, borax, POCl3, epoxy chloropropane, the Trisodium trimetaphosphate, preferred borax, Trisodium trimetaphosphate.
The method of use of above-mentioned compsn: by metering the aqueous dispersions of the mixture of glutinous rice starch/Yodo Sol GH 28, starch or treated starch is heated to slaking more than 80 ℃, regulating pH before or after the slaking is 8～11, mixes moulding again with linking agent; Perhaps glutinous rice starch/Yodo Sol GH 28, starch or treated starch, linking agent are mixed forming aqueous dispersions in water, regulating pH is 8～11, is heated to slaking moulding more than 80 ℃; Perhaps glutinous rice starch/Yodo Sol GH 28, starch or treated starch, linking agent are mixed forming aqueous dispersions in water, be heated to slaking more than 80 ℃, regulating pH then is 8～11, moulding; Above-mentionedly obtain to such an extent that compsn room temperature or heating were placed 0.5～10 day, promptly get cross-linking products.
Above-mentioned compsn can with the composite application of following composition: comprise liquid plasticizer, like glycerine, polyoxyethylene glycol, terepthaloyl moietie, Ucar 35, butyleneglycol, pyrrolidone, plant wet goods liquid; Medicine, health care composition, biological activity, permeate promotor; Polymers such as Z 150PH, natural gum, PVP K120, ROHM or its sodium salt, gelatin, Mierocrystalline cellulose and verivate thereof, protein, polypeptide, DNA, sodium-alginate; And binder components such as tackifier, antiseptic-germicide, toughener, wetting Agent for Printing Inks such as kaolin, titanium oxide, zinc oxide, micropowder silica gel, Ucar 35, sorbyl alcohol, food and cosmetics additive etc.Above-mentioned softening agent, medicine etc. add composition can be as required before or after slaking, linking agent add before or after, add before and after the pH regulator.
The compsn of glutinous rice starch/Yodo Sol GH 28 of the present invention has plasticity-before cross moulding; Can be processed into random shape; As be coated with and form pressure sensitive adhesive paster, film forming, be put into die for molding and process products such as various sheets, column, be particularly useful for carrier and sustained-release preparation and the percutaneous administration patch and the film of medicine or other composition.
Glutinous rice starch/Yodo Sol GH 28 provided by the invention can be used as water-retaining agent, tackifier, tamanori, thickening material, solubilizing agent use, and is used for medicinal tablet, capsule, gelifying agent, emulsion, paste, film, cataplasma and patch as the pharmaceutical prepn auxiliary material.
Glutinous rice starch/Yodo Sol GH 28 provided by the invention can be used as the moity of catablasm base material; With ZX-I, linking agent, weighting agent, wetting Agent for Printing Inks, pH regulator agent, cross-linking regulator, etc. additive form cross-linking system, be used to prepare medicine cataplasma or paster.
Glutinous rice starch/Yodo Sol GH 28 provided by the invention is water-soluble or have a water-absorbent; Has higher viscosity and intensity; Can be used as tackifier and tamanori uses; Its cross-linked composition possess hydrophilic property, but water absorption and swelling but water insoluble, characteristics be viscosity can through form, tamanori consumption and crosslinking degree regulate; Can with compatibilities such as water miscible polymkeric substance, tensio-active agent, hydrogel and nanoparticle or micella; Be suitable for the load of medicines of different nature such as synthetic drug, Chinese medical concrete, micro mist, obtain to have the pressure sensitive adhesive, medicine film, tablet of suitable viscosity and drug release character etc., the needs of adaptation different pharmaceutical transdermal absorption formulation.
The cross-linked composition that makes through above-mentioned preparation method is particularly useful for the patch of Chinese medical concrete and micro mist; Have drug loading height, skin adhesion good, notice and painless repeatedly; Can room temperature again can comparatively high temps (below 100 ℃) hybrid medicine be coated with, press mold processing, can the direct slicing packing after the coating.Therefore, the pressure-sensitive adhesive product use range among the present invention is wide, does not especially need high-temperature operation, has overcome the hot-fusible pressure-sensitive adhesive high-temperature fusion to the waste to the energy of the infringement of medicine isoreactivity composition and high temperature; On the other hand, can not need dry by the fire, produce and packing can serialization, overcome the problem that existing cataplasma water soluble pressure-sensitive adnesive exists except that moisture.In addition, the product among the present invention does not use any organic solvent, has the environmental protection characteristics.Therefore; The present invention will have broad application prospects at medical and field of food; Use as water-retaining agent, tackifier, tamanori, thickening material, solubilizing agent, and be used for medicinal tablet, capsule, gelifying agent, emulsion, paste, film, cataplasma and patch as the pharmaceutical prepn auxiliary material.
In a word, multipolymer of the present invention has good viscosity, water-absorbent, ventilation property, and therefore, the present invention is applicable to pharmaceutical pressure sensitive adhesive, medicine sustained and controlled release carrier material application.
Description of drawings:
Fig. 1 is the nmr spectrum of the glutinous rice starch/Yodo Sol GH 28 (AS1 and AS2) of glutinous rice starch, embodiment 1 and 2 preparations.
Fig. 2 is the infrared spectrogram of glutinous rice starch, AS1 and AS2.
Embodiment:
With embodiment the present invention is further explained below.
Instance 1:
In a four-hole boiling flask, add glutinous rice starch 6g, zero(ppm) water 60g is heated to 80 ℃ of gelatinizations 30 minutes under nitrogen protection and agitation condition; Cool to 60 ℃, add several sodium hydroxide solutions and regulate pH=9～10, take by weighing Potassium Persulphate 0.1g,, slowly be added drop-wise in the reactor drum, keep homo(io)thermism to stir 10～30 minutes with the less water dissolving; Add 1g vinylformic acid and 5g NSC 20956 then, reacted 3 hours down at 65～70 ℃; It is neutral to regulate pH, and discharging after the portion water is removed in decompression, dry, grind, and obtains glutinous rice starch/Yodo Sol GH 28 AS1.
Instance 2:
In a four-hole boiling flask, add glutinous rice starch 6g, zero(ppm) water 40g is heated to 90 ℃ of gelatinizations 20 minutes under nitrogen protection and agitation condition; Cool to 60 ℃, add several saturated sodium bicarbonate aqueous solutions and regulate pH=9, take by weighing Potassium Persulphate 0.1g,, slowly be added drop-wise in the reactor drum, keep homo(io)thermism to stir 10 minutes with the less water dissolving; Add 1g methylacrylic acid and 2g Bing Xisuandingzhi then, reacted 12 hours down at 65～70 ℃; It is neutral to regulate pH, discharging after the portion water that reduces pressure away, and dry, grinding obtains glutinous rice starch/Yodo Sol GH 28 AS2.
Fig. 1 is the nmr spectrum of the glutinous rice starch/Yodo Sol GH 28 (AS1 and AS2) of glutinous rice starch, embodiment 1 and 2 preparations.With the nmr spectrum contrast of glutinous rice starch, the methyl on methylacrylic acid and the butyl acrylate units, the characteristic peak of methylene radical are appearring in the spectrogram of AS1 and AS2 between 0.9～1.8ppm.
Fig. 2 is the infrared spectrogram of glutinous rice starch, AS1 and AS2.Can find out that AS1 and AS2 are at 1712cm
-1The characteristic peak of ester C=O has appearred in the place, 1400,1560cm
-1The charateristic avsorption band of carboxylate salt appears in the place, and the stretching vibration peak of C-O obviously strengthens at 1030～1150cm-1 place, show pass through graft copolymerization after.The above results shows that (methyl) acrylic acid and two kinds of monomers of (methyl) Bing Xisuandingzhi successfully have been grafted on the starch chain.
Instance 3:
In a four-hole boiling flask, add glutinous W-Gum 1g, zero(ppm) water 100g is heated to 90～100 ℃ of gelatinizations 20 minutes under nitrogen protection and agitation condition; Cool to 60 ℃, add several 10% sodium hydroxide solutions, making pH is 9～10, takes by weighing Potassium Persulphate 0.2g, with the less water dissolving, slowly is added drop-wise in the reactor drum, keeps homo(io)thermism to stir 10 minutes; Add 8g methylacrylic acid, 6g vinylformic acid, 4g isopropyl acrylate and 2g Isooctyl acrylate monomer then, reacted 16 hours down at 65～70 ℃; Add NaOH solution and regulate pH neutrality, discharging after the portion water that reduces pressure away, dry, grinding obtains glutinous rice starch/Yodo Sol GH 28 AS3.
Instance 4:
In a four-hole boiling flask, add glutinous rice starch 10g, zero(ppm) water 100g is heated to 85 ℃ of gelatinizations 25 minutes under nitrogen protection and agitation condition; Cool to 60 ℃, add several sodium carbonate solutions, pH=8 takes by weighing Potassium Persulphate 0.02g, with the less water dissolving, slowly is added drop-wise in the reactor drum, keeps homo(io)thermism to stir 20 minutes; Add 0.5g Hydroxyethyl acrylate and 0.5g stearyl methacrylate then, reacted 3 hours down at 65～70 ℃; Discharging after the portion water is removed in decompression, and is dry, grind, and obtains glutinous rice starch/Yodo Sol GH 28 AS4.
Instance 5:
In a four-hole boiling flask, add Radix Et Rhizoma Rhei rice starch 20g, zero(ppm) water 200g is heated to 90～95 ℃ of gelatinizations 40 minutes under nitrogen protection and agitation condition; Cool to 60 ℃, add several sodium hydrogen carbonate solutions, pH=9 takes by weighing ammonium persulphate 0.02g, with the less water dissolving, slowly is added drop-wise in the reactor drum, keeps homo(io)thermism to stir 10 minutes; The mixture that adds 0.3g Rocryl 400 and 0.7g Isooctyl methacrylate then reacted 4 hours down at 65～70 ℃; It is neutral to regulate pH, discharging after the portion water that reduces pressure away, and dry, grinding obtains glutinous rice starch/Yodo Sol GH 28 AS5.
Instance 6:
In a four-hole boiling flask, add waxy corn starch 5g, zero(ppm) water 60g is heated to 80～90 ℃ of gelatinizations 30 minutes under nitrogen protection and agitation condition; Cool to 60 ℃, add several sodium hydroxide solutions, pH=11 takes by weighing ydrogen peroxide 50 0.3g, with the less water dissolving, slowly is added drop-wise in the reactor drum, keeps homo(io)thermism to stir 10 minutes; The mixture that adds 3.6g methylacrylic acid, 2.4g vinylformic acid and 4g NSC 11786 then reacted 12 hours down at 65～70 ℃; It is neutral to regulate pH, discharging after the portion water that reduces pressure away, and dry, grinding obtains glutinous rice starch/Yodo Sol GH 28 AS6.
Embodiment 7:
In a four-hole boiling flask, add small Semen setariae starch 4g, zero(ppm) water 60g is heated to 80～90 ℃ of gelatinizations 30 minutes under nitrogen protection and agitation condition; Cool to 60 ℃, add several sodium hydroxide solutions, pH=10.Take by weighing ydrogen peroxide 50 0.2g,, slowly be added drop-wise in the reactor drum, keep homo(io)thermism to stir 10 minutes with the less water dissolving; The mixture that adds 1g methylacrylic acid, 5g TEB 3K, 4g N-Hexyl methacrylate then reacted 12 hours down at 65～70 ℃; It is neutral to regulate pH, discharging after the portion water that reduces pressure away, and dry, grinding obtains glutinous rice starch/Yodo Sol GH 28 AS7.
Embodiment 8:
In a four-hole boiling flask, add oxidation glutinous rice starch 4g, zero(ppm) water 60g is heated to 80～90 ℃ of gelatinizations 30 minutes under nitrogen protection and agitation condition; Cool to 60 ℃, add several sodium carbonate solutions, make pH be about 10, take by weighing 2,2-azo [2-(2-tetrahydroglyoxaline-2-yl) propane] dihydrochloride 0.1g with the less water dissolving, slowly is added drop-wise in the reactor drum, keeps homo(io)thermism to stir 10 minutes; The mixture that adds 1g methylacrylic acid, 1g vinylformic acid, 0.5g Jia Jibingxisuanyizhi, 4g Bing Xisuandingzhi then reacted 24 hours down at 70～75 ℃; Discharging after the portion water that reduces pressure away, dry, grinding obtains glutinous rice starch/Yodo Sol GH 28 AS8.
Embodiment 9:
In a four-hole boiling flask, add toxilic acid esterification glutinous rice starch 4g, zero(ppm) water 60g is heated to 80～90 ℃ of gelatinizations 30 minutes under nitrogen protection and agitation condition; Cool to 60 ℃, add several sodium carbonate solutions, pH=8.5 takes by weighing ydrogen peroxide 50 0.1g, with the less water dissolving, slowly is added drop-wise in the reactor drum, keeps homo(io)thermism to stir 10 minutes; The mixture that adds 2g methylacrylic acid, 1.5g ethyl propenoate, 4g Bing Xisuandingzhi then reacted 12 hours down at 65～70 ℃; It is neutral to regulate pH, discharging after the portion water that reduces pressure away, and dry, grinding obtains glutinous rice starch/Yodo Sol GH 28 AS9.
Embodiment 10:
In a four-hole boiling flask, add acetic acid esterification glutinous rice starch 6g, zero(ppm) water 60g is heated to 80～90 ℃ of gelatinizations 30 minutes under nitrogen protection and agitation condition; Cool to 60 ℃, add several sodium carbonate solutions, take by weighing ydrogen peroxide 50 0.1g,, slowly be added drop-wise in the reactor drum, keep homo(io)thermism to stir 30 minutes with the less water dissolving; The mixture that adds 2g methylacrylic acid, 1.5g methyl acrylate, 2g Bing Xisuandingzhi, 1.5g vinylformic acid n-octyl then reacted 12 hours down at 65～70 ℃; It is neutral to regulate pH, discharging after the portion water that reduces pressure away, and dry, grinding obtains glutinous rice starch/Yodo Sol GH 28 AS10.
Embodiment 11:
In a four-hole boiling flask, add laurylene base succinic acid esterification glutinous rice starch 10g, zero(ppm) water 60g is heated to 100 ℃ of gelatinizations 30 minutes under nitrogen protection and agitation condition; Cool to 60 ℃, add several sodium carbonate solutions, take by weighing cerous ammonium nitrate 0.3g,, slowly be added drop-wise in the reactor drum, keep homo(io)thermism to stir 10 minutes with the less water dissolving; The mixture that adds 5g methylacrylic acid, 1.5g octadecyl acrylate, 2g n propyl methacrylate, 2.5g vinylformic acid n-octyl then reacted 12 hours down at 75～80 ℃; It is neutral to regulate pH, and discharging after the portion water is removed in decompression, dry, grind, and obtains glutinous rice starch/Yodo Sol GH 28 AS11.
Embodiment 12:
In a four-hole boiling flask, add glutinous sorghum rice starch 10g, zero(ppm) water 60g is heated to 90～100 ℃ of gelatinizations 20 minutes under nitrogen protection and agitation condition; Cool to 60 ℃, add several sodium carbonate solutions, take by weighing Potassium Persulphate 0.1g,, slowly be added drop-wise in the reactor drum, keep homo(io)thermism to stir 10 minutes with the less water dissolving; The mixture that adds 2g Rocryl 410,1.5g dodecyl acrylate, 2g n propyl methacrylate, 1.5g vinylformic acid n-octyl then reacted 2 hours down at 65～70 ℃; Discharging after the portion water that reduces pressure away, dry, grinding obtains glutinous rice starch/Yodo Sol GH 28 AS12.
Embodiment 13:
In a four-hole boiling flask, add the glutinous Starch rice 10g of stearic acid esterification, zero(ppm) water 60g is heated to 80～90 ℃ of gelatinizations 30 minutes under nitrogen protection and agitation condition; Cool to 60 ℃, add several sodium carbonate solutions, take by weighing Potassium Persulphate 0.5g,, slowly be added drop-wise in the reactor drum, keep homo(io)thermism to stir 10 minutes with the less water dissolving; Add 4g vinylformic acid then, reacted 16 hours down at 65～70 ℃; It is neutral to regulate pH, discharging after the portion water that reduces pressure away, and dry, grinding obtains glutinous rice starch/Yodo Sol GH 28 AS13.
Embodiment 14:
In a four-hole boiling flask, add glutinous rice starch 10g, zero(ppm) water 40g is heated to 90 ℃ of gelatinizations 20 minutes under nitrogen protection and agitation condition; Cool to 60 ℃, add several saturated sodium bicarbonate aqueous solutions and regulate pH=9, take by weighing Potassium Persulphate 0.02g,, slowly be added drop-wise in the reactor drum, keep homo(io)thermism to stir 10 minutes with the less water dissolving; Add 0.5g methylacrylic acid and 0.5g Bing Xisuandingzhi then, reacted 3 hours down at 60 ℃; It is neutral to regulate pH, discharging after the portion water that reduces pressure away, and dry, grinding obtains glutinous rice starch/Yodo Sol GH 28 AS14.
Embodiment 15:
In a four-hole boiling flask, add octenyl succinate glutinous rice starch 6g, zero(ppm) water 60g is heated to 80～90 ℃ of gelatinizations 30 minutes under nitrogen protection and agitation condition; Cool to 60 ℃, add several sodium carbonate solutions, take by weighing ydrogen peroxide 50 0.1g,, slowly be added drop-wise in the reactor drum, keep homo(io)thermism to stir 10 minutes with the less water dissolving; The mixture that adds 0.5g methacrylic methyl esters, 1g methacrylic isoamyl valerate, 1g vinylformic acid ester in the ninth of the ten Heavenly Stems, 0.5g isodecyl acrylate then reacted 2 hours down at 65～70 ℃; Discharging after the portion water that reduces pressure away, dry, grinding obtains glutinous rice starch/Yodo Sol GH 28 AS15.
10% viscosity in aqueous solution of glutinous rice starch/Yodo Sol GH 28 that embodiment 1～15 makes is seen table 1.
5% viscosity in aqueous solution of table 1 glutinous rice starch/Yodo Sol GH 28
| Sample | Viscosity (cp) | Sample | Viscosity (cp) |
| AS1(1∶1) | 1672 | AS9(4∶7.5) | 3895 |
| AS2(1∶2) | 4667 | AS10(6∶7) | 1499 |
| AS3(1∶20) | 2148 | AS11(10∶12) | 2910 |
| AS4(10∶1) | 576 | AS12(10∶7) | 1017 |
| AS5(20∶1) | 297 | AS13(10∶4) | 1574 |
| AS6(1∶2) | 3641 | AS14(10∶1) | 745 |
| AS7(4∶10) | 1672 | AS15(2∶1) | 1369 |
| AS8(4∶6.5) | 3108 | Pure glutinous rice starch | 381 |
Rich power flies the DV-ii+PRO rotational viscosimeter, and No. 21 rotating cylinders, are measured under the 60 commentaries on classics/min conditions by 25 ℃.
1～15 glutinous rice starch/Yodo Sol GH 28 10g of making; After 10g glutinous rice starch, 15g glycerine, 15g water, 1g sodium hydrogencarbonate mixing slaking; The Trisodium trimetaphosphate aqueous solution 5g of adding 5%, press mold between backing film and protective membrane is placed after 4 days; Form adhesive patches, be designated as TP1～TP15 respectively.Performance is seen table 3.
Table 2 is compositions of glutinous rice starch/acrylic acid ester copolymer composition.
Table 1 glutinous rice starch/acrylic acid ester copolymer composition is formed
| Sample number | Glutinous rice starch/Yodo Sol GH 28/g | Starch or treated starch/g | Linking agent/g |
| CAS16 | AS5/9.8 | Borax/0.1 Trisodium trimetaphosphate/0.1 | |
| CAS17 | AS4/8 AS12/1.999 | Trisodium trimetaphosphate/0.001 | |
| CAS18 | AS1/1 | Glutinous rice starch/8.5, CMS/0.5 | Trisodium trimetaphosphate/0.025 |
| CAS19 | 6g AS8， 1gAS9 | 2g acetic ester glutinous rice starch | Tripoly phosphate sodium STPP 1g |
| CAS20 | AS3/0.001 | Oxidation glutinous rice starch/9.998 | Trisodium trimetaphosphate/0.001 |
| CAS21 | AS3/1 | 8.8g toxilic acid esterification glutinous rice starch | Trisodium trimetaphosphate/0.2 |
| CAS22 | 2g?AS6 | 7g oxidation glutinous rice starch, 1g W-Gum | POCl3 0.1g 0.3g borax |
| CAS23 | 4g?AS11 | 3g sticks W-Gum, 2g yam starch | 0.05g Trisodium trimetaphosphate, 0.95g borax |
| CAS24 | AS10/3， AS7/1 | Sad esterification glutinous rice starch/5, sweet potato starch/0.9 | Epoxy chloropropane 0.1 |
| CAS25 | AS1/0.5 | Glutinous rice starch/9, CMS/0.5 | Trisodium trimetaphosphate/1 |
Embodiment 16:
Compsn CAS16 uses: 9.8g AS5,10g water, 6g glycerine, 0.1g borax, Trisodium trimetaphosphate 0.1g; After the mixing, regulate pH9.5, in mould, add thermomaturation with sodium hydrogencarbonate; After a week is placed in sealing; The cross linked gel TP15 that obtains wetting, water cut 30%, can drying dewatering obtains xerogel.
Embodiment 17:
Compsn CAS17 uses: 8g AS4,1.999g AS12,15g water, 8g glycerine, 0.001g Trisodium trimetaphosphate; After the mixing, regulate between pH8, in mould, add thermomaturation with sodium hydrogencarbonate; After placing a week; The cross linked gel film TP16 that obtains wetting, water cut 40%, can drying dewatering obtains xerogel.
Embodiment 18:
Compsn CAS18 uses: 1g AS1,8.5g glutinous rice starch, 0.5g CMS, 30g water, 10g glycerine, 0.3g sodium hydroxide, mix the post-heating slaking, and be cooled to room temperature; Add 0.5g diclofenac, 5% Trisodium trimetaphosphate aqueous solution 0.5g then; Mix, at backing and be coated with film forming between the silicon paper, place a week after; Obtain containing the paster TP17-1 of diclofenac, water cut is about 55%.Change diclofenac into Ibuprofen BP/EP, obtain paster TP17-2, water cut about 56%.
Embodiment 19:
Compsn CAS19 uses: 6g AS8,1g AS9,2g acetic ester glutinous rice starch, 170g water, 1g yellow soda ash, 1g carbomer U10; The 1g PEG 400 mixes the post-heating slaking, adds 7g PVP-1 and 10% Trisodium trimetaphosphate aqueous solution 10g then; Mix; Obtain the povidone iodine gel agent,, water cut 90%; Baking removes most of moisture after the slaking, in mould, rolls film forming, place a week after, the povidone iodine membrane agent TP18 that obtains wetting, water cut 44%; Drying dewaters and obtains the PVP-1 dry film, water cut 5%.
Embodiment 20:
Compsn CAS20 uses: 0.001g AS3,9.998g toxilic acid esterification glutinous rice starch, 2g gelatin are dissolved in 12g water, 6g glycerine, 1g sodium hydroxide, 0.5g phenylformic acid, 5% Trisodium trimetaphosphate aqueous solution 0.02g; Mix the post-heating slaking; Press mold, the cross linked gel film TP19 that must wet.
Embodiment 21
Compsn CAS21 uses: 1g AS3,8.8g toxilic acid esterification glutinous rice starch, 12g water, 6g glycerine, 1g sodium hydroxide; Mix the post-heating slaking; Sneak into 7g Chinese medical concrete (press official method extract refining dog skin plaster medicinal extract), 0.5g azone and 10% Trisodium trimetaphosphate aqueous solution 2g then, mix, at backing film be coated with between the silicon paper and roll film forming; After placing a week, obtain refining dog skin plaster paster TP20.
Embodiment 22:
Compsn CAS22 uses: 2g AS6,7g oxidation glutinous rice starch, 1g W-Gum, 0.5g Z 150PH, 6g water, 26g glycerine, 3g Macrogol 200; The 2g sodium hydrogencarbonate, POCl3 0.1g, the slaking of 0.3g borax mixing post-heating, calendering is in flakes in the mould; After placing a week; The crosslinked TP21 sheet type that obtains wetting, water cut is about 5%, can drying dewaters to obtain dry plate.
Embodiment 23:
Compsn CAS23 uses: 4g AS11, the glutinous W-Gum of 3g, 2g yam starch, 1g PVP K120,20g water, 16g glycerine, 2g sodium hydrogencarbonate, 0.05g Trisodium trimetaphosphate, the slaking of 1g borax mixing post-heating; Sneak into 2g YUNNAN BAIYAO powder, the 0.2g Sorbic Acid, calendering is in flakes in the mould; After placing a week; The crosslinked paster TP22 that obtains wetting, water cut 40%, can drying dewatering obtains dry plate.
Embodiment 24
Compsn CAS24 uses: 3g AS10,1g AS7, the sad esterification glutinous rice starch of 5g, 0.9g sweet potato starch, 0.5g guar gum, 10g water, 8g glycerine, 1g Macrogol 200; The 2g sodium hydrogencarbonate; 0.2g Whitfield's ointment, epoxy chloropropane 0.1g, mix the post-heating slaking, in the mould calendering in flakes, place a week after; The crosslinked TP23 sheet type that obtains wetting, can drying dewatering obtains dry plate.
Embodiment 25
CAS25 uses: 0.5g AS1, and 9g glutinous rice starch, 0.5g CMS mix, and add glycerine 4g; The 1g Trisodium trimetaphosphate, 1g sodium hydrogencarbonate, 180g water; Mix, after the steam cure, add 1g extract solution from aloe, 3g honey, 0.1g phosphatide; Mix, process aquagel membrane TP24, be used for skin.
Embodiment 26
AS13 is used for cataplasma: 1g Ibuprofen BP/EP (being dissolved into 2ml ethanol), 5g AS13,5g PVP K30,0.5g NP700; Carbomer 8g, glycerine 10g, zinc oxide 0.3g, kaolin 1g; Dihydroxyaluminum aminoacetate 0.2g fully dissolves or swelling in 40g water, slowly adds lactic acid aqueous solution (10%) 5ml then, after mixing, is coated on the non-woven fabrics with waterproof layer; The upper cover upper protective film, behind the placement 10h, crosslinked solidifying forms cataplasma paster TP25.
Embodiment 27
AS12 is used for cataplasma: 1g 5 FU 5 fluorouracil (being dissolved into 2ml ethanol), 0.1g AS 12,5g NP800, carbomer 8g; The yellow glue 3g in west, peach gum 2g, glycerine 10g, zinc oxide 0.3g, kaolin 1g, Tai-Ace S 150 0.2g fully dissolve or swelling in 40g water; Slowly add lactic acid aqueous solution (10%) 5ml then, after mixing, be coated on the non-woven fabrics with waterproof layer; The upper cover upper protective film, behind the placement 10h, crosslinked solidifying forms cataplasma paster TP26.
Embodiment 28
AS2 is used for cataplasma: 1g Whitfield's ointment (being dissolved into 2ml ethanol), 10g AS2,0.4g NP700, gelatin 5g; Glycerine 10g, titanium oxide 0.3g, aluminum chloride 0.1g fully dissolve or swelling in 30g water; Slowly add aqueous tartaric acid solution (1%) 10ml then, after mixing, be coated on the non-woven fabrics with waterproof layer; The upper cover upper protective film, behind the placement 2h, crosslinked solidifying forms cataplasma paster TP27.
The performance of 23 ℃ of following each pasters of table 3
Annotate: 1. tack: test according to GB4852-84; Hold viscous force: according to GB4851-84 test, weight 500g; 180 ° of stripping strengths: test according to GB2792-81.
2. gas permeability test:
Several volumes are pack into the zero(ppm) water of 8g of the phial of 10ml, and bottleneck diameter is 1.2cm (A=1.13cm
2).Membrane sample is cut into the circle of diameter 2.0cm, covers bottleneck with circular sample then, with teflin tape the contact position is sealed again,, put into climatic chamber with the analytical balance W1 that weighs.The internal medium of climatic chamber remains on 37 ℃ of temperature, relative humidity 65%.After 72h hour, take out bottle, be cooled to room temperature, W2 once more weighs.Through the quality W=W1-W2 that bottle dries out, just can calculate in the membrane 24h, the vapour transmission amount of unit surface, calculation formula is following:
Table 3 patche is through rat skin in vitro cumulative in vitro infiltration capacity (g/cm
2)
| Paster | 2h | 4h | 6h | 8h | 16h | 24h |
| TP16-1 (diclofenac) | 81 | 126 | 193 | 242 | 487 | 604 |
| TP16-2 (Ibuprofen BP/EP) | 267 | 456 | 719 | 831 | 913 | 1297 |
| TP23 (Whitfield's ointment) | 368 | 587 | 1045 | 1462 | 1789 | 2543 |
| TP24 (Ibuprofen BP/EP) | 224 | 342 | 536 | 751 | 826 | 973 |
| TP25 (5 |
167 | 257 | 478 | 635 | 796 | 879 |
(Franz diffusion cell, 37 ℃, performance liquid detects)
Claims (7)
1. the compsn of a glutinous rice starch/Yodo Sol GH 28, the quality that it is characterized in that it is formed and is comprised:
Glutinous rice starch/Yodo Sol GH 28 0.01%～99.98%
Starch or treated starch 0～99.98%
Linking agent 0.01%～10%
Described glutinous rice starch/Yodo Sol GH 28, it is the multipolymer of glutinous rice starch and vinylformic acid and esters monomer thereof; Described starch is W-Gum, wheat starch, sweet potato starch, yam starch, glutinous rice starch; Treated starch is cationic starch, CMS, Sumstar 190, phosphate ester starch, acetate starch, toxilic acid esterification starch and the alkyl esterification starch that contains 5～18 carbon atoms; Described linking agent is selected from one or more in tripoly phosphate sodium STPP, borax, POCl3, epoxy chloropropane, the Trisodium trimetaphosphate;
The preparation method is: by metering the aqueous dispersions of the mixture of glutinous rice starch/Yodo Sol GH 28, starch or treated starch is heated to slaking more than 80 ℃, regulating pH before or after the slaking is 8～11, mixes moulding again with linking agent; Perhaps
Glutinous rice starch/Yodo Sol GH 28, starch or treated starch, linking agent are mixed the formation aqueous dispersions in water, regulating pH is 8～11, is heated to slaking moulding more than 80 ℃; Perhaps
Glutinous rice starch/Yodo Sol GH 28, starch or treated starch, linking agent are mixed the formation aqueous dispersions in water, be heated to slaking more than 80 ℃, regulating pH then is 8～11, moulding;
Above-mentioned compsn room temperature that obtains or heating were placed 0.5～10 day, promptly got cross-linking products;
The step that the preparation method of described glutinous rice starch/Yodo Sol GH 28 comprises: under nitrogen protection, with the amidin gelatinization, adding alkali, to regulate pH be 8～12 under 80～100 ℃; Cool to then below 60 ℃, slowly add vinylformic acid and esters monomer thereof after the adding water soluble starter, 60～80 ℃ were reacted 3～24 hours down; The pH that adds the alkali regulation system is extremely neutral, steams then and removes moisture content, and dry, pulverizing obtains the powder of glutinous rice starch/Yodo Sol GH 28; Described initiator is Potassium Persulphate, H2O2, ammonium persulphate or cerous ammonium nitrate, and consumption is 0.01%～5% of a monomer total amount.
2. according to the compsn of the described a kind of glutinous rice starch/Yodo Sol GH 28 of claim 1, it is characterized in that described glutinous rice starch is one or more mixtures of the starch of glutinous rice, glutinous rice, glutinous corn, Radix Et Rhizoma Rhei rice, small Semen setariae, milled glutinous broomcorn millet, glutinous sorghum rice; Described vinylformic acid and esters monomer thereof are selected from vinylformic acid, methylacrylic acid and (methyl) acrylic ester monomer, and ester group wherein contains 1～18 carbon atom.
3. according to the compsn of the described a kind of glutinous rice starch/Yodo Sol GH 28 of claim 2, described vinylformic acid and esters monomer thereof are selected from one or more in vinylformic acid, methylacrylic acid, Hydroxyethyl acrylate, Rocryl 400, methyl acrylate, ethyl propenoate, vinylformic acid n-propyl, isopropyl acrylate, n-butyl acrylate, NSC 20949, vinylformic acid n-pentyl ester, vinylformic acid isopentyl ester, the just own ester of vinylformic acid, Isooctyl acrylate monomer, vinylformic acid n-octyl, isodecyl acrylate, vinylformic acid ester in the positive last of the ten Heavenly stems, vinylformic acid ester in the different ninth of the ten Heavenly Stems, TEB 3K, Jia Jibingxisuanyizhi, n propyl methacrylate, isopropyl methacrylate, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, methylacrylic acid n-pentyl ester, methacrylic isoamyl valerate, the just own ester of methylacrylic acid, Isooctyl methacrylate, n octyl methacrylate, isodecyl methacrylate, methylacrylic acid ester in the positive last of the ten Heavenly stems, the methylacrylic acid ester in the different ninth of the ten Heavenly Stems.
4. according to the compsn of the described glutinous rice starch/Yodo Sol GH 28 of claim 3; It is characterized in that the mass ratio of glutinous rice starch and vinylformic acid and esters monomer thereof is 0.05-20 in described glutinous rice starch/Yodo Sol GH 28: 1, wherein water-soluble monomer accounts for the 10-100% of monomer total mass.
5. the preparation method of the described glutinous rice starch/acrylic acid ester copolymer composition of claim 1; It is characterized in that the aqueous dispersions of the mixture of glutinous rice starch/Yodo Sol GH 28, starch or treated starch being heated to slaking more than 80 ℃ by metering; Regulating pH before or after the slaking is 8～11; Mix moulding again with linking agent; Perhaps
Glutinous rice starch/Yodo Sol GH 28, starch or treated starch, linking agent are mixed the formation aqueous dispersions in water, regulating pH is 8～11, is heated to slaking moulding more than 80 ℃; Perhaps
Glutinous rice starch/Yodo Sol GH 28, starch or treated starch, linking agent are mixed the formation aqueous dispersions in water, be heated to slaking more than 80 ℃, regulating pH then is 8～11, moulding;
Above-mentioned compsn room temperature that obtains or heating were placed 0.5～10 day, promptly got cross-linking products.
6. the application of the compsn of the described glutinous rice starch/Yodo Sol GH 28 of claim 1; It is characterized in that using, and be used for medicinal tablet, capsule, gelifying agent, emulsion, paste, film, cataplasma and patch as the pharmaceutical prepn auxiliary material as water-retaining agent, tackifier, tamanori, thickening material, solubilizing agent.
7. according to the application of the compsn of the described glutinous rice starch/Yodo Sol GH 28 of claim 6; It is characterized in that described compsn and other macromolecular material, liquid plasticizer, medicine, permeate promotor, wetting Agent for Printing Inks, tensio-active agent, tamanori, fungistat, mental compound additive combination; Said component can add gelifying agent, paste, film, controlled release preparation and the percutaneous administration patch of formation medicine as required before and after adding front and back and pH regulator at glutinous rice starch/acrylic acid ester copolymer composition slaking front and back, linking agent.
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