CN1480224A - Starch hydrogel - Google Patents

Starch hydrogel Download PDF

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Publication number
CN1480224A
CN1480224A CNA031786774A CN03178677A CN1480224A CN 1480224 A CN1480224 A CN 1480224A CN A031786774 A CNA031786774 A CN A031786774A CN 03178677 A CN03178677 A CN 03178677A CN 1480224 A CN1480224 A CN 1480224A
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China
Prior art keywords
starch
weight
compositions
polyvinylpyrrolidone
water
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CNA031786774A
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Chinese (zh)
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CN1308044C (en
Inventor
K・哈希姆
K·哈希姆
M・达赫兰
K·Z·M·达赫兰
K·巴哈里
N·莫西德
阿比丁
N·A·阿比丁
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MALAYSIA NUCLEAR TECH INST
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MALAYSIA NUCLEAR TECH INST
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Publication of CN1480224A publication Critical patent/CN1480224A/en
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  • Materials For Medical Uses (AREA)
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  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

The hydrogel forming composition contains up to 10 wt.% of the starch, up to 5 to 7.5 wt.% of polyvinylpyrrolidon, up to 5 to 10 wt.% of polyvinyl alcohol, up to 1% to 3 wt.% of water-soluble cellulose and water. The hydrogel is prepared by exposing a half-gelled material made of the composition to an electron beam or a [gamma]-ray to the extent that the total beam absorption amounts to 5 to 50 kGy.

Description

Starch hydrogel
Technical field
The present invention relates to starch hydrogel, more specifically, the present invention relates to the starch hydrogel of crosslinking with radiation, it especially is fit to medicine and surgical operation and uses, for example as being used for the application of wound, as that contact with artificial cartilage with lens and material drug delivery system as burn, thropic ulcer and decubital ulcer.
Background technology
The wound dressing of gauze used a lot of years.They have can not prevent the exsiccant shortcoming of wound, and the result forms stem organization on wound, and they allow infectious agent such as antibacterial and fungus near wound.They are adhered on the wound, make them be difficult to remove, and also can remove the tissue of the new growth that has linked to each other with them simultaneously, and the dressing wound can cause patient's pain and discomfort so again.
In seeking alternative gauze application, in recent years, multiple biology or biosynthesis material, for example hydrocolloid, alginate, absorbable thin polymer film, especially hydrogel have been developed and have been used for wound dressing.
Hydrogel is that they are flexible than the advantage of gauze application, and is resilient, no matter is suitable for covering the wound of Any shape thus, and they have the ability that absorbs moisture and juice, do not make the wound drying.They seal up wound fully, prevent the infection of antibacterial and fungus.And although they are attached on the skin firmly, they are easy to remove, and can not produce pain to the patient, also can not remove newborn tissue.
For example,, especially under electron beam or the gamma-radiation, water-soluble polymer such as polyvinylpyrrolidone, Polyethylene Glycol, polyvinyl alcohol, poly(ethylene oxide) and polyacrylic aqueous solution are carried out crosslinked, can prepare hydrogel by being exposed under the radiation.The maximum hydrogel that is used for wound dressing and other medical applications that can buy in the market also comprises polysaccharide, as agar or carrageenin.
K.Hashim etc. are at " crosslinking with radiation of mixture that is used for the starch/water soluble polymer of hydrogel ", Proceedings of Takasaki Workshop, Takasaki, Japan, 1-2 November1999 have proposed agar or the carrageenin that western grain starch (Sago starch) can replace being used for these hydrogels.This paper discloses from western grain starch and polyvinylpyrrolidone or polyvinyl alcohol and has prepared hydrogel.
The west grain starch is the commodity that can extensively obtain in the area of sago palm growth, and is cheaply more a lot of than the pure type of the agar of present use and carrageenin.Other starch also can extensively obtain, and is more cheap than the material of these current uses.Therefore, if can prepare hydrogel based on Xi Gu and other starch, these hydrogels have makes them be suitable for the character that wound dressing and other medical treatment and surgical operation are used, and the price that can greatly reduce acquisition is used for the product of these purposes.
Summary of the invention
Summary of the invention
The invention provides the compositions that forms hydrogel, comprise and reach 30%, the starch of preferred 5 to 15% weight, 5 to 20%, the polyvinylpyrrolidone of preferred 5 to 7.5% weight reaches 15%, preferably reaches the polyvinyl alcohol of 7.5% weight, 1 to 10%, the preferably nearly water-soluble cellulose and the water of 5% weight.
The polyvinylpyrrolidone of a large amount and polyvinyl alcohol can make hydrogel elasticity reduce, and need higher radiation dose when crosslinked.The water-soluble cellulose of a large amount increases the swellbility of hydrogel, not only can increase water absorption thereupon, and can increase the viscosity of the solution of preparation hydrogel.
With independent by polyvinylpyrrolidone or polyvinyl alcohol, or compare with the hydrogel of agar or carrageenin combined preparation, starch can increase the intensity of hydrogel.
The preferable amount of the component of compositions of the present invention is the radiating starch of 7.5% weight, the polyvinylpyrrolidone of 7.5% weight, the carboxymethyl cellulose of the polyvinyl alcohol of 5% weight and 3% weight.
Starch can be radiating or non--radiating starch, preferred western grain starch, tapioca or corn starch.The radiant energy of starch reduces its molecular dimension, makes it be easy to dissolving.
Water-soluble cellulose is preferably carboxymethyl cellulose.
By forming half-gel and being exposed to ionizing radiation, electron beam or cobalt-60 sources for example, to total absorbed dose in 5 to 50kGy scope, can prepare hydrogel from said composition.Before half-gel radiation, can carry out autoclaving and handle, so that polyvinyl alcohol dissolves fully, and makes the hydrogel sterilization, so only need lower radiation dose, because under this low radiation dose, differ hydrogel is sterilized.
Preferably, earlier be dissolved in the distilled water respectively each composition in the proper ratio, starch and cmc soln begin gel point at starch to be mixed to about 90 ℃ temperature, vigorous stirring, under about 70 ℃ to 90 ℃ temperature, continuous slowly stirring, add polyvinylpyrrolidone and poly-vinyl alcohol solution, continue heating simultaneously, up to preparing clarifying semigel solution.Should be transferred in the plastic pattern by half agglomerative solution, be cooled to room temperature.Preferably with polyethylene or this mould of polyethylene terephthalate film phonograph seal, radiation is so that crosslinked polymer is finished gelling, and, if desired, the sterilization gel.
Preferably make polyvinylpyrrolidone and poly-vinyl alcohol solution, kept at least 12 hours down at about 70 ℃ before use.
It can be the gel adhesion of sheet form that the higher radiation dose that use is higher than about 20kGy can cause forming.
Use more that low radiation dose can not cause forming the gel adhesion, but can cause forming paste or semiliquid gel, it can only use by tubular container.
The hydrogel of adhesion has high gel strength, high resiliency and pliability, and have very high swellability and adhesiveness, they are suitable for wound dressing surprisingly thus.They can also be used for conventional many other purposes used of hydrogel, for example as culture medium.
The specific embodiment
The following example illustrates the present invention.All in an embodiment percentage ratios are weight percentage.
Embodiment 1
Use the western grain starch of 7.5% (a); (b) tapioca or (c) corn starch, 7.5% polyvinylpyrrolidone, 7.5% polyvinyl alcohol and 3.0% carboxymethyl cellulose prepare a series of hydrogels.
Be dissolved in by the composition that each is independent and form solution in the distilled water, mixed solution under about 90 ℃ temperature, gentle agitation up to obtaining clarifying semigel solution, is used the electron beam irradiation of 25kGy dosage, makes gel.
The character of hydrogel is listed in the table 1.
Table 1
Starch Gel strength (MPa) Elongation (%) Water absorption (%)
Xi Gu ????2.33×10 -2 ????296 ????5516
Maninot esculenta crantz. ????1.47×10 -2 ????300 ????6012
Corn ????2.28×10 -2 ????276 ????4466
Embodiment 2
Use 7.5% western grain starch, 7.5% polyvinylpyrrolidone, 7.5% polyvinyl alcohol and 3.0% carboxymethyl cellulose prepare a series of hydrogels.
In some cases, pre-radiation starch under 100kGy.
Be dissolved in by the composition that each is independent and form solution in the distilled water, mixed solution under about 90 ℃ temperature, gentle agitation up to obtaining clarifying semigel solution, is used the electron beam irradiation of 25kGy or 40kGy dosage.Before radiation, the autoclaving that some samples carried out under 121 ℃ temperature 1 hour is handled.
Also prepared the carboxymethyl cellulose content by the displaced contrast hydrogel of the distilled water of same amount.
The character of hydrogel is listed in the table 2.Table 2
The pre-radiation of starch Autoclaving Dosage (kGy) Gel strength (MPa) Elongation (%) Water absorption (%)
There is not (no CMC) contrast Not ????25 ??4.59 ????200 ????1125
Do not have Not ????25 ??2.37×10 -2 ????125 ????4526
Do not have Not ????40 ??2.88×10 -2 ????80 ????3833
(100kGy) arranged Not ????25 ??1.52×10 -2 ????276 ????7674
Do not have Be ????25 ??2.28×10 -2 ????236 ????2816
(100kGy) arranged Be ????25 ??1.45×10 -2 ????276 ????5726
Embodiment 3
Prepare a series of hydrogels from pre-radiating western grain starch, polyvinylpyrrolidone, polyvinyl alcohol and water-soluble cellulose derivative under 100kGy, it is by each composition is dissolved in the distilled water, heated solution under the agglomerative temperature of starch, up to obtaining clarifying semigel solution, handled 1 hour at 121 ℃ of following autoclavings subsequently, radiation makes under the dosage of 25kGy.
The solution that is used to prepare hydrogel has following composition:
A) 30% pre-radiating starch, 7.5% polyvinylpyrrolidone, 7.5% polyvinyl alcohol and 3% carboxymethyl cellulose
B) 7.5% pre-radiating starch, 20% polyvinylpyrrolidone, 7.5% polyvinyl alcohol and 3% carboxymethyl cellulose
C) 7.5% pre-radiating starch, 7.5% polyvinylpyrrolidone, 15% polyvinyl alcohol and 3% carboxymethyl cellulose
D) 7.5% pre-radiating starch, 7.5% polyvinylpyrrolidone, 7.5% polyvinyl alcohol and 10% carboxymethyl cellulose
E) 7.5% pre-radiating starch, 7.5% polyvinylpyrrolidone, 7.5% polyvinyl alcohol and 3% hydroxypropyl cellulose
The character of hydrogel is listed in the table 3.Table 3
Hydrogel Gel strength (MPa) Elongation (%) Water absorption (%)
????a ??3.417×10 -2 ????196 ????1151
????b ??2.708×10 -2 ????340 ????3445
????c ??1.817×10 -2 ????188 ????3563
????d ??1.567×10 -2 ????232 ????3685
????e ??3.133×10 -2 ????220 ????1595

Claims (10)

1. a compositions that forms hydrogel comprises the nearly starch of 30% weight, the polyvinylpyrrolidone of 5 to 20% weight, the nearly polyvinyl alcohol of 15% weight, the nearly water-soluble cellulose and the water of 10% weight.
2. compositions that forms hydrogel comprises the starch of 5 to 15% weight, the polyvinylpyrrolidone of 5 to 7.5% weight, the polyvinyl alcohol of 1 to 10% weight, 1 to 10%, the preferably nearly water-soluble cellulose and the water of 5% weight.
3. compositions that forms hydrogel comprises the starch of 7.5% weight, the polyvinylpyrrolidone of 7.5% weight, the carboxymethyl cellulose of the polyvinyl alcohol of 5% weight and 3% weight.
4. according to any one compositions among the claim 1-3, wherein said starch is western grain starch, tapioca or corn starch.
5. according to any one compositions among the claim 1-4, wherein said starch is radiating starch.
6. according to any one compositions among the claim 1-4, wherein said water-soluble cellulose is a carboxymethyl cellulose.
7. method for preparing hydrogel comprises from forming semigel according to the compositions of any one the claim 1-6, make its be exposed to ionizing radiation down to total absorbed dose in 5 to 50kGy scope.
8. according to the method for claim 7, wherein be dissolved in the distilled water respectively each composition in the proper ratio, starch and cmc soln begin gel point at starch to be mixed to about 90 ℃ temperature, vigorous stirring, under 70 ℃ to 90 ℃ temperature, continuous slowly stirring, add polyvinylpyrrolidone and poly-vinyl alcohol solution, continue heating simultaneously, up to preparing clarifying semigel solution.
9. according to the method for claim 7 or 8, wherein make polyvinylpyrrolidone and poly-vinyl alcohol solution, in 70 ℃ of baking ovens, kept at least 12 hours before use.
10. according to any one method among the claim 7-9, wherein before radiation, semigel is carried out autoclaving and handle.
CNB031786774A 2002-07-26 2003-07-21 Starch hydrogel Expired - Fee Related CN1308044C (en)

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MYPI20022825 MY144738A (en) 2002-07-26 2002-07-26 Starch hydrogels
MYPI20022825 2002-07-26

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Cited By (6)

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CN100389145C (en) * 2006-09-29 2008-05-21 北京大学 Water gel containing natural high molecule and its radiation preparing method
CN101982202A (en) * 2010-11-02 2011-03-02 华东理工大学 Medical hydrogel dressings and preparation method thereof
CN107969662A (en) * 2017-12-08 2018-05-01 周起行 A kind of tender and crisp tasty and refreshing marinated ternip production method
CN107981283A (en) * 2017-12-08 2018-05-04 周起行 A kind of marinated radish preparation method full of nutrition
CN109674581A (en) * 2018-09-15 2019-04-26 深圳市浓华生物电子科技有限公司 A kind of transparent flexible moisture film is cured the wound patch and preparation method
CN113750979A (en) * 2021-10-08 2021-12-07 北京工商大学 Yellow water polysaccharide-based hydrogel and preparation method and application thereof

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DE602006010656D1 (en) * 2006-02-02 2010-01-07 Euro Celtique Sa Hydrogel for wound treatment
FR2908775B1 (en) * 2006-11-17 2012-08-31 Biomatlante HYDROGEL AND ITS BIOMEDICAL APPLICATIONS
CN101219983B (en) * 2007-12-29 2011-08-10 安徽智新生化有限公司 Method for producing improved vitamin A acetic ester
JP5618053B2 (en) * 2010-03-24 2014-11-05 株式会社日本コンタクトレンズ Contact lens and manufacturing method thereof
JP6081156B2 (en) * 2012-11-15 2017-02-15 アルケア株式会社 Hydrogel
CN102961784B (en) * 2012-11-29 2014-09-10 华南理工大学 BC (Bacterial Cellulose)/PVA (Polyvinyl Alcohol) composite material, as well as preparation method and application thereof
CN113244443B (en) * 2021-04-28 2022-07-26 广州大学 Hydrogel dressing and preparation method and application thereof
CN114752079B (en) * 2022-05-11 2024-02-20 齐鲁工业大学 Starch-based physical crosslinked hydrogel and preparation method and application thereof

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GB9415739D0 (en) * 1994-07-30 1994-09-21 Scimat Ltd Gel wound dressing

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100389145C (en) * 2006-09-29 2008-05-21 北京大学 Water gel containing natural high molecule and its radiation preparing method
CN101982202A (en) * 2010-11-02 2011-03-02 华东理工大学 Medical hydrogel dressings and preparation method thereof
CN101982202B (en) * 2010-11-02 2013-09-18 华东理工大学 Medical hydrogel dressings and preparation method thereof
CN107969662A (en) * 2017-12-08 2018-05-01 周起行 A kind of tender and crisp tasty and refreshing marinated ternip production method
CN107981283A (en) * 2017-12-08 2018-05-04 周起行 A kind of marinated radish preparation method full of nutrition
CN109674581A (en) * 2018-09-15 2019-04-26 深圳市浓华生物电子科技有限公司 A kind of transparent flexible moisture film is cured the wound patch and preparation method
CN109674581B (en) * 2018-09-15 2022-06-17 浙江维力华生物科技有限公司 Transparent flexible water film wound treatment plaster and preparation method thereof
CN113750979A (en) * 2021-10-08 2021-12-07 北京工商大学 Yellow water polysaccharide-based hydrogel and preparation method and application thereof
WO2023056893A1 (en) * 2021-10-08 2023-04-13 北京工商大学 Yellow water polysaccharide-based hydrogel, preparation method therefor, and application thereof

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CN1308044C (en) 2007-04-04
TWI316950B (en) 2009-11-11
JP2004059926A (en) 2004-02-26
TW200407381A (en) 2004-05-16

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