CN1821289A - Method for preparing nano montmorillonite modified natural emulsion medical product - Google Patents
Method for preparing nano montmorillonite modified natural emulsion medical product Download PDFInfo
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- CN1821289A CN1821289A CNA2006100330327A CN200610033032A CN1821289A CN 1821289 A CN1821289 A CN 1821289A CN A2006100330327 A CNA2006100330327 A CN A2006100330327A CN 200610033032 A CN200610033032 A CN 200610033032A CN 1821289 A CN1821289 A CN 1821289A
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Abstract
The present invention discloses the preparation process of nanometer montmorillonite modified natural latex for medical product. Montmorillonite, which may be natural montmorillonite mineral, nanometer montmorillonite, organic montmorillonite treated with C12-C18 alkyl trimethyl ammonium chloride or ammonium bromide or nanometer montmorillonite through mechanical and chemical grinding, is added into natural rubber latex in the sulfurizing or cooperating stage, and through the subsequent dispersion, pressurizing or dipping, washing, filtering and sulfurizing drying, the modified product is obtained. The present invention has simple technological process, and the prepared medical product has excellent ageing resistance, high tensile and breaking strength, and good microbe permeation resistance.
Description
Technical field
The present invention relates to the natural rubber latex is the preparation method of medical products such as the condom of raw material and medical gloves, latex examination gloves, catheter, tube for blood transfusion,latex.
Background technology
Natural rubber latex originates from Para rubber tree (Hevea brasiliensis), is a kind of natural polymer product.Natural rubber latex prepares curable product following advantage: directly by the process for processing of natural product latex, complete processing is simple, easily gelling, and good film-forming property, the wet gel strength height, easily sulfuration, cost is low, and environmental pollution is little, belongs to environment-friendly type production; Goods elasticity is big, the intensity height, and creep is little, excellent combination property; From the natural biological product, no synthetic materials low-molecular-weight component and additive etc. are little to the human influence; Be a kind of renewable resource material, be not subjected to the influence of Nonrenewable resources such as oil, meet the requirement of Sustainable development.Therefore, the medical product with the natural rubber latex preparation is the widely used medical products in countries in the world.Because the natural rubber latex product properties is superior, cheap, meet China's consumption national conditions, China's mass production and use at present comprises natural rubber latex goods such as all kinds of medical catheters, surgical glove, latex examination gloves and condom.Expect 2005, China will produce 2,400,000,000 of condoms, 800,000,000 of latex examination glovess, and 300,000,000 pairs of medical glovess are more than tube for blood transfusion,latex 1500 myriametres.Quite grow one period in future, in China is developing country basic, that the level of economic development is not high, people in the countryside account for the overwhelming majority like this with the agricultural, these will be leading product, and consumption will improve year by year, especially when incidents such as burst communicable disease,, its demand is increased greatly for avoiding that numerous people are produced harm, in that time as SARS outburst in 2003 and 2004 " bird flu " appearance, the latex examination gloves consumption has increased several times.In addition, China will adhere to executive plan fertility fundamental state policy for a long time, and from now on, vast Rural areas also will further increase the demand of condom.
But natural emulsion medical product is still needed and will be done following improvement:
1, because goods major parts such as latex glove and condom are thin products, adds the restriction of curable product, make that goods ubiquity ageing-resistant performance is not enough, shelf time short, easy aging shortcoming such as be clamminess anti-aging agent.
2, owing to can't add many strengthening agents, its anti-opening with tear-resistant intensity can not meet the demands, and product is prone to fracture phenomena.Therefore, it is necessary that the natural emulsion gloves are carried out enhancing modified, but must solve the dispersion of supporting material and interface in conjunction with problem, and this also is one of outstanding difficult problem of latex industry.
3, need further to improve of the effective obstruct of traditional latex thin products, to satisfy the use of product under the different occasions to virus infiltration.
Summary of the invention
For addressing the above problem, the purpose of this invention is to provide a kind of preparation method of nano montmorillonite modified natural emulsion medical product, prepared medical product have better ageing-resistant, stretch-proof and tear, antimicrobial penetrating quality.
For achieving the above object, the preparation method of nano montmorillonite modified natural emulsion medical product of the present invention is as follows: be used to the original montmorillonoid soil from the clay mineral, or na montmorillonite, or, obtain the nano imvite that lamellar spacing is 5～500 nanometers through the mechanochemistry method for grinding through 12 organic montmorillonoids to octadecyl trimethyl ammonium chloride or brometo de amonio processing; With the natural rubber latex is raw material, in raw material prevulcanized or compounding operation, above-mentioned gained nano imvite is added equably, is distributed to the natural rubber latex Ruzhong, by dipping or extrusion, leaching, sulfuration drying, finished product.
Described mechanochemistry method for grinding can be ball milled, colloid milling, sand-blast, vibrations mill method or impact grinding method or the like, adopts the wet processes of adding grinding aid, handles 2-24 hour.
Described grinding aid is polypropylene or polyethylene or polystyrene micro mist or its admixed finepowder, and addition is the 10-25% of polynite amount.
Described nano imvite is with 0.5～3.9: 100 dried part of weight ratio adds described natural rubber latex Ruzhong.
As a kind of preferred version, described nano imvite is with 0.5～3.0: 100 dried part of weight ratio adds described natural rubber latex Ruzhong.This scheme is particularly useful for preparing latex prophylactic, medical gloves or latex examination gloves.
As another preferred version, described nano imvite is with 1～3.5: 100 dried part of weight ratio adds described natural rubber latex Ruzhong.This scheme is particularly useful for preparing latex catheter.
As another preferred version, described nano imvite is with 2～3.9: 100 dried part of weight ratio adds described natural rubber latex Ruzhong.This scheme is particularly useful for preparing the latex tube for blood transfusion,latex.
Because adopt above technical scheme, its effect is conspicuous:
Because having adopted mechanochemistry method for grinding such as comprising ball milled, colloid milling, sand-blast, vibrations mill method or impact grinding handles polynite, and, therefore can produce the positive effect of following several respects in conjunction with adopting the wet processes of adding grinding aid: the one, can peeling off of more effective realization montmorillonite layer make it produce real nanometer polynite; Make the further miniaturization of polynite particle, when obtaining lamellar spacing and reach nano-scale, also obtain the more polynite of small-particle; Can change polynite particle surface chemical property, increase its dispersion in latex, and strengthen it and combine with the interface of rubber hydrocarbon.These effects are that the mode of polynite directly being sneaked into latex and can only handle by simple agitation that has adopted at present be to be beyond one's reach, because fiercer stirring can make mechanical stability of latex destroyed and produce to solidify production can't be continued.
Because of the nano imvite lamella that adds can be scattered in the latex to peel off state, and evenly be adsorbed on the rubber particles surface, behind latex coagulation, forming good interface with rubber phase combines, the polynite disperse phase plays the effect of physical crosslinking point, improved and the rubber hydrocarbon macromole between the effect of Van der Waals force and the entanglement of molecular chain, when little loading level, montmorillonite layer structure and coacervate thereof just produce stronger restriction to rubber macromolecular chain mobility, and the material tensile modulus is improved; Simultaneously, because the high-modulus nanoparticle can meet with stresses and can meet with stresses greatly than base rubber, the system that guaranteed is stablized ability of anti-deformation, stops crackle to spread to rubber phase effectively, thereby the stretch-proof of material, tearing toughness are increased substantially.In addition, the iris action of nano imvite laminated structure, diffusion and the permeation pathway of oxygen in material prolonged greatly, hindered the dispersal behavior of carrier of oxygen molecule in sizing material consumingly, the crystal layer structure of polynite has also limited high molecular motion, therefore, the goods heatproof air aging performance improves greatly, has also improved obstruct and impermeabilisation effect to microorganisms such as viruses.
The contriver has carried out performance test to latex catheter, latex tube for blood transfusion,latex and the latex prophylactic that is made by method of the present invention, the results are shown in following table:
| Sample | Tensile strength (MPa) | Tensile yield (%) | 500% tensile modulus (MPa) | |||
| Before aging | Aging velocity of variation % | Before aging | Aging velocity of variation % | Before aging | Aging velocity of variation % | |
| Latex prophylactic | 26.8 | -23.0 | 960 | -9.0 | 2.2 | -10.0 |
| Latex catheter | 27.0 | -22.0 | 960 | -5.4 | 2.3 | -8.0 |
| The latex tube for blood transfusion,latex | 28.0 | -21.0 | 970 | -5.8 | 2.4 | -9.0 |
As seen, the prepared various medical products of method of the present invention have good ageing-resistant, stretch-proof and tear, antimicrobial penetrating quality.
Embodiment
Embodiment 1
Produce the basic technology prescription following (in mass) of latex prophylactic, medical gloves, latex examination gloves:
Drc is 60% concentrated natural latex 100
Nano imvite 0.5-3.0
Dispersion agent (polyoxyethylene nonylphenol ether: alkylphenol polyoxyethylene) 0.3
Dry ferment 0.1
KOH 0.05
Sulfur 1
Promotor PX (N-ethyl-N-phenyl zinc dithiocarbamate) 0.8
Promotor ZDC (zinc diethyldithiocarbamate) 1
Antioxidant 264 (2,6 ditertiary butyl p cresol) 1.5
ZnCO
3 1
Implementation step:
At first the organic montmorillonoid of 0.5-3.0 part 12 to octadecyl trimethyl ammonium chloride or brometo de amonio processing mixed with 4-5 times of deionized water, add 0.075 part of dispersion agent and 10-25% grinding aid polypropylene (in the polynite amount) again, adopt methods such as ball milled, colloid milling, sand-blast, vibrations mill method or impact grinding that polynite was handled 2-24 hour then, obtain the nanometer polynite.
Get drc and be 100 parts of 60% concentrated natural latexes, add 0.225 part of dispersion agent, add above-mentioned gained nano imvite again, be mixed with stable emulsion.By above-mentioned prescription sulphur, promotor PX, promotor ZDC, antioxidant 264 are made the dispersion that concentration is 20-60% with deionized water respectively; Potassium hydroxide is made the dispersion that concentration is 1.0-30% with deionized water; Casein is made the dispersion that concentration is 5-15% with deionized water.Then above-mentioned each component is joined in the latex.Last comprise that according to the conventional production process of latex prophylactic, gloves prevulcanized, maturation, dipping, leaching, the demoulding, drying and other steps make finished product again.
Embodiment 2
Produce the basic technology prescription following (in mass) of latex catheter:
Drc is 60% concentrated natural latex 100
Nano imvite 1-3.5
Dispersion agent (emulsifying agent T: the sorbitan fatty acid ester Soxylat A 25-7) 0.3
Dry ferment 0.1
KOH 0.05
Sulfur 1
Promotor PX (N-ethyl-N-phenyl zinc dithiocarbamate) 0.8
Promotor ZDC (zinc diethyldithiocarbamate) 1
Antioxidant 264 (2,6 ditertiary butyl p cresol) 1.5
ZnCO
3 1
Implementation step:
At first 1-3.5 part na montmorillonite is mixed with 4-5 times of deionized water, add 0.075 part of dispersion agent and 10-25% grinding aid polyethylene (in the polynite amount) again, adopt methods such as ball milled, colloid milling, sand-blast, vibrations mill method or impact grinding that polynite was handled 3-24 hour then, obtain the nanometer polynite.
Get drc and be 100 parts of 60% concentrated natural latexes, add 0.225 part of dispersion agent, add above-mentioned gained nano imvite again, be mixed with stable emulsion.By above-mentioned prescription sulphur, promotor ZDC, promotor PX, antioxidant 264 are made the dispersion that concentration is 20-60% with deionized water respectively, potassium hydroxide is made dispersion that concentration is 1-30%, casein is made the dispersion that concentration is 5-15% with deionized water with deionized water, then above-mentioned each component is joined in the latex.And then comprise that according to the conventional production process of latex catheter prevulcanized, maturation, dipping, chlorination, coating, the demoulding, drying and other steps make finished product.
Embodiment 3
Produce the basic technology prescription following (in mass) of latex tube for blood transfusion,latex:
Drc is 60% concentrated natural latex 100
Nano imvite 2-3.9
Dispersion agent (peregal: fatty alcohol-polyoxyethylene ether) 0.2
Sulfur 1
Altax (benzothiazyl disulfide) 0.8
Promotor TT (tetramethyl-thiuram disulfide) 0.8
Antioxidant 264 (2,6 ditertiary butyl p cresol) 1.5
ZnCO
3 1
Implementation step:
At first the original montmorillonoid soil of 2-3.9 part from clay mineral mixed with 4-5 times of deionized water, add the polyethylene of 0.075 part of dispersion agent and 10-25% and the admixed finepowder of polystyrene (in the polynite amount) again, adopt methods such as ball milled, colloid milling, sand-blast, vibrations mill method or impact grinding that polynite was handled 2-24 hour then, obtain the nanometer polynite.
Get drc and be 100 parts of 60% concentrated natural latexes, add 0.225 part of dispersion agent, add above-mentioned gained nano imvite again, be mixed with stable emulsion.By above-mentioned prescription sulphur, promotor TT, altax, antioxidant 264 are made the dispersion that concentration is 20-60% with deionized water respectively, then above-mentioned each component is joined in the latex, the conventional production process according to the latex tube for blood transfusion,latex comprises that prevulcanized, extrusion, bubble are washed, drying and other steps is made finished product again.
Claims (10)
1, a kind of preparation method of nano montmorillonite modified natural emulsion medical product, it is characterized in that: be used to original montmorillonoid soil from the clay mineral, or na montmorillonite, or, obtain the nano imvite that lamellar spacing is 5～500 nanometers through the mechanochemistry method for grinding through 12 organic montmorillonoids to octadecyl trimethyl ammonium chloride or brometo de amonio processing; With the natural rubber latex is raw material, in raw material prevulcanized or compounding operation, above-mentioned gained nano imvite is added equably, is distributed to the natural rubber latex Ruzhong, by dipping or extrusion, leaching, sulfuration drying, finished product.
2, preparation method according to claim 1 is characterized in that: described mechanochemistry method for grinding is ball milled, colloid milling, sand-blast, vibrations mill method or impact grinding method, adopts the wet processes of adding grinding aid, handles 2-24 hour.
3, preparation method according to claim 2 is characterized in that: described grinding aid is polypropylene or polyethylene or polystyrene micro mist or its admixed finepowder, and addition is the 10-25% of polynite amount.
4, preparation method according to claim 1 is characterized in that: described nano imvite is with 0.5～3.9: 100 dried part of weight ratio adds described natural rubber latex Ruzhong.
5, preparation method according to claim 4 is characterized in that: described nano imvite is with 0.5～3.0: 100 dried part of weight ratio adds described natural rubber latex Ruzhong.
6, preparation method according to claim 4 is characterized in that: described nano imvite is with 1～3.5: 100 dried part of weight ratio adds described natural rubber latex Ruzhong.
7, preparation method according to claim 4 is characterized in that: described nano imvite is with 2～3.9: 100 dried part of weight ratio adds described natural rubber latex Ruzhong.
8, preparation method according to claim 5 is characterized in that: described medical product is latex prophylactic, medical gloves or latex examination gloves.
9, preparation method according to claim 6 is characterized in that: described medical product is a latex catheter.
10, preparation method according to claim 7 is characterized in that: described medical product is the latex tube for blood transfusion,latex.
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Cited By (9)
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| CN100457812C (en) * | 2006-12-25 | 2009-02-04 | 中国地质大学（武汉） | Process for preparing attapulgite and natural rubber nano composite material |
| CN101664565A (en) * | 2009-09-06 | 2010-03-10 | 中国热带农业科学院橡胶研究所 | Nano hydroxylapatite/natural rubber latex composite medical rubber latex and preparation method thereof |
| CN106432828A (en) * | 2016-11-17 | 2017-02-22 | 无锡市长安曙光手套厂 | Desensitizing latex glove material |
| CN107746481A (en) * | 2017-09-16 | 2018-03-02 | 南京工程学院 | A kind of NR latex/clay organic aerogel composite and preparation method thereof |
| CN107955238A (en) * | 2017-11-10 | 2018-04-24 | 中红普林（北京）医疗用品高新技术研究院有限公司 | A kind of ultra-thin NBR latex gloves and preparation method thereof |
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| CN1121442C (en) * | 2000-12-07 | 2003-09-17 | 财团法人工业技术研究院 | Nano polymer composite material and its prepn. |
| CN1194998C (en) * | 2002-08-20 | 2005-03-30 | 华南理工大学 | Nano-class rubber-laminated inorganic substance composition and its preparing process |
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- 2006-01-18 CN CNB2006100330327A patent/CN100351293C/en not_active Expired - Fee Related
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| CN100457812C (en) * | 2006-12-25 | 2009-02-04 | 中国地质大学（武汉） | Process for preparing attapulgite and natural rubber nano composite material |
| CN101664565A (en) * | 2009-09-06 | 2010-03-10 | 中国热带农业科学院橡胶研究所 | Nano hydroxylapatite/natural rubber latex composite medical rubber latex and preparation method thereof |
| CN101664565B (en) * | 2009-09-06 | 2013-02-20 | 中国热带农业科学院橡胶研究所 | Nano hydroxylapatite/natural rubber latex composite medical rubber latex and preparation method thereof |
| CN106432828A (en) * | 2016-11-17 | 2017-02-22 | 无锡市长安曙光手套厂 | Desensitizing latex glove material |
| CN107746481A (en) * | 2017-09-16 | 2018-03-02 | 南京工程学院 | A kind of NR latex/clay organic aerogel composite and preparation method thereof |
| CN107955238A (en) * | 2017-11-10 | 2018-04-24 | 中红普林（北京）医疗用品高新技术研究院有限公司 | A kind of ultra-thin NBR latex gloves and preparation method thereof |
| CN107955238B (en) * | 2017-11-10 | 2020-07-14 | 中红普林（北京）医疗用品高新技术研究院有限公司 | Ultrathin butyronitrile latex glove and preparation method thereof |
| CN108530695A (en) * | 2018-04-27 | 2018-09-14 | 陕西杨凌陕特农业发展有限公司 | A kind of rubber and preparation method thereof containing honey |
| CN111621069A (en) * | 2019-02-27 | 2020-09-04 | 北京化工大学 | Graphene oxide and/or layered silicate natural rubber composite material for space balloon and preparation method thereof |
| CN114106362A (en) * | 2020-08-31 | 2022-03-01 | 中国石油化工股份有限公司 | Method for optimizing physical properties of emulsion polymerized styrene butadiene rubber |
| CN114106362B (en) * | 2020-08-31 | 2024-01-05 | 中国石油化工股份有限公司 | Method for optimizing physical properties of emulsion polymerized styrene-butadiene rubber |
| CN115990284A (en) * | 2023-01-06 | 2023-04-21 | 杭州沸创生命科技股份有限公司 | Slurry for coating hemostatic gauze and hemostatic gauze prepared from slurry |
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