CN102020816B - Polyvinyl formal sponge material with uniform abscesses and rapid imbibition and preparation method thereof - Google Patents
Polyvinyl formal sponge material with uniform abscesses and rapid imbibition and preparation method thereof Download PDFInfo
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- CN102020816B CN102020816B CN2010105455749A CN201010545574A CN102020816B CN 102020816 B CN102020816 B CN 102020816B CN 2010105455749 A CN2010105455749 A CN 2010105455749A CN 201010545574 A CN201010545574 A CN 201010545574A CN 102020816 B CN102020816 B CN 102020816B
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- 239000000463 material Substances 0.000 title claims abstract description 40
- 206010000269 abscess Diseases 0.000 title claims abstract description 20
- 238000005213 imbibition Methods 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229920002554 vinyl polymer Polymers 0.000 title abstract 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 24
- 238000004132 cross linking Methods 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical group O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000008098 formaldehyde solution Substances 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 229930040373 Paraformaldehyde Natural products 0.000 claims abstract description 4
- 229920002866 paraformaldehyde Polymers 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 31
- 239000011148 porous material Substances 0.000 claims description 28
- 239000007788 liquid Substances 0.000 claims description 20
- 239000000126 substance Substances 0.000 claims description 16
- 239000002699 waste material Substances 0.000 claims description 15
- 239000006260 foam Substances 0.000 claims description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 11
- 238000004140 cleaning Methods 0.000 claims description 11
- 239000007791 liquid phase Substances 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 9
- -1 catalyzer Substances 0.000 claims description 8
- 239000003995 emulsifying agent Substances 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 230000008859 change Effects 0.000 claims description 5
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical group O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 5
- 238000006359 acetalization reaction Methods 0.000 claims description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical group CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
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- 238000005520 cutting process Methods 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
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- 229910052708 sodium Inorganic materials 0.000 claims description 3
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- 239000003350 kerosene Substances 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 229920001214 Polysorbate 60 Polymers 0.000 claims 1
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- 230000008014 freezing Effects 0.000 claims 1
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims 1
- 235000010989 polyoxyethylene sorbitan monostearate Nutrition 0.000 claims 1
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- 229940113124 polysorbate 60 Drugs 0.000 claims 1
- 229920000053 polysorbate 80 Polymers 0.000 claims 1
- 238000004506 ultrasonic cleaning Methods 0.000 claims 1
- 238000003756 stirring Methods 0.000 abstract description 14
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- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 10
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000003377 acid catalyst Substances 0.000 description 4
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- 239000001117 sulphuric acid Substances 0.000 description 3
- 235000011149 sulphuric acid Nutrition 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- 239000004141 Sodium laurylsulphate Substances 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 229940030225 antihemorrhagics Drugs 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 230000000025 haemostatic effect Effects 0.000 description 2
- 230000036541 health Effects 0.000 description 2
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- PXFBZOLANLWPMH-UHFFFAOYSA-N 16-Epiaffinine Natural products C1C(C2=CC=CC=C2N2)=C2C(=O)CC2C(=CC)CN(C)C1C2CO PXFBZOLANLWPMH-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 240000003183 Manihot esculenta Species 0.000 description 1
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
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- 229920000159 gelatin Polymers 0.000 description 1
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Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention discloses a polyvinyl formal sponge material with uniform abscesses and rapid imbibition and a preparation method thereof. The material comprises polyvinyl alcohol, a cross-linking agent, a catalyst and a pore-forming agent, wherein the cross-linking agent is formaldehyde or paraformaldehyde or formaldehyde solution. The preparation method comprises the following steps of: stirring 2-9 parts of polyvinyl alcohol in 100-200 parts of water of which the temperature is 60-98 DEG C to obtain solution, and adding 0.05-8 parts of pore-forming agent to the solution; fully emulsifying the pore-forming agent to form evenly dispersed continuous solution phase; then adding 1-26 parts of catalyst and 1-15 parts of cross-linking agent or 5-50 parts of recovered liquid waste, 1-8 parts of catalyst and 1-15 parts of cross-linking agent, and mixing; pouring the mixture into a mould after 1-60 min for cross-linking reaction for 0.1-2 hours to form the abscesses under the action of the pore-forming agent; and continuing to heat and cure for 2-18 hours to prepare the polyvinyl formal sponge material. The invention has the advantages of good hydrophily, high compression strength, high dry wetting rate, high imbibition ratio and the like.
Description
Technical field
The present invention relates to be applied to the PVF sponge in fields such as quick imbibition and cleaning, filtration, quick local hemostasis, medical carrier and the cold compress that good, the affine performance of consistency is good, the product percentage of open area high, rate of liquid aspiration is fast, liquid absorbency rate is big and the hot compress that relate in particular to a kind of field of medicaments are with PVF sponge and preparation method thereof.
Background technology
Z 150PH (hereinafter to be referred as PVA) acetals high-absorbent material has the excellent water-absorbing oil absorptiveness, has obtained widespread use in fields such as electronic industry, daily cleaning, health care, kitchen guarding, building materials.Along with rapid economy development and people are to the continuous pursuit of comfortable healthy living in recent years, markets such as industry cleaning and filtration articles for use, life cleaning supplies, medical treatment product are vast.
Particularly the PVF class material in certain degree of acetalization scope has superpower water-retaining capacity, and its suction multiple can reach several times to tens times of own wt.In addition; Its most outstanding characteristics will be calculated after rate of liquid aspiration as its " magic power ", the imbibition soft exquisiteness and whippy character and be applied to medical field; With traditional yarn dry goods, absorbent cotton class, gelatin class hemostatic material by comparison; Its hemostasis, expansion and comfort property etc. have a clear superiority in, and development potentiality and market outlook are splendid.The PVA sponge of crosslinked foaming has following performance:
Outward appearance is that cystose (sheet), pipe, the abscess of open-celled structure is fine and closely woven, can obtain various beautiful colors through dyestuff or pigmented tinting; Mechanical property shows as: be the bigger hard foam of compressive modulus of elasticity under the dry state, have bigger shock resistance and tear resistance, but tensile strength be lower, suction back wet elasticity is excellent; Little below temperature 60 degree to the influence of sponge physicals; Product has excellent chemical stability, the acid-fast alkali-proof performance; Product has high water absorbing capacity and water retention property, and rate of water absorption is fast, and liquid absorbency rate is high, and the suction back is soft fine and smooth.
In the present disclosed patented technology, adopt the method for starch filled foaming mostly.Promptly under appropriate temperature earlier with starch filled in PVA solution, expansion at a certain temperature after the starch suction, the formation abscess that in mixed system, plants oneself is washed starch off behind the PVA crosslinking curing at a certain temperature again.The product that uses this kind technical matters to produce, starch cleans up than difficulty fully, and residual starch can grow mould and cause product rotten, has limited the product application scope.And in this kind technical matters, the starch utility value is low, and water loss is big, and starch and acid catalyst can not be recycled, and is unfavorable for economizing on resources and cutting down cost.
Like patent publication No. is in the PVF foam preparation processes of CN101508747 and CN101508814; All with kind starch granuless such as tapioca(flour), yam starch, W-Gums as weighting material, behind Z 150PH colloidal sol curing molding, re-use big water gaging starch wash fallen.Though used properties-correcting agent such as emulsifying agent, trimeric cyanamide and silicon-dioxide in the preparation link.
The technology that other is used for industrial filtering net and cleans civilian sponge; Though introduce other macromolecular materials or the sponge physical and mechanical properties carried out modification through different methods; But starch filled traditional method as pore former has all been used in the formation of foaming of sponge and sponge abscess.
Patent publication No. is to relate to the high water absorption polyvinyl alcohol foam among the CN1557872; By the polymerization degree is the continuous hole-opening foaming body that 2000～3200 full-bodied PVF post-foaming obtains, and directly mixes back curing molding under 50～60 ℃ of conditions by Z 150PH, formaldehyde, acid and chemical foaming agent.This kind method employing sodium hydrogencarbonate and organic acid reaction are emitted gas and are reached the foaming purpose, but foaming products obtained therefrom sponge cell diameter is bigger, and are difficult to control evenly.Because of material such as yellow soda ash or sodium hydrogencarbonate and inorganic acid strong reaction rapid; Abrupt release goes out a large amount of gases, and escape of gas is serious, so yellow soda ash and sodium hydrogencarbonate addition are bigger; Simultaneously also consume more acid catalyst, this kind method is difficult in the suitability for industrialized production and is applied.
Patent publication No. is that CN1095387 has introduced the medical and health use polyvinyl alcohol foam material, and it has increased oxalic dialdehyde in raw material be whipping agent with adopting sodium hydrogencarbonate, through the polymerization casting mold demoulding of getting blisters, washing machine-shaping.This kind method relies on the HV high density characteristic of polyvinyl alcohol solution, through high-speed stirring and add the mode that sodium hydrogencarbonate produces carbonic acid gas, reaches the purpose of foaming.But in suitability for industrialized production, carry out the high speed very difficulty of getting blisters to the polyvinyl alcohol solution of HV high density, too high to the requirement of power of motor and whisking appliance, whole whipping appts moves very unstable, and the slurry injection molding is difficulty very also.In addition, full-bodied Z 150PH colloidal sol holds that tolerance is not high, and gas is easy to break, converges and escapes during stirring, and the coarse inequality in products obtained therefrom aperture, is difficult to the control pore size distribution.
And patent publication No. is that disclosing with Z 150PH and chitosan among the CN101613512 is raw material, is linking agent with formaldehyde, is the porous polyethylene alcohol formal foam with bacterinertness of auxiliary material preparation with sulfuric acid, tensio-active agent, water.According to its disclosed data, the material water-intake rate that this method is produced is more than 1000%, and 50 seconds time of suction height is less than 150 seconds, becomes softness, tough, resilient sponge after the imbibition.And introduced chitosan because of material, made it also have the characteristics of certain inhibition bacterium, can be used on the surgical dressing.But when introducing chitosan, but increase the intensity of material, reduced material rate of water absorption and soften, rapid expansible performance when especially having weakened the material suction, thereby said material does not have advantage when being used in quick imbibition and quick-acting haemostatic powder.In addition; Though tensio-active agents such as sodium lauryl sulphate have been used in this invention, improved the dispersion effect of bubble at sol system, this Technology has been used the acid catalyst of more amount; And the tensio-active agent acid resistance that it is selected for use also is not very outstanding; Sodium lauryl sulphate is the meeting oxygenolysis in acid solution, so obviously shortening of the transformation period of bubble behind the adding acid catalyst is easy to occur gas-liquid layering or bubble and converges escaping phenomena.
In the patent documentation of more than announcing, the one, starch filled method foaming obtains spongy mass, and the 2nd, can react the method filling-foam of emitting gas through entrained gas or interpolation and obtain spongy mass.The former is because of the starch wash problem, and water loss is big on the one hand, thereby two aspects restrict its use in the high-end field because being difficult to clean thoroughly influences product quality; If latter's technology controlling and process is bad, then the finished product rate is very low.The present invention is through different physical propertys and chemical property that continuous liquid-phase system shows under different condition, effectively solves the various defectives that sample that two kinds of methods produce exists,
Summary of the invention
For solving above-mentioned middle problem and the defective that exists, the invention provides a kind of PVF sponge material and preparation method thereof.Overcome finished product rate that conventional production methods causes low and go mouldy, quality problems such as xanthochromia.In addition, the present invention can satisfy the demands of different of different application field to product performance at physical performance indexs such as regulated in wider range sponge pore size, elasticity, intensity, rate of water absorption and water absorbent rates.Said technical scheme is following:
The PVF sponge material of the even quick imbibition of abscess comprises:
Said material comprises Z 150PH, linking agent, catalyzer, pore former, and the emulsifying agent that adds according to the pore former that uses; Said linking agent is formaldehyde, Paraformaldehyde 96 or formaldehyde solution; Said catalyzer is one or more in hydrochloric acid, phosphoric acid, nitric acid, the sulfuric acid; Said pore former is water soluble organic substance matter or non-water soluble substance; Wherein, the alcoholysis degree of Z 150PH is between 60%～90%, and mean polymerisation degree is between 800～2000.
The preparation method of the PVF sponge material of the even quick imbibition of abscess comprises:
2～9 parts Z 150PH, 10～200 parts of temperature are stirred into solution in being 60～98 ℃ water; And in solution, add 0.05～8 part pore former; After fully emulsified or dissolving forms finely dispersed continuous liquid phase with pore former; Add 1～26 part catalyzer and 1～15 part linking agent or 5～50 parts recovery waste liquid, 1～8 part catalyzer and 1～15 part linking agent and mix, pour mould after 1～60 minute into and carry out crosslinking reaction, after 0.1～2 hour successive liquid-phase system takes place to change and forms abscess; Continued to add thermomaturation 2～18 hours; With pouring out mould after the cooling of the product of slaking, reclaim waste liquid, and cut again after product tentatively cleaned, deeply cleans and be made for the PVF sponge material.
The beneficial effect of technical scheme provided by the invention is:
Production process is not used starch, and last raffinate is clarifying raffinate behind the products solidifying, and is recyclable, thereby has solved the problem because of using acid that starch brings and residual aldehydes not to reuse; Production technique is the foaming method of using gas filling not; When having solved the production of gas filling-foam method, the product surface gas that contacts with mould breaks, and forms dead skin; The product upper surface that contacts with air is then because of escape of gas; Also form the dead skin of no abscess, thereby cause very high product scrap stock, reduce the product utilization rate greatly; Solved the product rate of closed hole height that gas filling-foam method is produced, the shortcoming that the product rate of water absorption is slow; Utilized water-soluble substances as pore former, it forms in water and stablizes mixed solution, and pore size is controlled, controlled porosity, and the product abscess is very evenly attractive in appearance; Simultaneously, the product elasticity of producing gained through this kind inventive method is excellent, and rate of water absorption improves greatly, and water retention also improves a lot than other method; In addition, because of this technological cycle has been used the waste liquid of products solidifying process generation, and produce the no dead skin in products obtained therefrom surface, product extremely is easy to clean, and bigger saving water of productive use has reduced production energy consumption, has reduced to produce and has discharged.
This stable processing technique, production efficiency is high, and life cycle of the product is short.
Embodiment
For making the object of the invention, technical scheme and advantage clearer, do to describe in detail further in the face of embodiment of the present invention down:
Present embodiment provides the PVF sponge material of the even quick imbibition of a kind of abscess, and this material comprises:
Z 150PH, linking agent, catalyzer and pore former and necessary emulsifying agent, said linking agent is formaldehyde, Paraformaldehyde 96 or formaldehyde solution; Said catalyzer is one or more in hydrochloric acid, phosphoric acid, nitric acid, the sulfuric acid; Above-mentioned pore former is water soluble organic substance matter or non-water soluble substance; Above-mentioned water soluble organic substance comprise propyl alcohol, Virahol, just/water soluble organic substances such as brothers/butanols, USP Kosher, terepthaloyl moietie, polyoxyethylene glycol, ETHYLE ACETATE, ethyl propionate, Vinylpyrrolidone polymer, SEPIGEL 305, sodium cellulosate, THF, wilkinite, organic synthesis soil, but Vinylpyrrolidone polymer, polyoxyethylene glycol, SEPIGEL 305, sodium cellulosate and organic synthesis soil are preferential.
Above-mentioned water-insoluble organism comprises non-water soluble substance such as paper fiber, corn cob, zeyssatite, kerosene, whiteruss, sherwood oil, methylethylketone.
The alcoholysis degree of above-mentioned Z 150PH is between 60%～90%, and mean polymerisation degree is between 800～2000.
Present embodiment also provides the preparation method of the PVF sponge material of the even quick imbibition of a kind of abscess; Be included under certain condition linear polyethylene alcohol polymer is carried out crosslinking curing; In earlier stage adding the pore former blend in the crosslinking curing link dissolves each other; Phase system takes place to change and forms the perforate foam in the intensification solidification process, after cross-linking curing, obtains the sponge product, and sponge cuts, is packaged to be novel quick imbibition sponge material after cleaning.The following embodiment of its concrete making processes:
Embodiment 1
2 parts Z 150PH, 20 parts of temperature are stirred into solution in being 90 ℃ water; In the process that stirs, in solution, add 2 parts pore former, 0.01 part emulsifying agent; After the finely dispersed continuous liquid phase of the fully emulsified formation of pore former, add 3 parts formaldehyde solution, 50% sulphuric acid soln that the back adds 2 parts, pour in the mould after the full and uniform mixing; Be warming up to 90 ℃ of slakings 4 hours after reaction successive liquid-phase system generation in 1 hour transformation formation abscess down at 75 ℃; Shift out mould with after the product after the slaking cooling, and waste liquid is recycled, product is rolled wash; Cleaning up the back cuts product, sterilize and packs under the varying environment condition according to application need.
Embodiment 2
5 parts Z 150PH, 80 parts of temperature are stirred formation solution in being 90 ℃ water; In the process that stirs, in solution, add 0.2 part pore former, 0.01 part emulsifying agent, after the finely dispersed continuous liquid phase of the fully emulsified formation of pore former, add 5 parts formaldehyde solution; Sulphuric acid soln that the back adding is 10 part 50% or 10 parts recovery waste liquid, 4 parts linking agent mix; Pour into after 10 minutes and carry out crosslinking reaction in the mould after 0.5 hour, the successive liquid-phase system added thermomaturation 8 hours after taking place to change and forming abscess under 70 ℃; Pour out mould after the product cooling with slaking; Reclaim waste liquid, and cut again after product tentatively cleaned, deeply cleans and be made for the PVF sponge material, be made for the PVF sponge material.
Embodiment 3
Elder generation is abundant dispersed with stirring in 95 ℃ of water with 7 parts Z 150PH 100 parts of temperature; Under agitation condition, add the abundant together dispersing and dissolving of 4 parts of pore formers, or the cooling back adds 4 parts pore former dispersed with stirring; Add 9 parts linking agent, 15 parts catalyzer successively; Or add 15 parts catalyzer, 9 parts of linking agents successively, or add 20 parts recovery waste liquid, 10 parts catalyzer, 10 parts linking agent successively, or add 20 parts recovery waste liquid, 9 parts linking agent, 10 parts catalyzer successively; Stir and pour in the mould after 15 minutes; In mould, carry out crosslinking reaction after 1 hour, after the successive liquid-phase system take place to change forms abscess, continue heating crosslinking reaction 12 hours under 76 ℃ of temperature; Product after the slaking is shifted out mould and the waste liquid that produces is recycled; Product is cleaned; According to application need product is cut and packs.
Embodiment 4
8 parts Z 150PH, 120 parts of temperature are stirred into solution in being 100 ℃ water; In the process of stirring, in solution, add 6 parts pore former, abundant formaldehyde solution, 18 part of 50% sulphuric acid soln of back adding that dissolves 10 parts of back addings; Stir and pour in the mould after 20 minutes; Afterwards 80 ℃ of following crosslinking reactions 15 hours, the product after the slaking is shifted out mould and waste liquid is recycled, product is rolled wash; Cleaning up the back cuts, sterilizes and pack at varying environment condition decline product according to application need.
Embodiment 5
9 parts Z 150PH, 60 parts of temperature are stirred into solution in being 100 ℃ water; In the process that stirs, in solution, add and pour mould into after 0.77 part pore former, 22 parts recovery waste liquid, 8 parts the linking agent of catalyzer and 8 parts of linking agent or 30 parts of catalyzer and 7 parts stir 28 minutes and carried out crosslinking reaction 16 hours, be made for the PVF sponge material.
Embodiment 6
Is fully to stir in 105 ℃ of water until dissolving fully 9 parts Z 150PH 200 parts of temperature; Cooling back adds 15 parts formaldehyde solution under agitation condition, stirs to add 50 parts after 30 minutes and reclaim waste liquids, and 26 parts of concentrated hydrochloric acids, 8 parts of pore formers, stirring was poured in the mould after abundant together, 95 ℃ of following crosslinking curings 18 hours; Product after solid is shifted out mould, reclaim waste liquid, and product is tentatively cleaned, cut again after deeply cleaning and be made for the PVF sponge material, product is cut, sterilizes and packs under the varying environment condition according to application need at last.
The principle of the foregoing description pore-forming: earlier with the pore former homodisperse or be dissolved in the polyvinyl alcohol solution; Form the even liquid phase of successive; Z 150PH reacts through catalyst and linking agent at a certain temperature; And from external phase, separate and separate out, thereby form three-dimensional penetrating foam sponge body.
Products obtained therefrom demoulding after cooling off after the foregoing description slaking; And the waste liquid that reaction process is produced recycles and reuses; Afterwards the circulation form of product through drying-immersion-drying more tentatively cleaned, or roll the method for washing through two rollers that rotate continuously and tentatively clean.
Preliminary clean the back cut preceding or cut after product is dried, be immersed in the solution that contains ozone or hydrogen peroxide, or be immersed in the ultrasonic cleaner of flowing water, carry out deep cleaning through the method for ozone, hydrogen peroxide oxidation method or ultrasonic vibration.
Above-mentioned PVF sponge material is the PVF porous foam; Has three-dimensional open-celled structure; Average foam diameter is between 10 μ m～1500 μ m, and percentage of open area is between 15%～90%, and porosity is between 60%～96%; Its degree of acetalization is between 25%～98%, but degree of acetalization is preferential between 25%～70%.
Above-mentioned PVF sponge forms different size according to mould size and shape, and the sponge after will cleaning as required cuts, cleans once more, dry or compress; The cutting profile of said sponge is: the quick imbibition of tabular, sheet, circle shape, bar-shaped or other polymorphic structure, filter or the quick-acting haemostatic powder material fast.
The above is merely preferred embodiment of the present invention, and is in order to restriction the present invention, not all within spirit of the present invention and principle, any modification of being done, is equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (4)
1. the PVF sponge material of the even quick imbibition of abscess is characterized in that, said material comprises Z 150PH, linking agent, catalyzer, pore former, and the emulsifying agent that adds according to the pore former that uses; Said linking agent is formaldehyde, Paraformaldehyde 96 or formaldehyde solution; Said catalyzer is one or more in hydrochloric acid, phosphoric acid, nitric acid, the sulfuric acid; Said pore former is water soluble organic substance or non-water soluble substance; Wherein, the alcoholysis degree of Z 150PH is between 60%～90%, and mean polymerisation degree is between 800～2000;
Said water soluble organic substance is selected from propyl alcohol, Virahol, USP Kosher, terepthaloyl moietie, polyoxyethylene glycol, ETHYLE ACETATE, ethyl propionate, Vinylpyrrolidone polymer, SEPIGEL 305, sodium cellulosate and THF;
Said non-water soluble substance is selected from kerosene, whiteruss, sherwood oil and methylethylketone non-water soluble substance;
Said emulsifying agent comprises tween 80, polysorbate60, Supragil GN, at least a in the OP-10 emulsifying agent.
2. the preparation method of the PVF sponge material of the even quick imbibition of abscess according to claim 1; It is characterized in that, 2～9 parts Z 150PH are stirred into solution in 10～200 parts of temperature are 60～98 ℃ water, and in solution, add 0.05～8 part pore former; After the finely dispersed continuous liquid phase of the fully emulsified formation of pore former; Add 1～26 part catalyzer and 1～15 part linking agent and mix, pour mould after 1～60 minute into and carry out crosslinking reaction, after 0.1～2 hour successive liquid-phase system takes place to change and forms abscess; Continued to add thermomaturation 2～18 hours; With pouring out mould after the cooling of the product of slaking, reclaim waste liquid, and cut again after product tentatively cleaned, deeply cleans and be made for the PVF sponge material.
3. the preparation method of PVF sponge material according to claim 2 is characterized in that, the method for the sponge product being carried out deep cleaning is ozone, hydrogen peroxide oxidation method or ultrasonic cleaning process.
4. the preparation method of PVF sponge material according to claim 2 is characterized in that, said PVF sponge material is the PVF porous foam; Has three-dimensional open-celled structure; Average foam diameter is between 10 μ m～1500 μ m, and percentage of open area is between 15%～90%, and porosity is between 60%～96%; Its degree of acetalization is between 50%～85%; Said PVF sponge size and specification decide according to mold shape and size, and can be as required with sponge cut, dry or compress, wherein cut and can use normal temperature to cut or freezing cutting.
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| CN103274519A (en) * | 2013-06-08 | 2013-09-04 | 郑州大学 | Black Locust particle/polyvinyl formal composite filler and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103274519A (en) * | 2013-06-08 | 2013-09-04 | 郑州大学 | Black Locust particle/polyvinyl formal composite filler and preparation method thereof |
| CN103274519B (en) * | 2013-06-08 | 2014-10-15 | 郑州大学 | Black Locust particle/polyvinyl formal composite filler and preparation method thereof |
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