CN102924772B - Rubber composition used for anti-fire shoes and manufacturing method thereof - Google Patents
Rubber composition used for anti-fire shoes and manufacturing method thereof Download PDFInfo
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- CN102924772B CN102924772B CN201210464198.XA CN201210464198A CN102924772B CN 102924772 B CN102924772 B CN 102924772B CN 201210464198 A CN201210464198 A CN 201210464198A CN 102924772 B CN102924772 B CN 102924772B
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Abstract
The invention relates to a rubber composition used for anti-fire shoes and a manufacturing method of the rubber composition. The rubber composition comprises a base rubber composed of 90-100 in parts by weight of chloroprene rubber and 0-10 in parts by weight of cis-1, 4-polybutadiene rubber and other complexing agents. The rubber composition is obtained through mixing the components according to the formula amount. According to the invention, through choosing proper base rubber, a flame retardant and other complexing agents, the finally prepared rubber composition used for the anti-fire shoes has the advantages of good wear resistance, oil resistance, acid-base resistance, flame retardancy, insulativity and the like, and increases each indicator of the anti-shoes to a large extent, and has a better protection for the firemen in the harsh environment.
Description
Technical field
The present invention relates to rubber combination technical field, relate in particular to a kind of rubber combination for the manufacture of fire-fighting footwear and manufacture method thereof.
Background technology
In general, rubber composition for footwear must be able to support wearer's body weight, the load that bears motion generation and impact intensity of force, improves comfort level, security and the anti-skid of shoes.
Fire-fighting footwear are to wear in the severe environment such as fire for firefighter, the special type protection footwear that protection both feet and shank escape injury.What fire fighter was engaged in is the work that has certain risk, the footwear of its dress need to possess waterproof simultaneously, heat insulation, anti-skidding, anti-ly pierces through, insulation, resistance toly pound, the performance such as side and bear building-up close firm, wear-resisting, resistance to complications.
Because the scene of a fire structure of matter occurs constantly to change, especially in the scene of a fire existing at a large amount of acid, alkali, oily substance, based on the gap of the oil resistant of rubber own, acid-proof alkaline, make the distortion that is distorted of the fire-fighting footwear of quality of rubber materials, abrasion increase, tensile strength at yield reduces, hardness increases etc., reduce rapidly the barrier propterty of fire fighter's boots, accelerate the damage of boots footwear so that do not reach the effect of protection, cause firemen to be burnt by acid-base material, affect the process of fire-fighting work.Therefore, fire-fighting footwear also should have the performance of oil resistant, acid and alkali-resistance, can meet the requirement under the complex environment of the scene of a fire.
CN 2732023Y discloses a kind of protection rubber shoes for fire fighter.It by boots at the bottom of, boots head, boot upper and the leg of a boot form, the steel plate middle level at the bottom of boots is stainless steel flaggy, there is insulating paper layer its inner side, there is rubber insulation in the outside in rubber middle level; Rubber outsole at the bottom of boots, the rubber boot head back-up coat of boots head, the rubber boot upper back-up coat of boot upper and the rubber outer of the leg of a boot are fire-retardant acid and alkali-resistance rubber layer.This utility model has improved anti-puncture performance and withstand voltage properties at the bottom of boots, and flame retardant properties and the heat-proof quality of whole boots are good, acid-alkali-corrosive-resisting and anti-ly pound, anti-cutting, greatly improve the defencive function to fire fighter's pin and calf, can meet the needs of fire brigade.
CN 1875063A discloses a kind of rubber composition for footwear, and said composition comprises: (1) 100 parts by weight of rubber shaped polymer; (2) 1 weight part～150 weight part masterbatch, described masterbatch obtains in the following way: mediate mutually with the mineral filler of 5 weight part～300 weight parts polymer-modified at least one of 100 weight parts, be combined with the polymer-modified of at least one atomic group containing functional group on the described polymer-modified multipolymer that is selected from conjugated diolefine polymer, comprise conjugated diene monomer and vinylaromatic hydrocarbon or their hydrogenated products.
CN 101365746A discloses a kind of sole rubber combination, it is characterized in that, mixed the rubber stiffener (D) of 2 ~ 50 mass parts with respect to the component of polymer of 100 mass parts, described component of polymer is by the vinyl cis-polybutadiene rubber (A) of 10 ~ 90 quality %, (A) of 10 ~ 50 quality % polydiene (B) in addition and thermoplastic polymer (C) formation of 2 ~ 50 quality %, described vinyl cis-polybutadiene rubber (A) contains 1, 4-cis-polybutadiene (A) and 1, 2-polyhutadiene crystalline fibers (B), described 1, the average fiber length of 2-polyhutadiene crystalline fibers (B) is below 200NM, its average aspect ratio is below 10, staple length is that the crystalline fibers number below 200NM is 90 above/25 μ m
2, and fusing point is more than 170 ℃.
After retrieval great mass of data, the prior art of fire-fighting footwear is summarized, find that great majority research concentrates in the texture improvement of fire-fighting footwear, the technology that part is studied rubber composition for footwear, also seldom effectively improves for fire-fighting footwear.
Summary of the invention
The object of the invention is to the deficiency for existing fire-fighting footwear, proposed a kind of fire-fighting rubber composition for footwear and manufacture method thereof with advantages such as oil resistant, acid and alkali-resistance, wear-resisting, fire-retardant, insulation.
For reaching this object, the present invention by the following technical solutions:
A kind of fire-fighting rubber composition for footwear, described rubber combination comprises following component by weight:
Chloroprene rubber 90 ~ 100;
Cis-1,4-polybutadiene rubber 0 ~ 10;
Antimonous oxide 5 ~ 20;
Promoting agent 3 ~ 5;
Vulcanizing agent 2 ~ 5;
Strengthening agent 22 ~ 50;
Promotor 1.5 ~ 2;
Dispersion agent 0.3 ~ 3.
The present invention, by selecting the rational proportion of rational basic glue and adjustment basis glue and Synergist S-421 95, strengthens the synergy of basic glue and Synergist S-421 95, solves the problem of prior art, prepares the good fire-fighting rubber composition for footwear of various aspects of performance.
The parts by weight of chloroprene rubber of the present invention can select 90.1 ~ 99.8,93 ~ 98,94.5 ~ 96,95 etc.; The parts by weight of described cis-1,4-polybutadiene rubber can select 0.2 ~ 9.6,0.75 ~ 9.2,1.2 ~ 8,2 ~ 6,3.3 ~ 5,4 etc.In the time that the parts by weight of cis-1,4-polybutadiene rubber are 0, in described fire-fighting rubber composition for footwear, do not contain cis-1,4-polybutadiene rubber.
The main glue of the present composition is selected chloroprene rubber, and itself is chloride, and flame retardant effect is relatively good, then adds a small amount of cis-1,4-polybutadiene rubber and improve wear-resisting and improve roll banding.Weighting agent is selected fire-retardant filler antimonous oxide, adds a small amount of carbon black and dyes black.
Shoe rubber can be divided into natural rubber and synthetic rubber two classes.Except oil resistant, flame retardant properties, the comprehensive physical better performances of natural rubber, particularly outstanding is elasticity, cold-resistant and performance of technical process, but will improve its flame retardant properties during for fire-fighting footwear, must in sizing material, add a large amount of fire retardants.The addition of fire retardant is excessive, causes refining glue processing difficulties, and its physical and mechanical properties is degenerated, and cost increases, and therefore fire-fighting footwear employing of the large end day combustion rubber is dissatisfactory.
The chloroprene rubber that the present invention adopts is widely used in weathering resistance product, viscose glue sole, coating and rocket fuel.Technical feature and the natural rubber of chloroprene rubber are more approaching, have the properties such as not available ageing-resistant, the oil resistant of natural rubber, fire-retardant, resistance to chemical attack simultaneously.General title chloroprene rubber is Multifunctional rubber, both can be used as conventional rubber and has used, and can be used as again special gelatin and uses.In chloroprene rubber, add appropriate fire retardant, flame retardant effect is better.Although elastomeric processing performance, not as natural rubber, is pressed different ratios cooperation by chloroprene rubber and cis-1,4-polybutadiene rubber, both can improve performance of technical process, the physical and mechanical properties of chloroprene rubber, can reduce costs again.The winter hardiness of cis-1,4-polybutadiene rubber is good, and second-order transition temperature, temperature limit of brittleness and Tc are low, and the thermotolerance of chloroprene rubber and binding property are good, and maximum operation (service) temperature is 100 ~ 130 ℃, but winter hardiness is poor.Chloroprene rubber and cis-1,4-polybutadiene rubber are also used the regularity that can break chloroprene rubber molecular structure, reduce and use crystallization velocity and the second-order transition temperature of glue, improve winter hardiness and the wear resistance of cross-linked rubber.
The selection of fire retardant and consumption directly affect the cost of flame retardant properties, physical and mechanical properties and the shoemaking of rubber.Rubber combination of the present invention also comprises the antimonous oxide of 5 ~ 20 weight parts.Described antimonous oxide flame retardant effect obviously, low price, ample supply and prompt delivery, do not affect other Synergist S-421 95 performance in formula, and there is the performance of improving rubber.The parts by weight of antimonous oxide of the present invention can select 5.2 ~ 18.9,7 ~ 14,9.5 ~ 12.3,11 etc.
As the preferred technical solution of the present invention, described rubber combination comprises following component by weight:
Chloroprene rubber 90 ~ 98;
Cis-1,4-polybutadiene rubber 2 ~ 10;
Antimonous oxide 6 ~ 19;
Promoting agent 3 ~ 4.3;
Vulcanizing agent 2.2 ~ 5;
Strengthening agent 23 ~ 45;
Promotor 1.5 ~ 1.95;
Dispersion agent 0.5 ~ 2.6.
Activating agent for rubber can promote sulfuration, activation and the reinforcement anti-aging effect of rubber, can strengthen sulfidation, reaches stability, processing safety raising, significantly reduce fraction defective, improve rubber item resistance to tearing, wear resistance, meanwhile, can improve anti-aging, the anti-crawl agentdefiection fragility energy of rubber product.Stearic acid selected by promoting agent of the present invention or/and Zinic stearas all can commercially availablely obtain.Two kinds of promoting agents can be used alone, and also can mix use, mix to use to obtain obvious synergy.The parts by weight of described promoting agent can select 3.01 ~ 4.86,3.02 ~ 4.2,3.3 ~ 4,3.52 ~ 3.8,3.6 etc.
Vulcanizing agent of the present invention is that magnesium oxide is or/and zinc oxide, further preferential oxidation magnesium and zinc oxide.The parts by weight optional 2.05 ~ 4.9,2.21 ~ 4.85,2.3 ~ 4.5,2.75 ~ 4.2,3 ~ 4,3.6 etc. of described vulcanizing agent.The sulfuration of rubber refers to that the linear macromolecule of rubber forms the chemical change process of tridimensional network by chemically crosslinked.The chemical transformation of rubber experience series of complex, from the mixing cross-linked rubber that becomes elastomeric or hard of plasticity, thereby obtains more perfect physical and mechanical properties and chemical property, improves and expanded the use value of elastomeric material.The vulcanization of rubber, the curing system being conventionally made up of vulcanizing agent, promotor and promoting agent forms.Linear macromolecule chain in rubber, under chemical action, by being formed by connecting as the cancellated process in space of chemical bond, is called sulfuration (solidify, be cross-linked).Owing to containing chlorine atom in chloroprene rubber molecule, the activity at two keys position is declined, therefore can not adopt the vulcanization process of other polydiene to vulcanize, can not adopt sulfur sulfide system sulfuration, need to adopt Metal-oxide vulcanization system sulfuration.The sulfidation of chloroprene rubber is zinc oxide and rubber molecule chain reaction, forms ether formula key and forms crosslinked.Chloroprene rubber uses separately zinc oxide still can not obtain satisfied sulfided state, and adopt zinc oxide, magnesium oxide rationally also to use, can make chloroprene rubber obtain the security of suitable vulcanization rate, the degree of depth and processing, the while also can be improved the resistance toheat of vulcanized rubber.
Strengthening agent of the present invention is selected from the mixture of a kind of in carclazyte, carbon black N234, carbon black N220 or carbon black N330 or at least two kinds, and preferably carclazyte LT-102 is or/and carbon black N330.Described carclazyte LT-102, for the product that Dongguan Long Tai Chemical Co., Ltd. produces, can commercially availablely obtain.The parts by weight of described strengthening agent can select 22.2 ~ 48.6,26 ~ 43,30 ~ 40,32 ~ 37,35 etc.Carclazyte can be crosslinked with cis-1,4-polybutadiene rubber, forms crosslinking structure, plays strengthening action.Carbon black can not only improve the intensity of rubber item, and can improve the processing characteristics of sizing material, gives wear resisting property, tear resistance, resistance toheat and cold tolerance etc. that goods are good, extends the work-ing life of goods.Described carbon black N234 is fine intermediate super abrasion furnace black high structure, and carbon black N330 is high abrasion furnace black(HAF), and carbon black N220 is that height is stretched medium super abrasion furnace black surely.Carbon black can make rubber have high wear resistance, tensile strength etc. as strengthening agent.Association reaction between carbon black and rubber is the fundamental cause of carbon black to reinforcing rubber.First the wetting carbon black of the rubber molecule of viscous state, is then well adsorbed on carbon blacksurface, forms physical bond.Carbon black of the present invention is nano level carbon black, nano level carbon black uneven surface has a large amount of edges and fin, the active site of these high surface energies causes there is very strong physics/physics chemical action with polymkeric substance, the interaction of polymer surfaces is also strengthened thereupon, so just increased the probability that polymer segment contacts with carbon blacksurface, black-reinforced effect strengthens.Three kinds of carbon blacks can be used alone, and also can mix use, mix to use to obtain obvious synergy.
In order to reduce curing temperature, shorten curing time, improve the physical and mechanical properties of sulfide, when rubber vulcanizes, must add vulcanization accelerator.Promotor of the present invention is selected from the mixture of a kind of in accelerant CZ, Vulcanization accelerator TMTD, vulkacit D, altax, accelerator DZ, accelerant N A-22 or accelerant NOBS or at least two kinds, and further preferred accelerators DM is or/and accelerant N A-22.Accelerant N A-22 to chloroprene rubber be that a kind of vulcanization rate is fast, operational safety, good promotor that sulfided state is high, can meet the processing requirement of fire-fighting footwear completely.Typical but non-limiting example comprises: the mixture of accelerant CZ and altax, the mixture of accelerator DZ and accelerant NOBS, the mixture of vulkacit D and Vulcanization accelerator TMTD, the mixture of accelerant CZ and accelerant NOBS, the mixture of accelerator DZ and vulkacit D, the mixture of Vulcanization accelerator TMTD and accelerant CZ, the mixture of accelerant NOBS, accelerator DZ and vulkacit D, the mixture of Vulcanization accelerator TMTD, accelerant CZ and accelerant NOBS, the mixture of accelerator DZ, altax, Vulcanization accelerator TMTD and accelerant CZ.Vulcanization accelerator can be used alone, and also can mix use, mixes to use to obtain obvious synergy.The parts by weight of described promotor can select 1.52 ~ 1.98,1.58 ~ 1.9,1.6 ~ 1.8,1.72 etc.
Dispersion agent of the present invention is dispersion agent FL.Dispersion agent mainly improves carbon black and the dispersiveness of other powders in rubber.In sizing material, adapted dispersion agent can be accelerated powder lot dispersing, prevents roll banding, reduces incipient scorch and shorten process period.The parts by weight of dispersion agent of the present invention can select 0.32 ~ 2.98,0.4 ~ 2.55,0.8 ~ 2.3,1.2 ~ 2,1.75 etc.
Chloroprene rubber of the present invention is selected CR B30S; Described cis-1,4-polybutadiene rubber is selected BR150.Those skilled in the art can be known corresponding product from prior art.
, can there is degradation with aging in the impact of the envrionment conditionss such as rubber is heated in prolonged application, oxygen, light.Be heated in process of production simultaneously, the shearing action of mechanical workout, can occur to decompose and separating phenomenon.Therefore,, in order to prevent the aging of styrene-butadiene rubber(SBR) and to decompose, need add anti-aging agent.Anti-aging agent of the present invention is selected from the mixture of a kind of in anti-aging agent RD, antioxidant 4010NA, antioxidant 4020, antioxidant D NP or antioxidant MB or at least two kinds.Typical but non-limiting example comprises: the mixture of antioxidant MB and antioxidant D NP, the mixture of antioxidant 4020 and antioxidant 4010NA, the mixture of anti-aging agent RD and antioxidant MB, the mixture of antioxidant D NP and antioxidant 4020, the mixture of antioxidant 4010NA, anti-aging agent RD, antioxidant MB and antioxidant D NP, the mixture of antioxidant MB, antioxidant D NP, antioxidant 4020, antioxidant 4010NA and anti-aging agent RD.Anti-aging agent RD: 2,2,4-trimethylammonium-1,2-dihyaroquinoline polymer; Antioxidant D NP:N, N-bis-(betanaphthyl) Ursol D; Antioxidant MB: 2-mercaptobenzimidazole, antioxidant 4010NA: N-sec.-propyl-N ' phenyl-Ursol D, antioxidant 4020: N-(1,3-dimethylbutyl)-N'-diphenyl-para-phenylene diamine, five kinds of anti-aging agent can be used alone, also can mix use, mix to use to obtain obvious synergy, and can add and there is synergistic stablizer.
As the preferred technical solution of the present invention, described rubber combination comprises following component by weight:
CR B30S 92~96；
BR150 3~8；
Antimonous oxide 7 ~ 16;
Stearic acid 3.2 ~ 4;
Magnesium oxide 1.3 ~ 2;
Zinc oxide 1 ~ 2.5;
LT-102 20~30；
Carbon black N330 5 ~ 8;
Altax 0.8 ~ 1;
Accelerant N A-22 0.75 ~ 0.84;
Dispersion agent FL 0.9 ~ 2.
Preferably, described rubber combination comprises following component by weight:
CR B30S 95；
BR150 6；
Antimonous oxide 8;
Stearic acid 3.5;
Magnesium oxide 1.4;
Zinc oxide 2;
LT-102 24；
Carbon black N330 5;
Altax 1;
Accelerant N A-22 0.8;
Dispersion agent FL 1.
Technical solution of the present invention can also be chosen as: described rubber combination comprises following component by weight:
CR B30S 90；
BR150 10；
Antimonous oxide 8;
Stearic acid 3;
Magnesium oxide 3;
Zinc oxide 1;
LT-102 30；
Carbon black N330 5;
Altax 1;
Accelerant N A-22 1;
Dispersion agent FL 1.
" comprising " of the present invention, mean it except described component, can also comprise other components, these other components give described rubber combination different characteristics.In addition, " comprising " of the present invention, can also replace with enclosed " being " or " by ... composition ".
For example the present invention can also comprise the mixture of a kind of in softening agent, tinting material and weighting agent or at least two kinds.For example: the mixture of softening agent and tinting material, the mixture of softening agent and weighting agent, the mixture of tinting material and weighting agent, the mixture of softening agent, tinting material and weighting agent.
Softening agent add the stress that can weaken polymer molecule interchain, increase polymer molecular chain movability, reduced the degree of crystallinity of polymer molecular chain, thereby the plasticity of polymkeric substance is increased, improved the processing characteristics of rubber.In formula, adopt phosphoric acid ester and the clorafin softening agent as chloroprene rubber, not only can plasticising, also play fire retardation simultaneously.
According to the regulation in " fire fighter put out a fire Protective Boots " (GA6-2004), the color of fire-fighting footwear should adopt black, therefore should select black colorant, and the carbon black that the present invention selects can play the effect of tinting material simultaneously.
Calcium carbonate selected by weighting agent or/and superfine talcum powder.Weighting agent can increase sizing material volume, reduces costs, and in sizing material, is easy to disperse, and improves processing performance, and improves the mechanical property of product, has very high cost performance.
A manufacture method for fire-fighting rubber composition for footwear described above, forms each component of described rubber combination by formula ratio is mixing.Person of ordinary skill in the field has the ability to know these prior aries, and can select concrete, suitable preparation method, in order to prepare fire-fighting rubber composition for footwear of the present invention.For example can carry out the preparation of rubber combination of the present invention with reference to GBT 6038-1993 " batching of rubber test sizing material, mixing and vulcanizing equipment and schedule of operation ".
Below for utilizing mixer mixing to manufacture the preferred parameter of rubber combination:
Improve the speed of closed-smelting machine rotor and be one of effective measures of strengthening mixing process, rotating speed doubles, and mixing cycle approximately shortens 30 ~ 50%.But rotor speed can be accelerated heat-dissipating, cause compound viscosity to reduce, mechanical shearing effect reduces, and is unfavorable for disperseing, and therefore needs to select rational speed range.It is 25 ~ 40rpm that rubber combination of the present invention carries out the rotor speed of Banbury mixer when mixing, for example, can select 26 ~ 38rpm, 28 ~ 35rpm, 32rpm etc., further preferred 35rpm.
In the mixing process of rubber combination, the off-capacity of banburying chamber can reduce shearing action and the kneading effect to sizing material, even occurs that sizing material skids and rotor idle running phenomenon, causes melting effect bad.Otherwise capacity is excessive, sizing material upset difficulty, makes top fasten position improper, a part of sizing material is detained at charging opening neck place, thereby makes sizing material mixing inhomogeneous, and mixing time is long, and easily causes equipment excess load, and energy consumption is large.The stacking factor of chamber body of mixer of the present invention is 0.55 ~ 0.7, for example, can select 0.56 ~ 0.69,0.59 ~ 0.65,0.62 ~ 0.64 etc., further preferably 0.6.
Preferably, the feed temperature when mixing is 65 ~ 80 ℃, for example, can select 65.2 ~ 78.6 ℃, 68 ~ 75 ℃, and 70 ~ 73.5 ℃, 72 ℃ etc., further preferably 75 ℃.Described feed temperature is the temperature of Banbury mixer fuselage, in the time that body temperature reaches 65 ~ 80 ℃, each component of formula ratio can be dropped into banburying chamber and carry out mixing.
Preferably, dump temperature is 105 ~ 125 ℃, for example, can select 105.2 ~ 124 ℃, 108 ~ 120 ℃, and 110 ~ 116 ℃, further preferably 125 ℃.Described dump temperature is the actual temperature of sizing material, in the time that the actual temperature of sizing material reaches 105 ~ 125 ℃, can carry out discharge.
Under similarity condition, adopt the required mixing time of mixer mixing sizing material than mill much shorter.Mixing requires a timing, and required mixing time improves and shortens with Banbury mixer rotating speed and ram piston pressure.Extend mixing time and can improve the dispersity of Synergist S-421 95 in sizing material, but also can reduce production efficiency.Mixing time is long easily to be caused again sizing material to cross refining and the physical and mechanical properties of cross-linked rubber is suffered damage, and also can cause sizing material " thermal history " to increase and easily occur incipient scorch phenomenon, therefore should shorten as far as possible the mixing time of sizing material.It is 400 ~ 750s that the present invention selects mixing time, for example, can select 402 ~ 745s, 430 ~ 725s, 520 ~ 703s, 562 ~ 645s, 585 ~ 622s, 600s etc., further preferred 650s.The selection of mixing time of the present invention can either improve the dispersity of Synergist S-421 95 in sizing material, can guarantee again the physical and mechanical properties of cross-linked rubber simultaneously.
When mixer mixing, sizing material all must be subject to the certain pressure effect of floating weight.In the time that rotor speed is constant, further improve pressure result little.In the time of mixing off-capacity, ram piston pressure can not play one's part to the full.Improve ram piston pressure and can reduce the non-packing space in confined chamber, make its filling extent improve approximately 10%.Along with the raising of capacity and rotating speed, the pressure of floating weight must increase.Ram piston pressure improves can accelerate mixing process sizing material heat-dissipating, and increases the watt consumption when mixing.The ram piston pressure of described Banbury mixer is 0.7 ~ 1.0MPa, for example, can select 0.72 ~ 0.95MPa, 0.75 ~ 0.9MPa, 0.86MPa etc., further preferred 0.8MPa.
Compared with prior art scheme, the present invention has following beneficial effect:
(1) the present invention, by selecting chloroprene rubber and cis-1,4-polybutadiene rubber as basic glue, both can improve performance of technical process, the physical and mechanical properties of chloroprene rubber, can reduce costs again, improves winter hardiness and the wear resistance of cross-linked rubber.
(2) by selecting rational fire retardant and other Synergist S-421 95s; make the fire-fighting rubber composition for footwear finally making there are good wear resistance, oil resistant, acid and alkali-resistance, flame retardant resistance, insulativity etc.; improve to a great extent the indices of fire-fighting footwear, fire fighter has been played in severe environment to better provide protection.
The present invention is described in more detail below.But following example is only simple and easy example of the present invention, does not represent or limit the scope of the present invention, and interest field of the present invention is as the criterion with claims.
Embodiment
For the present invention is described better, be convenient to understand technical scheme of the present invention, typical but non-limiting embodiment of the present invention is as follows:
Embodiment 1
A kind of fire-fighting rubber composition for footwear, comprises following component by weight:
Chloroprene rubber 100;
Antimonous oxide 5;
Promoting agent 3;
Vulcanizing agent 2;
Strengthening agent 50;
Promotor 2;
Dispersion agent 0.3.
Embodiment 2
A kind of fire-fighting rubber composition for footwear, comprises following component by weight:
Chloroprene rubber 90;
Cis-1,4-polybutadiene rubber 10;
Antimonous oxide 20;
Promoting agent 5;
Vulcanizing agent 5;
Strengthening agent 22;
Promotor 1.5;
Dispersion agent 3.
Embodiment 3
A kind of fire-fighting rubber composition for footwear, comprises following component by weight:
Chloroprene rubber 98;
Cis-1,4-polybutadiene rubber 2;
Antimonous oxide 19;
Promoting agent 4.3;
Vulcanizing agent 2.2;
Strengthening agent 45;
Promotor 1.5;
Dispersion agent 0.5.
Embodiment 4
A kind of fire-fighting rubber composition for footwear, comprises following component by weight:
Chloroprene rubber 90;
Cis-1,4-polybutadiene rubber 10;
Antimonous oxide 6;
Promoting agent 3;
Vulcanizing agent 5;
Strengthening agent 23;
Promotor 1.95;
Dispersion agent ~ 2.6.
Embodiment 5
A kind of fire-fighting rubber composition for footwear, comprises following component by weight:
CR B30S 92；
BR150 8；
Antimonous oxide 16;
Stearic acid 3.2;
Magnesium oxide 1.3;
Zinc oxide 2.5;
LT-102 30；
Carbon black N330 8;
Altax 1;
Accelerant N A-22 0.84;
Dispersion agent FL 0.9.
Embodiment 6
A kind of fire-fighting rubber composition for footwear, comprises following component by weight:
CR B30S 96；
BR150 3；
Antimonous oxide 7;
Stearic acid 4;
Magnesium oxide 2;
Zinc oxide 1;
LT-102 20；
Carbon black N330 5;
Altax 0.8;
Accelerant N A-22 0.75;
Dispersion agent FL 2.
Embodiment 7
A kind of fire-fighting rubber composition for footwear, comprises following component by weight:
CR B30S 90；
BR150 10；
Antimonous oxide 8;
Stearic acid 3;
Magnesium oxide 3;
Zinc oxide 1;
LT-102 30；
Carbon black N330 5;
Altax 1;
Accelerant N A-22 1;
Dispersion agent FL 1.
Embodiment 8
A kind of fire-fighting rubber composition for footwear, comprises following component by weight:
CR B30S 95；
BR150 6；
Antimonous oxide 8;
Stearic acid 3.5;
Magnesium oxide 1.4;
Zinc oxide 2;
LT-102 24；
Carbon black N330 5;
Altax 1;
Accelerant N A-22 0.8;
Dispersion agent FL 1.
Applicant's statement, person of ordinary skill in the field is on the basis of above-described embodiment, by the concrete content point value of above-described embodiment component, combined with the technical scheme of summary of the invention part, thereby the new numerical range producing, also be one of record scope of the present invention, the application, for making specification sheets simple and clear, is no longer enumerated these numerical ranges.
The manufacture method of fire-fighting rubber composition for footwear described in embodiment 1 ~ 7, forms each component of described rubber combination by formula ratio is mixing.Parameter control in manufacturing processed is as shown in table 1:
Processing parameter in table 1 rubber combination manufacturing processed
The rubber of the embodiment of the present invention 7 being made according to the performance test methods relating in " fire fighter put out a fire Protective Boots " GA6-2004 is tested, and test result is as shown in table 2:
Table 2 embodiment 7 the performance test results
Above test result is compared with specified standards value in " fire fighter put out a fire Protective Boots " GA6-2004, all can meet and be better than to a certain extent this standard.
Comparative example 1
Using disclosed embodiment 1 in CN 1875063A as comparative example 1 of the present invention.
Comparative example 2
Using disclosed embodiment 1 in CN 101365746A as comparative example 2 of the present invention.
The simultaneous test that the embodiment of the present invention 7 and comparative example 1 ~ 2 are carried out to performance test, result is as shown in table 3:
Table 3
| Project | Embodiment 7 | Comparative example 1 | Comparative example 2 |
| Hardness shoreA/ degree | 61.0 | 55 | 58 |
| Elongation at break/% | 742 | 720 | 100 |
| Tensile strength/kgfcm -2 | 35 | 16 | 14 |
| Wear loss/cm 2 | 1 | 1.5 | 1.8 |
As can be seen from the above table, the parameters of the embodiment of the present invention is all obviously better than disclosed technical scheme in comparative example 1 and 2.
Applicant's statement, the present invention illustrates detailed composition of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed composition, does not mean that the present invention must rely on above-mentioned detailed composition and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, and the selections of the equivalence replacement to the each raw material of product of the present invention and the interpolation of ancillary component, concrete mode etc., within all dropping on protection scope of the present invention and open scope.
Claims (28)
1. a fire-fighting rubber composition for footwear, is characterized in that, described rubber combination comprises following component by weight:
2. rubber combination as claimed in claim 1, is characterized in that, described rubber combination comprises following component by weight:
3. rubber combination as claimed in claim 1, is characterized in that, stearic acid selected by described promoting agent or/and Zinic stearas.
4. rubber combination as claimed in claim 1, is characterized in that, described vulcanizing agent is that magnesium oxide is or/and zinc oxide.
5. rubber combination as claimed in claim 4, is characterized in that, described vulcanizing agent is magnesium oxide and zinc oxide.
6. rubber combination as claimed in claim 1, is characterized in that, described strengthening agent is selected from the mixture of a kind of in carclazyte, carbon black N234, carbon black N220 or carbon black N330 or at least two kinds.
7. rubber combination as claimed in claim 6, is characterized in that, described strengthening agent is that carclazyte LT-102 is or/and carbon black N330.
8. rubber combination as claimed in claim 1, is characterized in that, described promotor is selected from the mixture of a kind of in accelerant CZ, Vulcanization accelerator TMTD, vulkacit D, altax, accelerator DZ, accelerant N A-22 or accelerant NOBS or at least two kinds.
9. rubber combination as claimed in claim 8, is characterized in that, described promotor is that altax is or/and accelerant N A-22.
10. rubber combination as claimed in claim 1, is characterized in that, described dispersion agent is dispersion agent FL.
11. rubber combinations as claimed in claim 1, is characterized in that, described chloroprene rubber is selected CRB30S.
12. rubber combinations as claimed in claim 1, is characterized in that, described cis-1,4-polybutadiene rubber is selected BR150.
13. rubber combinations as claimed in claim 1, is characterized in that, described rubber combination also comprises anti-aging agent; Described anti-aging agent is selected from the mixture of a kind of in anti-aging agent RD, antioxidant 4010NA, antioxidant 4020, antioxidant D NP or antioxidant MB or at least two kinds.
14. rubber combinations as claimed in claim 1, is characterized in that, described rubber combination comprises following component by weight:
15. rubber combinations as claimed in claim 1, is characterized in that, described rubber combination comprises following component by weight:
The manufacture method of 16. 1 kinds of fire-fighting rubber composition for footwear as described in one of claim 1-15, is characterized in that, each component of described rubber combination is formed by formula ratio is mixing.
17. methods as claimed in claim 16, is characterized in that, it is 25～40rpm that described rubber combination carries out the rotor speed of Banbury mixer when mixing.
18. methods as claimed in claim 17, is characterized in that, it is 35rpm that described rubber combination carries out the rotor speed of Banbury mixer when mixing.
19. methods as claimed in claim 16, is characterized in that, the stacking factor of chamber body of mixer is 0.55～0.7.
20. methods as claimed in claim 19, is characterized in that, the stacking factor of chamber body of mixer is 0.6.
21. methods as claimed in claim 16, is characterized in that, feed temperature is 65～80 ℃.
22. methods as claimed in claim 21, is characterized in that, feed temperature is 75 ℃.
23. methods as claimed in claim 16, is characterized in that, drop temperature is 105～125 ℃.
24. methods as claimed in claim 23, is characterized in that, drop temperature is 125 ℃.
25. methods as claimed in claim 16, is characterized in that, mixing time is 400～750s.
26. methods as claimed in claim 25, is characterized in that, mixing time is 650s.
27. methods as claimed in claim 16, is characterized in that, the ram piston pressure of described Banbury mixer is 0.7～1.0MPa.
28. methods as claimed in claim 27, is characterized in that, the ram piston pressure of described Banbury mixer is 0.8MPa.
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| CN201210464198.XA CN102924772B (en) | 2012-11-16 | 2012-11-16 | Rubber composition used for anti-fire shoes and manufacturing method thereof |
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| CN201210464198.XA CN102924772B (en) | 2012-11-16 | 2012-11-16 | Rubber composition used for anti-fire shoes and manufacturing method thereof |
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Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103421219A (en) * | 2013-08-30 | 2013-12-04 | 安徽金科橡塑制品有限公司 | Formula of abrasion-resistant rubber |
| CN103483652A (en) * | 2013-10-11 | 2014-01-01 | 昆山纯柏精密五金有限公司 | Rubber composition for firefighting shoes and preparation method thereof |
| CN103483653A (en) * | 2013-10-11 | 2014-01-01 | 昆山纯柏精密五金有限公司 | Rubber composition for firefighting shoes and preparation method thereof |
| CN103497382A (en) * | 2013-10-11 | 2014-01-08 | 昆山纯柏精密五金有限公司 | Antiskid rubber sole composition and preparation method thereof |
| CN103951861B (en) * | 2014-05-26 | 2016-06-08 | 南京东亚橡塑制品有限公司 | A kind of Flame-retardant sole material and preparation method thereof |
| CN104861242A (en) * | 2015-06-09 | 2015-08-26 | 苏州市湘园特种精细化工有限公司 | Chloroprene rubber |
| CN104861240A (en) * | 2015-06-09 | 2015-08-26 | 苏州市湘园特种精细化工有限公司 | Shock-reducing rubber |
| CN108822365A (en) * | 2016-11-02 | 2018-11-16 | 芜湖瑞德机械科技有限公司 | A kind of high temperature resistant neoprene and preparation method thereof modified based on seeds of a tung oil tree fruit powder |
| CN107629277B (en) * | 2017-11-02 | 2020-02-14 | 徐州工业职业技术学院 | Environment-friendly flame-retardant chloroprene shoe sole sizing material |
| CN114031824A (en) * | 2021-12-28 | 2022-02-11 | 际华三五三九制鞋有限公司 | Protective boot outsole sizing material for fire fighting |
| CN115772288A (en) * | 2022-12-07 | 2023-03-10 | 江苏盾王科技集团有限公司 | Flame-retardant insulating sole rubber material and refining process thereof |
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