CN1296428C - Polyvinyl alcohol composite gel and its synthesis process - Google Patents
Polyvinyl alcohol composite gel and its synthesis process Download PDFInfo
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- CN1296428C CN1296428C CNB2004100388085A CN200410038808A CN1296428C CN 1296428 C CN1296428 C CN 1296428C CN B2004100388085 A CNB2004100388085 A CN B2004100388085A CN 200410038808 A CN200410038808 A CN 200410038808A CN 1296428 C CN1296428 C CN 1296428C
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Abstract
The present invention discloses polyvinyl alcohol plural gel and a synthetic method thereof. The polyvinyl alcohol plural gel of the present invention is compounded by the raw materials of the following proportion by weight: 8 to 15 shares of polyvinyl alcohol, and preferable 8 to 12 shares of polyvinyl alcohol; 3 to 5 shares of plasticizing agents of glycerin, and preferable 3.8 to 5 shares of plasticizing agents of glycerin; 0.5 to 1.5 shares of dextran-40 or 2 to 4 shares of polyethylene glycol-4000, and preferable 1.0 to 1.5 shares of dextran-40 or 3 to 4 shares of polyethylene glycol-4000; 0.5 to 2 shares of crosslinking agents of borax, and preferable 0.5 to 1.5 shares of crosslinking agents of borax; 0.5 to 2 shares of maleic anhydride, and preferable 0.5 to 1.5 shares of maleic anhydride. The raw materials of the formula for synthesizing polyvinyl alcohol plural gel of the present invention has no toxin, and the gel has favorable biocompatibility, high mechanical strength and high density pore spaces and is used as immobilized carriers for enzymes, bacterial cells and cellular organs of animals and plants.
Description
Technical field
The present invention relates to a kind of polyvinyl alcohol plural gel and synthetic method thereof.
Background technology
Polyvinyl alcohol (PVA) is by the polyvinyl acetate (PVA) hydrolysis, a kind of high molecular weight water soluble polymer that forms through alcoholization, by certain processes moulding PVA hydrogel, with its snappiness, chemical stability, be easy to moulding, nontoxic, have no side effect and with characteristics such as tissue excellent biological compatibility and be widely used in industries such as building, electronics, weaving, medical science, fine chemistry industry, light industry.
Through years of development, people have invented the preparing carriers method and the technology of the synthetic and relevant polyvinyl alcohol of many polyvinyl alcohol gels, and this is constantly applied.The defective of common PVA hydrogel is the mechanical property deficiency, just can remedy this defective if in material, introduce crosslinking structure, can improve its mechanical property effectively, by chemical crosslink technique, radiation crosslinking method, freezing-scorification or compound with other material, PVA is carried out suitably modification, can prepare various performances, different structure ground high molecular polymer gel.
By retrieval to document and patent, the preparation method of at present relevant PVA gel is more, as the Li Huazi [improvement of the process for fixation of polyvinyl alcohol-boric acid, Research of Environmental Sciences, 2002,15 (5)] etc. to the improvement of polyvinyl alcohol-boric acid process for fixation, specifically be to adopt the method for time-delay entrapping method and adding chemical agent to regulate its intensity, proposed to utilize boric acid saturated solution hardened forming on the US 5290693 (1994) for another example, below all be to be linking agent with boric acid, compare its shortcoming with borax and be: the consumption of boric acid is many than borax, crosslinking time is longer, support strength is relatively poor relatively.Gudeman etc. are synthetic and characterized polyvinyl alcohol/polyacrylic acid hydrogel film to the pH sensitivity, white Chongqing equality [preparation of PVA-PAA IPN hydrogel and swelling property research thereof, polymer material science and engineering, 2002,18 (1)] utilize chemical crosslink technique and circulation freezing-the order approximatioss that thaws and combine, prepared the macromolecule hydrogel that has the interpenetrating polymer networks structure by polyvinyl alcohol and polypropylene compound, this gel has temperature sensitive character.But this kind preparation method complexity, difficulty is suitable for suitability for industrialized production.
Polyvinyl alcohol is the synthesized polymer material of rare environmentally safe, owing to it does not have toxicity, with low cost and form the concern that advantage that carrier has tough mechanical property etc. self is subjected to every field to microorganism.
Summary of the invention
The purpose of this invention is to provide a kind of polyvinyl alcohol plural gel.
Another object of the present invention provide a kind of simply, fast, the synthetic method of polyvinyl alcohol plural gel cheaply.
Polyvinyl alcohol plural gel of the present invention is to be composited by the following weight parts proportion raw material, 8～15 parts polyvinyl alcohol, preferred 8～12 parts polyvinyl alcohol; 3～5 parts of softening agent glycerol, preferred 3.8～5 parts of softening agent glycerol; 0.5～1.5 parts of dextran-40s or 2～4 parts of polyoxyethylene glycol-4000, preferred 1.0～1.5 parts of dextran-40s or 3～4 parts of polyoxyethylene glycol-4000; 0.5～2 parts of linking agent boraxs, preferred 0.5～1.5 part of linking agent borax; 0.5～2 parts of MALEIC ANHYDRIDE; Preferred 0.5～1.5 part of MALEIC ANHYDRIDE.Softening agent can not make then very little that polyvinyl alcohol is submissive fully, the interpolation of macromolecular material (dextran-40 or polyoxyethylene glycol-4000) can change some characteristic of plural gel in the prescription, as voidage, aperture and the carrier property etc. of carrier.The alcoholysis degree of polyvinyl alcohol is 99%, and the polymerization degree is between 1500～2000.The polymerization degree of preferably polyethylene alcohol is 1750 ± 50.If the polymerization degree unsuitable moulding of low then colloidal sol and cause the carrier physical strength to reduce, the viscosity of gelating soln increases when higher, and is mobile relatively poor, and operation is inconvenient, has influence on the preparation of carrier.
The synthetic method of polyvinyl alcohol plural gel of the present invention, may further comprise the steps, 100 parts water are heated to 85 ℃～95 ℃, slowly be dissolved into 8～15 parts of polyvinyl alcohol in the water, the limit edged stirs, after treating that polyvinyl alcohol dissolves fully, add 3～5 parts glycerol, after stirring, dextran or 2～4 parts of polyoxyethylene glycol-4000 of adding 0.5～1.5 part again, use a spot of water dissolution in advance), stir, when constantly stirring, add then and dissolved good 0.5～2 part borax (with 1: 1 hot water dissolving), the limit edged stirs, carry out gelation and handle, crosslinking time is 2～15 minutes, and the preferred gelation reaction time is 2～5 minutes; Crosslinking time specifically will be decided with total stuff amount, and when promptly the reaction solution volume was big, then cross-linking reaction time was longer.The MALEIC ANHYDRIDE (with 1: 1 hot water dissolving) that adds 0.5～2 part then lentamente constantly stirs, and till the no cotton-shaped coagulum, transparent, the slightly milky thickness colloidal sol of gained is polyvinyl alcohol plural gel in gelating soln.This plural gel liquid is freeze forming under-10～-30 ℃ temperature, at room temperature thaws.
Principle of the present invention is: polyvinyl alcohol is dissolved in the hot water, forms two diol type (didiol) gels with borax generation gelation reaction after the adding softening agent glycerol, and its structure is:
The gel that has added medium molecular dextran (40) again with the MALEIC ANHYDRIDE grafting, form macromolecular water-soluble plural gel solution, handle the cancellated insoluble carrier in space that can obtain higher mechanical strength and have certain porosity through cryogenic freezing again.
The general structure of the polyvinyl alcohol that the present invention is used is:
Polyvinyl alcohol (PVA)
The polymerization degree of the polyvinyl alcohol that the present invention is used is 1750 ± 50, if the polymerization degree unsuitable moulding of low then colloidal sol and cause the carrier physical strength to reduce, the viscosity of gelating soln increases when higher, and is mobile relatively poor, and operation is inconvenient, has influence on the preparation of carrier.The physical parameter of used polyvinyl alcohol is as shown in the table.
| Sequence number | Index name | Index |
| 1 | The polymerization degree | 1700-1800 |
| 2 | Color | White |
| 3 | Alcoholysis degree (mol%) | 99.0-99.8 |
| 4 | Saponification value | 3-12 |
| 5 | Remaining vinyl acetate between to for plastic weight % | 0.5×1.8 |
| 6 | Viscosity PaS | 0.028-0.032 |
| 7 | PH value of solution | 5.0-7.0 |
| 8 | Ash content is (with Na 2The O meter) % maximum | 1.0 |
| 9 | Performance density kg/m 3 | 400-432 |
| 10 | Relative density | 1.30 |
| 11 | Resin density kg/m 3 | 1294 |
| 12 | Specific volume m 3/kg | 7.7×10 4 |
| 13 | Hardness (Shore scleroscope, not plasticising) | ＞100 |
The softening agent glycerol (glycerine) that the present invention mentioned, comparing with propylene glycol, polyoxyethylene glycol, sorbyl alcohol etc. has stronger hydrogen bonding power, can satisfy film forming, extension requirement as good polyvinyl alcohol softening agent, and with the consistency of polyvinyl alcohol and the persistence in finished product.Following table is the physical parameter of glycerine.
| Sequence number | Index name | Index |
| 1 | Content (%) | ≥96％ |
| 2 | Ignition residue % | 0.001 |
| 3 | Sulphur compound | 0.0005％ |
| 4 | Arsenic (As) % | 0.00005 |
| 5 | Ammonium salt (NH +)％ | 0.0005 |
| 6 | Fatty acid ester % | ±0.05％ |
| 7 | Muriate (Cl-) | 0.0001％ |
The formula material of synthesizing polyethylene alcohol plural gel of the present invention is nontoxic, gel has excellent biological compatibility, higher physical strength and high-density hole, the fixation support that can be used as enzyme, microorganism cells, animal and plant cells device, for example can be used for microorganism cellss such as yeast (viable cell), caproic acid bacteria, leuconostoc mesentroides and aspergillus niger, the immobilization of enzymes such as glucoamylase, amylase.
The synthetic preparation of polyvinyl alcohol plural gel provided by the invention is compared than the synthesis technique of other gel, have that energy consumption is low, operation is simple, fast, process operation is convenient, be easy to control, the characteristics that cost is low.The polyvinyl alcohol plural gel carrier physical strength that forms is higher, immobilization efficiency is high, and biological activity is better, wear-resisting, acid and alkali-resistance.
By the comparison of the embodiment of the invention and Comparative Examples, illustrate that the made carrier of the present invention all has mechanical property preferably.And if the content of PVA is 7% when following, the carrier mechanical property is poor slightly.Along with the increase of polyvinyl alcohol content, the intensity of plural gel carrier increases thereupon, but porosity reduces, the aperture reduces; In experiment, look concrete purposes difference and adjust its content.
Description of drawings
Fig. 1 is the synthetic route chart of polyvinyl alcohol plural gel of the present invention.
Embodiment
The following examples can make those skilled in the art more fully understand the present invention, but do not limit the present invention in any way.
Embodiment 1:
(Lanzhou fiber nylon factory produces 8 parts of polyvinyl alcohol of alcoholysis degree 99%, the polymerization degree 1750 ± 50) is dissolved in 100 parts 85 ℃ the water, the limit edged stirs, after treating that polyvinyl alcohol dissolves fully, the glycerol that adds 4.4 parts, after stirring, add 1 part of dextran-40 (using a spot of water dissolution in advance), stir, when constantly stirring, add and dissolved 1 part of good borax then, the limit edged stirs, carry out gelation and handle, add 1 part of maleic acid anhydride solution after 2～5 minutes lentamente, constantly stir, no cotton-shaped coagulum in coagulant liquid, obtain transparent, have milky thickness colloidal sol slightly, be polyvinyl alcohol plural gel, more than operation is all carried out under 85 ℃ constant temperature.This plural gel liquid freeze forming under-24 ℃ temperature at room temperature thaws.
The comparative example A:: repeat embodiment 1, following difference is arranged: 6 parts of polyvinyl alcohol of alcoholysis degree 99% are dissolved in 100 parts 85 ℃ the water.Measure under the similarity condition in embodiment 1, the result shows: the viscosity of comparing the synthetic coagulant liquid with control experiment is lower, and the intensity of carrier is poor slightly after the cryogenic freezing moulding.
Embodiment 2
Repeat embodiment 1, following difference is arranged: use 10 parts of polyvinyl alcohol of alcoholysis degree 99% to be dissolved in 100 parts 85 ℃ the water.The viscosity of the plural gel solution that obtains " embodiment 1 " increases by 2.1%, the aperture of carrier, and porosity slightly reduces, and support strength is better.
Embodiment 3
Repeat embodiment 1, following difference is arranged: use 15 parts of polyvinyl alcohol of alcoholysis degree 99% to be dissolved in 100 parts 85 ℃ the water.The viscosity of the plural gel solution that obtains " embodiment 2 " increases by 1.6%, the aperture of carrier, and porosity reduces.The physical strength of carrier is higher behind the freeze forming.
Embodiment 4
Repeat embodiment 1, following difference is arranged: use 15 parts of polyvinyl alcohol of alcoholysis degree 99% to be dissolved in 100 parts 85 ℃ the water, add 3.5 parts polyoxyethylene glycol-4000.The viscosity of the plural gel solution that obtains " embodiment 2 " increases by 1.4%, the aperture of carrier, and porosity all increases to some extent than " embodiment 2 " and " embodiment 3 ".
Embodiment 5
In volume is 100 liters fixation support reactor, add 50 premium on currency, with more than the steam heating to 85 ℃, open and stir, the polyvinyl alcohol that slowly adds 4kg, after treating that polyvinyl alcohol dissolves fully, add 1.8 liters of glycerine, add 500g dextran-40 (using a spot of water dissolution in advance) after 10 minutes, slowly add 500g borax (with 1: 1 water dissolution) then, behind the gelation reaction 2～15 minutes, slowly add the MALEIC ANHYDRIDE (with 1: 1 water dissolution) of 500g, constantly stir no cotton-shaped coagulum in coagulant liquid, obtain transparent, have milky thickness colloidal sol slightly, be polyvinyl alcohol plural gel.
By the comparison of the embodiment of the invention and Comparative Examples, illustrate that the made carrier of the present invention all has mechanical property preferably.And the content of PVA is poor slightly in 7% mechanical property of carrier when following.Along with the increase of polyvinyl alcohol content, the intensity of plural gel carrier increases thereupon, but porosity reduces, the aperture reduces.
Claims (5)
1, a kind of polyvinyl alcohol plural gel, it is characterized in that: it is to be composited by the following weight parts proportion raw material, 8～15 parts polyvinyl alcohol, 3～5 parts of softening agent glycerol, 0.5～1.5 parts of dextran-40s or 2～4 parts of polyoxyethylene glycol-4000,0.5～2 parts of linking agent boraxs, 0.5～2 part of MALEIC ANHYDRIDE; The alcoholysis degree of polyvinyl alcohol is 99%, and the polymerization degree is between 1500～2000.
2, polyvinyl alcohol plural gel according to claim 1, it is characterized in that: the weight proportion of each raw material is, 8～12 parts polyvinyl alcohol, 3.8～5 parts of softening agent glycerol, 1.0～1.5 parts of dextran-40s or 3～4 parts of polyoxyethylene glycol-4000,0.5～1.5 parts of linking agent boraxs, 0.5～1.5 part of MALEIC ANHYDRIDE.
3, polyvinyl alcohol plural gel according to claim 1 and 2 is characterized in that: the polymerization degree of polyvinyl alcohol is 1750 ± 50.
4, the synthetic method of the described polyvinyl alcohol plural gel of claim 1, it is characterized in that: it may further comprise the steps, 100 parts water are heated to 85 ℃～95 ℃, slowly be dissolved into 8～15 parts of polyvinyl alcohol in the water, the limit edged stirs, after treating that polyvinyl alcohol dissolves fully, the glycerol that adds 3～5 parts, after stirring, add again and use a spot of water-soluble 0.5～1.5 part dextran or 2～4 parts of polyoxyethylene glycol-4000 in advance, stir, add the borax that has dissolved good 1: 1 hot water dissolving of 0.5～2 part of usefulness then when constantly stirring, the limit edged stirs, and carries out gelation and handles, crosslinking time is 2～15 minutes, the MALEIC ANHYDRIDE that adds 1: 1 hot water dissolving of 0.5～2 part of usefulness then lentamente constantly stirs, in gelating soln till the no cotton-shaped coagulum, gained is transparent, slightly milky thickness colloidal sol is polyvinyl alcohol plural gel.
5, the synthetic method of polyvinyl alcohol plural gel according to claim 4 is characterized in that: wherein the gelation reaction time of borax is 2～5 minutes.
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| CNB2004100388085A CN1296428C (en) | 2004-04-30 | 2004-04-30 | Polyvinyl alcohol composite gel and its synthesis process |
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| CNB2004100388085A CN1296428C (en) | 2004-04-30 | 2004-04-30 | Polyvinyl alcohol composite gel and its synthesis process |
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| CN1296428C true CN1296428C (en) | 2007-01-24 |
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| CN102382405B (en) * | 2010-09-03 | 2014-08-20 | 北京市理化分析测试中心 | Hydrogel and use thereof for cleaning and dedusting |
| CN102174237B (en) * | 2010-12-17 | 2012-10-24 | 北京理工大学 | Polyvinyl alcohol gel medium used for recycling explosion fragments and shooting bullets as well as preparation method and applications thereof |
| CN102774964B (en) * | 2011-05-13 | 2014-05-07 | 北京师范大学 | Microorganism immobilization carrier and its preparation method |
| CN102634157B (en) * | 2012-05-04 | 2013-06-12 | 浦江县金太郎玩具有限公司 | Transparent crystal glue material and preparation method of transparent crystal glue material |
| CN102703303B (en) * | 2012-06-21 | 2014-06-11 | 重庆大学 | Cellulose embedded particle airborne ethanol solid-state synchronous enzymolysis and fermentation combination system |
| DK3247195T3 (en) | 2015-01-19 | 2024-09-30 | Jiffy Int As | Biodegradable Fiber Plant Growth Containers and Methods |
| CN105132213B (en) * | 2015-07-28 | 2019-02-15 | 浙江大学 | A kind of scavenger and preparation method thereof of mural painting reinforcement material |
| CN105885064A (en) * | 2016-04-18 | 2016-08-24 | 北京化工大学 | Toughened polyvinyl alcohol composite hydrogel and application thereof |
| CN113481065A (en) * | 2021-06-18 | 2021-10-08 | 中国辐射防护研究院 | Foam gel and preparation method thereof |
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|---|---|---|---|---|
| CN1033460A (en) * | 1987-12-11 | 1989-06-21 | 国营陕西第九棉纺织厂 | Adhesive for composite cloth-lined paper and its making method |
| JP3105451B2 (en) * | 1996-04-30 | 2000-10-30 | アイセロ化学株式会社 | Biodegradable resin composition and molded article thereof |
| EP0799130B1 (en) * | 1994-12-22 | 2002-02-20 | Exxonmobil Oil Corporation | Method for producing a poly(vinyl alcohol) coated film |
| CN1405230A (en) * | 2001-09-20 | 2003-03-26 | 轻工业塑料加工应用研究所 | Hydrolytic biodegradable plastic shaping material and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1033460A (en) * | 1987-12-11 | 1989-06-21 | 国营陕西第九棉纺织厂 | Adhesive for composite cloth-lined paper and its making method |
| EP0799130B1 (en) * | 1994-12-22 | 2002-02-20 | Exxonmobil Oil Corporation | Method for producing a poly(vinyl alcohol) coated film |
| JP3105451B2 (en) * | 1996-04-30 | 2000-10-30 | アイセロ化学株式会社 | Biodegradable resin composition and molded article thereof |
| CN1405230A (en) * | 2001-09-20 | 2003-03-26 | 轻工业塑料加工应用研究所 | Hydrolytic biodegradable plastic shaping material and preparation method thereof |
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