CN1931909A - Composite material of modified micro plant fiber powder and natural rubber and its prepn process and application - Google Patents
Composite material of modified micro plant fiber powder and natural rubber and its prepn process and application Download PDFInfo
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- CN1931909A CN1931909A CNA2006100375807A CN200610037580A CN1931909A CN 1931909 A CN1931909 A CN 1931909A CN A2006100375807 A CNA2006100375807 A CN A2006100375807A CN 200610037580 A CN200610037580 A CN 200610037580A CN 1931909 A CN1931909 A CN 1931909A
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Abstract
The present invention discloses one kind of composite material of modified micro plant fiber powder and natural rubber and its preparation process and application. The composite material includes natural rubber or latex 100 weight portions, modified micro plant fiber powder 1-60 weight portions, sulfur 0.5-3.3 weight portions, promoter 1.2-4.3 weight portions, antiager 1-3 weight portions and other assistant. The preparation process includes mixing, forming, vulcanizing and other steps. The composite material has high tensile strength, high tearing strength, high ageing resistance, high virus permeation resistance, etc. and may be used widely in making urinary catheter, blood transfusion tube, condom, medical gloves and other products.
Description
Technical field
The present invention relates to the natural rubber is modified micro plant fiber powder matrix material of raw material and preparation method thereof, and the application in goods such as preparation catheter, tube for blood transfusion,latex, condom, medical gloves, latex examination gloves, foam materials, hand cart tyre, sole.
Background technology
Resource is the basis that development is continued, Sustainable utilization of resources is the basic premise condition of Sustainable development, therefore, must make great efforts to seek one " population, economy, society, environment and resource are coordinated mutually, can satisfy the contemporary people demand and don't the requirement capability that satisfies future generations is constituted the sustainable development path that endangers ".
Natural rubber originates from Para rubber tree, is important industrial raw material and strategic materials, always is subjected to countries in the world and payes attention to.Natural rubber has snappiness, low-heat-generation, high-wearing feature, insulativity, resistance to air loss and anti-tortuous performance, makes it can't be synthesized rubber and replaces.Especially at tire industry, because of wear resistance and splitting resistance under natural rubber anti-slippery, the high temperature all are better than general purpose synthetic rubber, so it is still the best raw material of making aircraft, cargo truck and cross-country vehicle tire, especially big with weight-carrying capacity, performance requriements is strict, as the tire of Boeing-747 airliner etc., must all make with natural rubber.
Be that the exhaustion that the China Synthetic Rubber Industry of raw material will face the petrochemical industry resource is failed with petrochemicals, and utilize light, heat, soil etc. relatively the natural rubber of unlimited resources production show its realistic meaning more especially.In addition, natural rubber processing belongs to the environment-friendly type processing of less energy-consumption, low environment pollution.And, by modification, can produce a series of alternative elastomeric products to natural rubber.Therefore, it is widely used in many industrial circles and industry, and enters huge numbers of families.
Aspect tire product, except that a large amount of rubber tyres that the automotive industry of growth at full speed adopts, China is bike, walkie fork lift truck and motorcycle big producing country, and to 2004, nearly 600,000,000 of China's year productivity tire quantity was the first in the world.
Aspect article of footwear, China is that the first in the world rubber overshoes are made big country, and the footwear that all have China to produce all over the world, natural rubber are widely used in to be made at the bottom of the leather shoes and micropore sole etc.
Aspect medical device product, natural rubber latex is used for producing in a large number comprises goods such as all kinds of medical catheters, surgical glove, latex examination gloves and condom.By 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.Curable product with the natural rubber latex preparation has following advantage: can be directly by natural rubber latex production, and technology is simple; The easy gelling of latex, easily sulfuration, good film-forming property, wet gel strength height; Goods elasticity is big, intensity is high, creep is little, excellent combination property, and no synthetic materials low-molecular-weight component and additive etc. are little to the human influence; Production cost is low, and environmental pollution is little, belongs to environment-friendly type production.Because natural rubber latex goods cost performance is good, meet China's consumption national conditions, quite growing one period in future will be leading product.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.
China is a large agricultural country, and crop by-product-vegetable fibre is first renewable resources.But in China, the utilization ratio of vegetable fibre is but very low.The vegetable fibre main component is a native cellulose fibre, have that intensity height, initial modulus height, easy dyeing, tooling cost are low, characteristics such as processing mechanization degree height, labour intensity are little, three-waste free pollution, economic benefit height, particularly biological degradability is good, can adapt to the environmental protection trend in the whole world.
Utilize the research of the compound preparation advanced composite material of rubber and natural plant fibre, become the focus of investigation of materials.Characteristics such as that the rubber-fibre matrix material has is in light weight, intensity is high, thermal conductivity is little, sound insulation and heat-proof quality are good, the while low cost of manufacture, applied range, and can degrade rapidly under field conditions (factors), therefore, utilize natural plant fibre to greatly develop recycling economy, both can improve agricultural performance, more can replenish the shortage of the Nonrenewable resources that the mankind face in a large number, its production has ecological benefits, economic benefit and social benefit three unities, and human kind sustainable development is had great strategic importance.
Therefore, all carried out a series of research work both at home and abroad, (Beijing University of Chemical Technology's journal such as Huang Li, 3 phases of calendar year 2001) straw powder is put into 75% NaOH solution and is soaked 48h after, isolate fiber and flushing, again through the bleaching after washing to neutral, make vegetable fibre with oven for drying at last, add again phenylformic acid, stearic acid, organosilane after drying again modified plant fibers, its shortcoming is the process complexity, and the alkaline purification meeting produces the waste water that environment is had pollution; Li Zhongmings etc. (plastics industry, 2000 4 phases) mix 5min with surface treatment agent with stalk in the high speed kneader, behind the dry 4h, be mixed with matrix material with polypropylene again in 80 ℃ of baking ovens; Also have other to comprise alkalization and graft modifications such as esterification pre-treatment, vinylbenzene, PMMA grafting processing, thermosetting resin coating, silane coupling agent and titanate coupling agent processing etc., adopted dry method and wet processing, dry process is simple but effect is often not really desirable; Though the wet method effect is obvious, adopts organic solvent more, the expensive and not environmental protection (Zheng Yutao, Mierocrystalline cellulose science and technology, 2005 1 phases) of price.
But all natural plant fibre-rubber composite and preparation methods that adopt at present remain in deficiency:
1, natural plant fibre raw material, because the wetting ability of hydroxyl in its cell walls polymkeric substance, bad with combining of nonpolar natural rubber, performance of composites is undesirable.
2, fiber not only can produce the change of mechanical property and dimensional properties under the moisture existence condition, but also is corroded easily.
3, thermostability is not enough, and the variable color degraded appears in the processing and preparing process.
4, chemical modification modes such as alkalization of adopting both at home and abroad at present and esterification pre-treatment, surface grafting, interface coupling, polymeric coating, and all there is the process complexity in Physical Processing modes such as thermal treatment, discharge process, Cement Composite Treated by Plasma, generation of waste materials is arranged, can produces characteristics such as pollution to environment, and great majority are to be applied to prepare thermoplastic resin or thermoset ting resin composite, use few aspect native rubber composite material.
These have all limited the application of vegetable fibre in rubber industry.
Summary of the invention
In order to solve defective and the deficiency that above-mentioned prior art exists, primary and foremost purpose of the present invention provides a kind of modified plant fibers-native rubber composite material, this matrix material has better interface combination and stretch-proof, tear resistance, thermostability and water tolerance improve, and have simple, pollution-free, eco-friendly characteristics simultaneously again.
Another object of the present invention is to provide the preparation method of above-mentioned modified plant fibers-native rubber composite material.
A further object of the present invention is to provide the application of above-mentioned modified plant fibers-native rubber composite material.
Purpose of the present invention is achieved through the following technical solutions: a kind of modified plant fibers-native rubber composite material comprises following components by weight portions: 100 parts in the latex of natural rubber or weight by dry rubber, 1～60 part of modified micro plant fiber powder, 0.5～3.3 part in sulphur, 1.2～4.3 parts of promotor, 1～3 part in anti-aging agent.
In order to realize the present invention better, described modified plant fibers-native rubber composite material also can select to add following other one or more processing aids, comprises 0.5～4 part in zinc oxide; 0.3 part of polyoxyethylene nonylphenol ether (alkylphenol polyoxyethylene); 0.3 part of emulsifying agent T (sorbitan fatty acid ester Soxylat A 25-7); 0.3 part of paregal O (fatty alcohol-polyoxyethylene ether); ZnCO
31 part; 0.1～0.5 part of dry ferment; KOH0.05～0.15 part; 0.2 part of vulkacit D; Na
2SiF
60.15～0.5 part; 1.2 parts in ammonium sulfate; 1.5 parts in formaldehyde; 1～20 part of high abrasion furnace black(HAF); 1～20 part of semi-reinforcing hydrocarbon black; 30～100 parts of reclaimed rubbers; 3 parts of stearic acid; 5～14 parts in heavy oil; 0.2 part of Whitfield's ointment; 10 parts in Vaseline; Pigment 1-15 part; 1～6 part of blowing agent H (dinitrosopentamethylene tetramine).
Described promotor comprises promotor PX (N-ethyl-N-phenyl zinc dithiocarbamate), promotor ZDC (zinc diethyldithiocarbamate), altax (benzothiazyl disulfide), promotor TT (tetramethyl-thiuram disulfide), promotor PX (N-ethyl-N-phenyl zinc dithiocarbamate), captax (benzothiazolyl mercaptan), accelerant CZ (N cyclohexyl 2 benzothiazole sulfenamide) or vulkacit D (vulkacit D) etc.
Described anti-aging agent comprises antioxidant 264 (2,6 ditertiary butyl p cresol), antioxidant DBH (to stupid diphenol dibenzyl ether), antioxidant MB (2-sulfenyl benzoglyoxaline), antioxidant A (N-phenyl-1-naphthylamine), antioxidant D FC (styroyl pentanoic) or antioxidant D (N-Phenyl beta naphthylamine) etc.
Described modified micro plant fiber powder is prepared from as follows: add chemical modifier and grinding aid in vegetable fibre, adopt mechanochemical method to handle then 0.5～24 hour, obtain modified micro plant fiber powder.Described chemical modifier addition is 5～15% of a vegetable fibre quality, and the grinding aid addition is 6～25% of a vegetable fibre quality.The particle diameter of described modified micro plant fiber powder is 50 nanometers to 10 micron.
Described fiber comprises arghan, sisal fibers, coir, treat banana stalk fasciated fiber, stalk fibre, cotton fiber, silky fibre, ramee, bamboo fibers, jute fibre or Caulis Sacchari sinensis fiber.
Described chemical modifier is any in diacetyl oxide, maleic anhydride, Tetra hydro Phthalic anhydride, stearic acid, oleic acid, linolic acid, linolenic acid, toxilic acid, the phthalic acid etc., and addition is 5～15% of a vegetable fibre quality.
Described grinding aid is polypropylene, polyethylene or polystyrene micro mist etc., and addition is 6～25% of a vegetable fibre quality.
Described mechanochemical method can be that the millstone type force chemical reactor is milled, ball milled, colloid milling, sand-blast, vibrations mill method or impact grinding method etc.
The preparation method of modified plant fibers-native rubber composite material of the present invention, comprise the steps: by weight ratio above-mentioned raw materials modified micro plant fiber powder, sulphur, promotor, anti-aging agent and other processing aid to be added in natural rubber or the latex, be distributed to equably in natural rubber or the latex, make the native rubber composite material that contains modified micro plant fiber powder by prevulcanized, maturation, dipping, leaching, the demoulding, sulfuration drying and other steps again.
The application of modified plant fibers-native rubber composite material in goods such as preparation catheter, tube for blood transfusion,latex, condom, medical gloves, latex examination gloves, foam materials, hand cart tyre, sole.
As a kind of preferred version, described modified plant fibers adds in described 100 parts of natural rubbers (weight by dry rubber) with 15～50 parts of weight, and this scheme is particularly useful for preparing the rubber hand cart tyre.
As another preferred version, described modified plant fibers adds in described 100 parts of natural rubbers (weight by dry rubber) with 30～60 parts of weight, and this scheme is particularly useful for preparing rubber soles.
As another preferred version, described modified plant fibers adds in described 100 parts of natural rubber latexes (weight by dry rubber) with 4～10 parts of weight, and this scheme is particularly useful for preparing latex catheter.
As another preferred version, described modified plant fibers adds in described 100 parts of natural rubber latexes (weight by dry rubber) with 3～15 parts of weight, and this scheme is particularly useful for preparing the latex tube for blood transfusion,latex.
As another preferred version, described modified plant fibers adds in described 100 parts of natural rubber latexes (weight by dry rubber) with 1～8 part of weight, and this scheme is particularly useful for preparing latex prophylactic, gloves.
As another preferred version, described modified plant fibers adds in described 100 parts of natural rubber latexes (weight by dry rubber) with 10～50 parts of weight, and this scheme is particularly useful for preparing the latex foam material.
Modified plant fibers-native rubber composite material of the present invention is the vegetable fibre that is used to from agriculture byproduct, handles and the modified plant fibers of acquisition through the exertin chemistry and the method for chemical modifier and grinding aid modification simultaneously; With natural rubber (latex) is raw material, in raw material cooperation, mixing or coprecipitated operation, above-mentioned gained modified micro plant fiber powder is added in the natural rubber (latex) equably together with other batchings, make native rubber composite material and the goods that contain modified micro plant fiber powder by operations such as molding sulfurations again.
The present invention compared with prior art has following advantage and beneficial effect:
Because having adopted mechanochemical methods such as comprising pan-milling, ball milled, colloid milling, sand-blast, vibrations mill method or impact grinding handles vegetable fibre, and in conjunction with adopting the processing mode that adds grinding aid and chemical modifier, this can produce the positive effect of following several respects: the one, and refinement that can more effective realization vegetable fibre, the crystalline structure of Mierocrystalline cellulose and xylogen is changed, the further miniaturization of fiber crystallite; Two can make grinding aid and chemical modifier produce mechanochemical grafting on vegetable fibre, thereby change the fiber surface chemical property, form the non-polarization modification, and the character of other chemical substance of fiber is changed, increase its dispersion in natural rubber, and strengthen its interface and combine with the non-polar high polymer chain.These effects are that the mode with sneaking into rubber after the direct pulverizing of vegetable fibre that has adopted at present is to be beyond one's reach, because this can make formed product performance, tensile strength, tensile modulus and tearing toughness variation, the more important thing is that the preparation method of employing has simply, no generation of waste materials, pollution-free, eco-friendly characteristics.
Because of passing through organic acid (acid anhydride) chemical modifier, grinding aid macromolecular material and power chemical mode are to the modification of plant cell wall fibrous matter, under the situation that does not change the vegetable fibre mechanical property, can improve its physics and chemical property, make modified plant fibers can be dispersed in the rubber, forming good interface with rubber phase combines, the vegetable fibre 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, rubber macromolecular chain mobility is produced stronger restriction, thereby make the stretch-proof of material, tear strength improves; Fibrous particle forms fibroreticulate skeleton and supports, and the system that guaranteed is stablized ability of anti-deformation, improves tensile modulus, elongation and the tension set performance of material.And vegetable fibre has changed its chemical stability and thermostability through physical and chemical modified, makes its work in-process be not easy variable color, heat-shrinkable and water-absorbent are little, resistance to chemical attack, do not damage by worms, antistatic, long service life.In addition, this vegetable fibre is from the Nature, and production cost is low, and environmental friendliness is pollution-free, therefore, can be referred to as green reinforced matrix material and goods.
Embodiment
The present invention is described in further detail below in conjunction with embodiment, but embodiments of the present invention are not limited thereto.
Embodiment 1 produces latex prophylactic
One, basic technology prescription following (by weight):
Concentrated natural latex (weight by dry rubber) 100
Modified plant fibers powder 1～5
Dispersion agent (polyoxyethylene nonylphenol ether: alkylphenol polyoxyethylene) 0.3
Dry ferment 0.1
KOH 0.15
Sulphur 1.2
Promotor PX (N-ethyl-N-phenyl zinc dithiocarbamate) 0.8
Promotor ZDC (zinc diethyldithiocarbamate) 0.4
Antioxidant 264 (2,6 ditertiary butyl p cresol) 1
ZnO 0.6
Two, implementation step:
At first get the plant arghan, add 5～15% maleic anhydride chemical modifiers (in the vegetable fibre quality), add 6～25% grinding aid polypropylene (in the vegetable fibre quality) again, adopt millstone type force chemical reactor method for grinding that vegetable fibre was handled 0.5～1 hour then, obtain modified micro plant fiber powder.
Get 100 parts of concentrated natural latexes (weight by dry rubber), add 0.3 part of dispersion agent, add 1～5 part of above-mentioned gained modified micro plant fiber powder again, be mixed with stable emulsion.By above-mentioned prescription sulphur, promotor PX, promotor ZDC, antioxidant 264, ZnO being made concentration with deionized water respectively is 20～60% dispersion; It is 1～30% dispersion that potassium hydroxide is made concentration with deionized water; It is 5～15% dispersion that casein food grade is made concentration with deionized water.Then above-mentioned each component is joined in the latex.Last again according to the conventional production process of latex prophylactic, comprise that prevulcanized, maturation, dipping, leaching, the demoulding, sulfuration drying and other steps make finished product.
Embodiment 2 produces medical gloves
One, basic technology prescription following (by weight):
Concentrated natural latex (weight by dry rubber) 100
Modified plant fibers powder 2～8
Dispersion agent (polyoxyethylene nonylphenol ether: alkylphenol polyoxyethylene) 0.3
Dry ferment 0.5
KOH 0.1
Sulphur 0.5
Promotor PX (N-ethyl-N-phenyl zinc dithiocarbamate) 0.8
Promotor ZDC (zinc diethyldithiocarbamate) 0.5
Antioxidant 264 (2,6 ditertiary butyl p cresol) 0.5
Antioxidant MB (2-sulfenyl benzoglyoxaline) 0.5
ZnO 0.5
Two, implementation step:
At first get the plant flaxen fiber, add 5～15% Tetra hydro Phthalic anhydride chemical modifiers (in the vegetable fibre quality), add 6～25% grinding aid polyethylene (in the vegetable fibre quality) again, adopt ball milled that vegetable fibre soil was handled 10～24 hours then, obtain modified micro plant fiber powder.
Get 100 parts of concentrated natural latexes (weight by dry rubber), add 0.3 part of dispersion agent, add 2～8 parts of above-mentioned gained modified micro plant fiber powders again, be mixed with stable emulsion.By above-mentioned prescription sulphur, promotor PX, promotor ZDC, antioxidant 264, antioxidant MB, ZnO being made concentration with deionized water respectively is 20～60% dispersion; It is 1.0～30% dispersion that potassium hydroxide is made concentration with deionized water; It is 5～15% dispersion that casein food grade is made concentration with deionized water.Then above-mentioned each component is joined in the latex.Last comprise that according to the conventional production process of emgloves prevulcanized, maturation, dipping, leaching, the demoulding, sulfuration drying and other steps make finished product again.
Embodiment 3 latex examination glovess
One, basic technology prescription following (by weight):
Concentrated natural latex (weight by dry rubber) 100
Modified plant fibers powder 2～8
Dispersion agent (polyoxyethylene nonylphenol ether: alkylphenol polyoxyethylene) 0.3
Dry ferment 0.5
KOH 0.1
Sulphur 0.6
Promotor PX (N-ethyl-N-phenyl zinc dithiocarbamate) 0.8
Promotor ZDC (zinc diethyldithiocarbamate) 0.5
Antioxidant 264 (2,6 ditertiary butyl p cresol) 0.5
Antioxidant MB (2-sulfenyl benzoglyoxaline) 0.5
ZnO 0.5
Two, implementation step:
At first get cotton fiber, add 5～15% maleic anhydride chemical modifiers (in the vegetable fibre quality), add 6～25% grinding aid polystyrene (in the vegetable fibre quality) again, adopt colloid milling that vegetable fibre soil was handled 1～2 hour then, obtain modified micro plant fiber powder.
Get 100 parts of concentrated natural latexes (weight by dry rubber), add 0.3 part of dispersion agent, add 2～8 parts of above-mentioned gained modified micro plant fiber powders again, be mixed with stable emulsion.By above-mentioned prescription sulphur, promotor PX, promotor ZDC, antioxidant 264, antioxidant MB, ZnO being made concentration with deionized water respectively is 20～60% dispersion; It is 1.0～30% dispersion that potassium hydroxide is made concentration with deionized water; It is 5～15% dispersion that casein food grade is made concentration with deionized water.Then above-mentioned each component is joined in the latex.Last comprise that according to the conventional production process of emgloves prevulcanized, maturation, dipping, leaching, the demoulding, sulfuration drying and other steps make finished product again.
Embodiment 4 produces latex catheter
One, basic technology prescription following (by weight):
Concentrated natural latex (weight by dry rubber) 100
Modified plant fibers powder 4～10
Dispersion agent (emulsifying agent T: the sorbitan fatty acid ester Soxylat A 25-7) 0.3
Dry ferment 0.1
KOH 0.05
Sulphur 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
Two, implementation step:
At first get the plant coir, add 5～15% stearic acid chemical modifiers (in the vegetable fibre quality), add 6～25% grinding aid polypropylene (in the vegetable fibre quality) again, adopt sand-blast that vegetable fibre soil was handled 12～24 hours then, obtain modified micro plant fiber powder.
Get 100 parts of concentrated natural latexes (weight by dry rubber), add 0.3 part of dispersion agent, add 4～10 parts of above-mentioned gained modified micro plant fiber powders again, be mixed with stable emulsion.By above-mentioned prescription sulphur, promotor PX, promotor ZDC, antioxidant 264, ZnO being made concentration with deionized water respectively is 20～60% dispersion; It is 1.0～30% dispersion that potassium hydroxide is made concentration with deionized water; It is 5～15% dispersion that casein food grade is made concentration with deionized water.Then above-mentioned each component is joined in the latex.Last comprise that according to the conventional production process of latex catheter prevulcanized, maturation, dipping, leaching, chlorination, coating, the demoulding, sulfuration drying and other steps make finished product again.
Embodiment 5 produces the latex tube for blood transfusion,latex
One, basic technology prescription following (by weight):
Concentrated natural latex (weight by dry rubber) 100
Modified plant fibers powder 3～15
Dispersion agent (paregal O: fatty alcohol-polyoxyethylene ether) 0.3
Sulphur 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
Two, implementation step:
At first get plant treat banana stalk fasciated fiber, add 5～15% oleic acid chemical modifiers (in the vegetable fibre quality), add 6～25% grinding aid polyethylene (in the vegetable fibre quality) again, adopt vibrations mill method that vegetable fibre soil was handled 5～24 hours then, obtain modified micro plant fiber powder.
Get 100 parts of concentrated natural latexes (weight by dry rubber), add 0.3 part of dispersion agent, add 3～15 parts of above-mentioned gained modified micro plant fiber powders again, be mixed with stable emulsion.Press above-mentioned prescription with sulphur, promotor TT, altax, antioxidant 264, ZnCO
3Making concentration with deionized water respectively is 20～60% dispersion, then above-mentioned each component is joined in the latex, and 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.
Embodiment 6 production latex foam materials
One, prescription following (by weight):
Concentrated natural latex (weight by dry rubber) 100
Modified plant fibers powder 10～50
Vulkacit D 0.2
Na
2SiF
6 0.5～1.5
Sulphur 1.6
Promotor PX (N-ethyl-N-phenyl zinc dithiocarbamate) 0.7
Captax (benzothiazolyl mercaptan) 0.7
Antioxidant DBH 1.5
Antioxidant MB (2-sulfenyl benzoglyoxaline) 1.5
ZnO 1.8
KOH 0.15
Ammonium sulfate 1.2
Formaldehyde 1.5
Two, implementation step:
At first get Caulis Sacchari sinensis fiber, add 5～15% linolic acid chemical modifiers (in the vegetable fibre quality), add 6～25% grinding aid polyethylene (in the vegetable fibre quality) again, adopt the impact grinding method that vegetable fibre soil was handled 1～5 hour then, obtain modified micro plant fiber powder.
Get 100 parts of concentrated natural latexes (weight by dry rubber), after removing the ammonia maturation, add 10～50 parts of above-mentioned gained modified micro plant fiber powders again, be mixed with stable emulsion.By above-mentioned prescription sulphur, promotor PX, captax, antioxidant DBH, antioxidant MB, ZnO being made concentration with deionized water respectively is 20～60% dispersion, then above-mentioned each component is joined in the latex, adds vulkacit D, Na
2SiF
6, KOH, ammonium sulfate and formaldehyde, enter frothing machine, comprise that according to the conventional production process of latex foam steps such as foaming, injection molding, gelling, sulfuration, the demoulding, washing, drying, finishing make finished product again.
Embodiment 7 productivity tires
One, basic technology prescription following (by weight):
Natural rubber 100
Modified plant fibers powder 15～50
High abrasion furnace black(HAF) 1～20
Semi-reinforcing hydrocarbon black 1～20
Reclaimed rubber 30
Sulphur 2
ZnO 4
Stearic acid 3
Captax (benzothiazolyl mercaptan) 1.4
Accelerant CZ (N cyclohexyl 2 benzothiazole sulfenamide) 1.2
Antioxidant A (N-phenyl-1-naphthylamine) 1
Antioxidant D FC (styroyl pentanoic) 1
Heavy oil 5～14
Whitfield's ointment 0.2
Two, implementation step:
At first get the straw fiber, add 5～15% toxilic acids chemistry properties-correcting agent (in the vegetable fibre quality), add 6～25% grinding aid polypropylene (in the vegetable fibre quality) again, adopt the millstone type force chemical reactor to mill then 1～2 hour, obtain modified micro plant fiber powder.
In rubber mixing machine, add 100 parts of natural rubbers, add above-mentioned gained modified micro plant fiber powder, carbon black, antioxidant A, antioxidant D FC, sulphur, captax, accelerant CZ, ZnO, stearic acid, reclaimed rubber, heavy oil, Whitfield's ointment successively by above-mentioned prescription, the conventional production process according to the rubber hand cart tyre comprises banburying, rolls, extrudes again, step such as moulding, sulfuration makes finished product.
Embodiment 8 production rubber soles
One, basic technology prescription following (by weight):
Natural rubber 100
Modified plant fibers powder 30～60
Vaseline 10
Reclaimed rubber 30～100
Pigment 1～15
Sulphur 3.3
Captax (benzothiazolyl mercaptan) 2.1
Altax (benzothiazyl disulfide) 1.1
Vulkacit D (vulkacit D) 1.1
Antioxidant D (N-Phenyl beta naphthylamine) 1.2
Blowing agent H (dinitrosopentamethylene tetramine) 1～6
Two, implementation step:
At first get the plant bamboo fibers, add 5～15% phthalic acid chemical modifiers (in the vegetable fibre quality), add 6～25% grinding aid polypropylene (in the vegetable fibre quality) again, adopt millstone type force chemical reactor grinding method that vegetable fibre was handled 1～2 hour then, obtain modified micro plant fiber powder.
In rubber mixing machine, add 100 parts in the dried glue of natural rubber, add above-mentioned gained modified micro plant fiber powder, antioxidant D, sulphur, captax, altax, vulkacit D, Vaseline, pigment, blowing agent H and reclaimed rubber successively by above-mentioned prescription, again according to the conventional production process of rubber soles comprise mixing, go into steps such as mould, sulfuration and make finished product.
Claims (9)
1, a kind of modified plant fibers-native rubber composite material, it is characterized in that comprising following components by weight portions: 100 parts in the latex of natural rubber or weight by dry rubber, 1～60 part of modified micro plant fiber powder, 0.5～3.3 part in sulphur, 1.2～4.3 parts of promotor, 1～3 part in anti-aging agent.
2, a kind of modified plant fibers-native rubber composite material according to claim 1 is characterized in that: described modified plant fibers-native rubber composite material also adds following one or more processing aid by weight: 0.5～4 part in zinc oxide; 0.3 part of polyoxyethylene nonylphenol ether (alkylphenol polyoxyethylene); 0.3 part of emulsifying agent T (sorbitan fatty acid ester Soxylat A 25-7); 0.3 part of paregal O (fatty alcohol-polyoxyethylene ether); ZnCO
31 part; 0.1～0.5 part of dry ferment; 0.05～0.15 part of KOH; 0.2 part of vulkacit D; Na
2SiF
60.15～0.5 part; 1.2 parts in ammonium sulfate; 1.5 parts in formaldehyde; 1～20 part of high abrasion furnace black(HAF); 1～20 part of semi-reinforcing hydrocarbon black; 30～100 parts of reclaimed rubbers; 3 parts of stearic acid; 5～14 parts in heavy oil; 0.2 part of Whitfield's ointment; 10 parts in Vaseline; Pigment 1-15 part; 1～6 part of blowing agent H (dinitrosopentamethylene tetramine).
3, a kind of modified plant fibers-native rubber composite material according to claim 1 is characterized in that: described promotor comprises N-ethyl-N-phenyl zinc dithiocarbamate, zinc diethyldithiocarbamate, benzothiazyl disulfide, tetramethyl-thiuram disulfide, N-ethyl-N-phenyl zinc dithiocarbamate, benzothiazolyl mercaptan, N cyclohexyl 2 benzothiazole sulfenamide or vulkacit D.
4, a kind of modified plant fibers-native rubber composite material according to claim 1, it is characterized in that: described anti-aging agent comprises 2,6 ditertiary butyl p cresol, to stupid diphenol dibenzyl ether, 2-sulfenyl benzoglyoxaline, N-phenyl-1-naphthylamine, styroyl pentanoic or N-Phenyl beta naphthylamine.
5, a kind of modified plant fibers-native rubber composite material according to claim 1, it is characterized in that described modified micro plant fiber powder is prepared from as follows: in vegetable fibre, add chemical modifier and grinding aid, adopt mechanochemical method to handle then 0.5～24 hour, obtain modified micro plant fiber powder; Described chemical modifier addition is 5～15% of a vegetable fibre quality, and the grinding aid addition is 6～25% of a vegetable fibre quality.
6, a kind of modified plant fibers-native rubber composite material according to claim 1 is characterized in that: described fiber comprises arghan, sisal fibers, coir, treat banana stalk fasciated fiber, stalk fibre, cotton fiber, silky fibre, ramee, bamboo fibers, jute fibre or Caulis Sacchari sinensis fiber;
Described chemical modifier is any in diacetyl oxide, maleic anhydride, Tetra hydro Phthalic anhydride, stearic acid, oleic acid, linolic acid, linolenic acid, toxilic acid, the phthalic acid, and addition is 5～15% of a vegetable fibre quality;
Described grinding aid is polypropylene, polyethylene or polystyrene micro mist, and addition is 6～25% of a vegetable fibre quality.
7, a kind of modified plant fibers-native rubber composite material according to claim 5 is characterized in that: described mechanochemical method is that the millstone type force chemical reactor is milled, ball milled, colloid milling, sand-blast, vibrations mill method or impact grinding method.
8, the preparation method of claim 1 or 2 described modified plant fibers-native rubber composite materials, comprise the steps: by weight ratio above-mentioned raw materials modified micro plant fiber powder, sulphur, promotor, anti-aging agent and processing aid to be added in natural rubber or the latex, be distributed to equably in natural rubber or the latex, make the native rubber composite material that contains modified micro plant fiber powder by prevulcanized, maturation, dipping, leaching, the demoulding, sulfuration drying step again.
9, claim 1 or the 2 described modified plant fibers-native rubber composite materials application in preparation catheter, tube for blood transfusion,latex, condom, medical gloves, latex examination gloves, foam materials, hand cart tyre, sole goods.
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| CNB2006100375807A CN100432134C (en) | 2006-09-07 | 2006-09-07 | Composite material of modified micro plant fiber powder and natural rubber and its prepn process and application |
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| CNB2006100375807A CN100432134C (en) | 2006-09-07 | 2006-09-07 | Composite material of modified micro plant fiber powder and natural rubber and its prepn process and application |
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| CN100432134C CN100432134C (en) | 2008-11-12 |
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| CNB2006100375807A Expired - Fee Related CN100432134C (en) | 2006-09-07 | 2006-09-07 | Composite material of modified micro plant fiber powder and natural rubber and its prepn process and application |
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