CN105330995A - Environment-friendly flame-retardant foaming rubber and preparation method thereof - Google Patents
Environment-friendly flame-retardant foaming rubber and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/16—Ethene-propene or ethene-propene-diene copolymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2411/00—Characterised by the use of homopolymers or copolymers of chloroprene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/14—Applications used for foams
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The invention provides environment-friendly flame-retardant foaming rubber and a preparation method thereof. Mixed materials sequentially undergo mixing and vulcanization foaming to manufacture the foaming rubber. By mass parts, the mixed materials comprise 60-100 parts of ethylene propylene terpolymer, x parts of neoprene, 5-10 parts of zinc oxide, 3-4 parts of magnesium oxide, 4-6 parts of stearic acid, 10-30 parts of carbon black, 10-30 parts of aluminum hydroxide, 10-30 parts of magnesium hydroxide, 10-20 parts of zinc borate, 10-20 parts of calcium carbonate, 10-20 parts of antimonous oxide, 1-2 parts of sulfur, 4-8 parts of vulcanization accelerator and 5-10 parts of foaming agent, wherein x is larger than 0 and smaller than 40. Noprene high in fire resistance is added into EPDM, the harm caused by direct adding of halogen retardant is avoided, and flame retardance of a body can be achieved. What is more important, zinc borate is adopted as the flame retardant and has synergistic flame retardant effects together with flame retardants such as aluminum hydroxide, magnesium hydroxide and antimonous oxide, and thus the problems that an EPDM foaming material is poor in flame retardance and not environmentally friendly and the mechanical property is affected are solved.
Description
Technical field
The present invention relates to field of rubber technology, particularly relate to a kind of environmental protection flame retardant bipeltate and preparation method thereof.
Background technology
The modernization of society makes rubber industry flourish, and rubber item is widely used in various industry.Rubber pange adopts rubber and other rubber ingredients, add whipping agent, goods are obtained through foaming, wherein, terpolymer EP rubber (EPDM) foam material is because of rebound resilience, electrical insulating property, low density high fillibility, lower temperature resistance, thermotolerance, the performance such as ozone resistance and weatherability of its excellence, both can be widely used in not high sports goods, all kinds of building and the industry such as refrigeration, air-conditioning of requirement for environmental conditions, the field such as automobile component, medicine, military project apparatus higher to environmental requirement can be widely used in again.
Terpolymer EP rubber (EPDM) is the multipolymer of ethene, propylene and a small amount of non-conjugated diene hydrocarbon; usually also fire retardant is comprised in EPDM foam material; generally can add Halogen and phosphorous fire retardant at present, or add other heavy dose of inorganic combustion inhibitors.But first method does not meet the social trend of environmental protection; Second method is many due to amount of flame-retardant agent, often reduces other performances of material, and reduce amount of flame-retardant agent be difficult to ensure flame retardant properties.Therefore, the environmental protection flame retardant bipeltate developing a kind of excellent property is necessary.
Summary of the invention
In view of this, the application provides a kind of environmental protection flame retardant bipeltate and preparation method thereof, and environmental protection flame retardant bipeltate provided by the invention has good flame retardant properties and mechanical property.
The invention provides a kind of environmental protection flame retardant bipeltate, obtained through mixing and sulfur foam successively by mixture;
In mass fraction, described mixture comprises:
The terpolymer EP rubber of 60 ~ 100 parts;
The chloroprene rubber of x part, 0 < x < 40;
The zinc oxide of 5 ~ 10 parts;
The magnesium oxide of 3 ~ 4 parts;
The stearic acid of 4 ~ 6 parts;
The carbon black of 10 ~ 30 parts;
The aluminium hydroxide of 10 ~ 30 parts;
The magnesium hydroxide of 10 ~ 30 parts;
The zinc borate of 10 ~ 20 parts;
The calcium carbonate of 10 ~ 20 parts;
The antimonous oxide of 10 ~ 20 parts;
The sulphur of 1 ~ 2 part;
The vulcanization accelerator of 4 ~ 8 parts;
The whipping agent of 5 ~ 10 parts.
Preferably, described terpolymer EP rubber is made up of the material comprising ethene, propylene and ethylidene norbornene.
Preferably, described chloroprene rubber comprises the anti-form-1 of 80wt% ~ 90wt%, 1, the 2-sovprene of 4-sovprene and 1wt% ~ 2wt%.
Preferably, described vulcanization accelerator comprises the thiuram type accelerator of the Thiourea accelerator of 1 ~ 2 part, the thiazole accelerator of 1 ~ 2 part and 2 ~ 4 parts.
Preferably, described vulcanization accelerator comprises the curing two (thiocarbonyl group dimethylamine) of the ethylene thiocarbamide of 1 ~ 2 part, the dibenzothiazyl disulfide of 1 ~ 2 part and 2 ~ 4 parts.
Preferably, described mixture also comprises the anti-aging agent of 1 ~ 2 part and the coupling agent of 5 ~ 10 parts.
Preferably, described mixture also comprises the antiradiation agent of 10 ~ 15 parts and the water-resisting agent of 5 ~ 10 parts.
The present invention also provides a kind of preparation method of environmental protection flame retardant bipeltate mentioned above, comprises the following steps:
By the stearic acid of terpolymer EP rubber, carbon black, aluminium hydroxide, magnesium hydroxide, 1/2 quality and the zinc oxide of 1/2 quality mixing, obtain terpolymer EP rubber master batch;
By mixing for the stearic acid of chloroprene rubber, magnesium oxide, zinc borate, calcium carbonate, antimonous oxide and 1/2 quality, obtain chloroprene rubber master batch;
By mixing for the zinc oxide of described terpolymer EP rubber master batch, described chloroprene rubber master batch, sulphur, vulcanization accelerator, whipping agent and 1/2 quality, obtain sizing material;
Described rubber vulcanization is foamed, obtains environmental protection flame retardant bipeltate.
Preferably, by the stearic acid of terpolymer EP rubber, carbon black, aluminium hydroxide, magnesium hydroxide, 1/2 quality and mixing temperature≤110 DEG C of the zinc oxide of 1/2 quality;
By temperature≤90 DEG C mixing for the stearic acid of chloroprene rubber, magnesium oxide, zinc borate, calcium carbonate, antimonous oxide and 1/2 quality;
By temperature≤70 DEG C mixing for the zinc oxide of described terpolymer EP rubber master batch, described chloroprene rubber master batch, sulphur, vulcanization accelerator, whipping agent and 1/2 quality.
Preferably, the temperature of described sulfur foam is 170 DEG C ~ 190 DEG C, and the pressure of described sulfur foam is 10MPa ~ 12MPa, and the time of described sulfur foam is 10min ~ 15min.
Compared with prior art, the present invention mainly adopts the mixture comprising terpolymer EP rubber, chloroprene rubber, zinc oxide, magnesium oxide, stearic acid, carbon black, aluminium hydroxide, magnesium hydroxide, zinc borate, calcium carbonate, antimonous oxide, sulphur, vulcanization accelerator and whipping agent, successively through mixing and sulfur foam, prepare environmental protection flame retardant bipeltate.The present invention mainly adds the chloroprene rubber of high flame retardant in EPDM, avoids the harm directly added halogen flame and bring, can realize ingrain fireproofing.The more important thing is, the present invention adopts zinc borate as fire retardant, produce the effect of cooperative flame retardant with these fire retardants of aluminium hydroxide, magnesium hydroxide, calcium carbonate and antimonous oxide, thus solve that EPDM foam material flame retardant properties is poor, the not environmentally problem such as influenced with mechanical property.
Embodiment
Be clearly and completely described the technical scheme in the embodiment of the present invention below, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
The invention provides a kind of environmental protection flame retardant bipeltate, obtained through mixing and sulfur foam successively by mixture;
In mass fraction, described mixture comprises:
The terpolymer EP rubber of 60 ~ 100 parts;
The chloroprene rubber of x part, 0 < x < 40;
The zinc oxide of 5 ~ 10 parts;
The magnesium oxide of 3 ~ 4 parts;
The stearic acid of 4 ~ 6 parts;
The carbon black of 10 ~ 30 parts;
The aluminium hydroxide of 10 ~ 30 parts;
The magnesium hydroxide of 10 ~ 30 parts;
The zinc borate of 10 ~ 20 parts;
The calcium carbonate of 10 ~ 20 parts;
The antimonous oxide of 10 ~ 20 parts;
The sulphur of 1 ~ 2 part;
The vulcanization accelerator of 4 ~ 8 parts;
The whipping agent of 5 ~ 10 parts.
Flame-retardant expanded rubber provided by the invention belongs to the high EPDM flame-retardant foam material of flame retardant properties, and has the features such as excellent mechanical property and environmental protection.
Environmental protection flame retardant bipeltate provided by the invention is obtained through mixing and sulfur foam successively by mixture; In mass fraction, described mixture comprises the terpolymer EP rubber of 60 ~ 100 parts, preferably includes the terpolymer EP rubber of 70 ~ 100 parts.In an embodiment of the present invention, the terpolymer EP rubber (EPDM) used is a kind of rubber of nonpolar, nodeless mesh.As preferably, the Third monomer of EPDM is ethylidene norbornene (ENB), and namely described terpolymer EP rubber is made up of the material comprising ethene, propylene and ethylidene norbornene.The source of the present invention to described terpolymer EP rubber is not particularly limited, and can adopt commercially available prod, as the terpolymer EP rubber EP35 that Japan SYnthetic Rubber Co. Ltd produces.
In mass fraction, the mixture of described environmental protection flame retardant bipeltate comprises the chloroprene rubber of x part, and 0 < x < 40, preferably includes the chloroprene rubber of 20 ~ 30 parts.Chloroprene rubber has another name called neoprene, is take chloroprene as the synthetic rubber that main raw material carries out α-be polymerized.The present invention adopts chloroprene rubber (CR) and the fire-retardant EPDM/CR bipeltate of the blended preparation of EPDM, makes it have the premium propertiess such as good flame retardant resistance, lower temperature resistance, heat-resisting, resistance to ozone and Weather-resistant.In an embodiment of the present invention, the chloroprene rubber used is sulphur adjustment type rubber.In an embodiment of the present invention, described chloroprene rubber is polarity, crystalline rubber.As preferably, described chloroprene rubber comprises the anti-form-1 of 80wt% ~ 90wt%, 1, the 2-sovprene of 4-sovprene and 1wt% ~ 2wt%.In a preferred embodiment of the invention, described chloroprene rubber comprises the anti-form-1 of 85wt%, 1, the 2-sovprene of 4-sovprene and 1.5wt%.The source of the present invention to described chloroprene rubber is not particularly limited, and can adopt commercially available prod, as the chloroprene rubber CR126 that German Lang Sheng group produces.
The embodiment of the present invention, on the basis that the chloroprene rubber and EPDM that will have high flame resistance are blended, adds suitable halogen-free phosphorus-free inflaming retarding agent, improves the flame retardant properties of rubber bubble material, is beneficial to environmental protection and application.In mass fraction, the mixture of described environmental protection flame retardant bipeltate comprises the aluminium hydroxide (ATH) of 10 ~ 30 parts, preferably includes the aluminium hydroxide of 10 ~ 15 parts.Described mixture comprises the magnesium hydroxide (MDH) of 10 ~ 30 parts, preferably includes the magnesium hydroxide of 10 ~ 15 parts.In the present invention, described aluminium hydroxide and magnesium hydroxide can form the flame-retardant system acting on EPDM.
In mass fraction, the mixture of described environmental protection flame retardant bipeltate comprises the calcium carbonate (CaCO of 10 ~ 20 parts
3), preferably include the calcium carbonate of 10 ~ 15 parts.Described mixture comprises the antimonous oxide (Sb of 10 ~ 20 parts
2o
3), preferably include the antimonous oxide of 10 ~ 15 parts.In the present invention, described calcium carbonate and antimonous oxide can be used as the flame-retardant system of chloroprene rubber.In addition, calcium carbonate also can increase the strength of materials and reduce costs.
In mass fraction, the mixture of described environmental protection flame retardant bipeltate comprises the zinc borate (ZB) of 10 ~ 20 parts, preferably includes the zinc borate of 10 ~ 15 parts.In the present invention, add this fire retardant of zinc borate, the effect of cooperative flame retardant can be formed with the flame-retardant system of EPDM and CR respectively, make flame-retardant expanded rubber have excellent flame retardant resistance.The present invention is to fire retardant ATH, fire retardant MDH, fire brake ZB, fire retardant CaCO
3with fire retardant Sb
2o
3source be not particularly limited, adopt commercially available prod.
In mass fraction, the mixture of described environmental protection flame retardant bipeltate comprises the stearic acid of the zinc oxide of 5 ~ 10 parts, the magnesium oxide of 3 ~ 4 parts and 4 ~ 6 parts.In one embodiment of the invention, described mixture comprises the stearic acid of the zinc oxide of 10 parts, the magnesium oxide of 4 parts and 6 parts.In the present invention, described zinc oxide, magnesium oxide and stearic acid form the surfactant system of the vulcanization of rubber, sulfuration can be made more abundant, also can play the effect ensureing mobility and antioxidant capacity, can also increase tensile strength and the anti-impact force of rubber; The product that described zinc oxide, magnesium oxide and stearic acid adopt this area conventional.The mixture of described environmental protection flame retardant bipeltate comprises the carbon black of 10 ~ 30 parts, preferably includes the carbon black of 15 ~ 20 parts.Described carbon black is the rubber reinforcing filler that this area is commonly used, and the present invention is not particularly limited it.
In mass fraction, the mixture of described environmental protection flame retardant bipeltate comprises the sulphur of 1 ~ 2 part, preferably includes the sulphur of 1.4 ~ 1.9 parts.Described sulphur is the vulcanizer that this area is commonly used, and the present invention is not particularly limited it.Correspondingly, described mixture comprises the vulcanization accelerator (referred to as promotor) of 4 ~ 8 parts, forms vulcanization system with sulphur.Described vulcanization accelerator uses with vulcanizing agent in Vulcanization Process of Rubber, curing time can be shortened, reduce curing temperature, reduce vulcanizing agent consumption and improve class rubber ingredients of the physical and mechanical properties of rubber etc., it can be divided into by chemical structure: dithiocarbamate(s), guanidine class, Thiourea, thiazoles and thiurams etc.
In the present invention, described vulcanization accelerator preferably include the Thiourea accelerator of 1 ~ 2 part, the thiazole accelerator of 1 ~ 2 part and 2 ~ 4 parts thiuram type accelerator as vulcanization accelerator TMTD.The present invention can all kinds of vulcanization accelerator used in combination, and facilitation effect is better.Wherein, described Thiourea accelerator is as accelerator NA-22 or promotor ETU; Described thiazole accelerator is as accelerator M or altax.In a preferred embodiment of the invention, described vulcanization accelerator comprises the curing two (thiocarbonyl group dimethylamine) of the ethylene thiocarbamide of 1 ~ 2 part, the dibenzothiazyl disulfide of 1 ~ 2 part and 2 ~ 4 parts.The source of the present invention to described vulcanization accelerator is not particularly limited, and generally adopts commercially available prod; Wherein, ethylene thiocarbamide is commercially available promotor ETU, and dibenzothiazyl disulfide is commercially available altax, and curing two (thiocarbonyl group dimethylamine) is commercially available Vulcanization accelerator TMTD.In one embodiment of the invention, described vulcanization accelerator comprises the Vulcanization accelerator TMTD of the promotor ETU of 1 part, the altax of 1.2 parts and 4 parts.In addition, in one embodiment of the invention, and with zinc oxide and promotor ETU (NA-22), double bond can be reduced in CR to the consumption of sulphur.
In mass fraction, the whipping agent that the mixture of described environmental protection flame retardant bipeltate comprises 5 ~ 10 parts preferably includes the whipping agent of 6 ~ 9 parts.In the present invention, described whipping agent matches with above-mentioned EPDM vulcanization system, prepares environmental protection flame retardant bipeltate.The embodiment of the present invention adopts blowing agent AC, and chemistry Cellmic C 121 by name, its gas forming amount is large, not combustion-supporting, has self-extinguishing, is beneficial to and is applied to environmental protection flame retardant bipeltate.
In mass fraction, the mixture of described environmental protection flame retardant bipeltate preferably also comprises the anti-aging agent of 1 ~ 2 part, more preferably also comprises the anti-aging agent of 1 ~ 1.4 part.Described anti-aging agent refers to prevent or suppress the factors disrupt product propertiess such as such as oxygen, heat, light, ozone and mechanical stress, extend goods storage and the Synergist S-421 95 in work-ing life, comprises the kind such as amine and phenols.The present invention preferably adopts amines antioxidants, more preferably adopts antioxidant 4010NA (N-sec.-propyl-N '-diphenyl-para-phenylene diamine).Described mixture preferably also comprises the coupling agent of 5 ~ 10 parts, more preferably also comprises the coupling agent of 8 ~ 10 parts.The present invention can adopt coupling agent to increase affinity in rubber item before inorganics and organic polymer, raising processing characteristics and mechanical property etc.Described coupling agent can be divided into silicon system, titanium system, aluminium system and chromium system etc., and the most frequently used is silane, titanic acid ester and aluminate coupling agent.In embodiments of the present invention, described coupling agent is preferably silane coupling agent, as Si69 and Si75 etc.In some embodiments of the invention, the mixture of described environmental protection flame retardant bipeltate also comprises the anti-aging agent of 1 ~ 2 part and the coupling agent of 5 ~ 10 parts.
In mass fraction, the mixture of described environmental protection flame retardant bipeltate preferably also comprises the antiradiation agent of 10 ~ 15 parts, more preferably also comprises the antiradiation agent (also claiming anti-irradiation agent) of 10 ~ 12 parts, can improve the radioprotective stability of rubber.Described mixture preferably also comprises the water-resisting agent of 5 ~ 10 parts, more preferably also comprises the water-resisting agent of 8 ~ 10 parts.In some embodiments of the invention, described mixture also comprises the antiradiation agent of 10 ~ 15 parts and the water-resisting agent of 5 ~ 10 parts.In other embodiments of the present invention, described mixture also comprises the water-resisting agent of the anti-aging agent of 1 ~ 2 part, the coupling agent of 5 ~ 10 parts, the antiradiation agent of 10 ~ 15 parts and 5 ~ 10 parts.
Environmental protection flame retardant bipeltate of the present invention is prepared by sulfur foam technique, and its cell size is suitable, be evenly distributed, and flame retardant properties is high, and mechanical property is good, also compares environmental protection.
Correspondingly, the embodiment of the present invention additionally provides a kind of preparation method of environmental protection flame retardant bipeltate mentioned above, comprises the following steps:
By the stearic acid of terpolymer EP rubber, carbon black, aluminium hydroxide, magnesium hydroxide, 1/2 quality and the zinc oxide of 1/2 quality mixing, obtain terpolymer EP rubber master batch;
By mixing for the stearic acid of chloroprene rubber, magnesium oxide, zinc borate, calcium carbonate, antimonous oxide and 1/2 quality, obtain chloroprene rubber master batch;
By mixing for the zinc oxide of described terpolymer EP rubber master batch, described chloroprene rubber master batch, sulphur, vulcanization accelerator, whipping agent and 1/2 quality, obtain sizing material;
Described rubber vulcanization is foamed, obtains environmental protection flame retardant bipeltate.
The embodiment of the present invention, in the process preparing environmental protection flame retardant bipeltate, is mixed into chloroprene rubber and replaces a part of EPDM, and adds the halogen-free phosphorus-free inflaming retarding agent of two kinds of systems, form cooperative flame retardant, make the bipeltate flame retardant properties that obtains high, mechanical property is good, also compares environmental protection.
In internal rubber mixer, the embodiment of the present invention adopts the zinc oxide of the stearic acid of terpolymer EP rubber, carbon black, aluminium hydroxide, magnesium hydroxide, 1/2 quality and 1/2 quality mixing, prepares terpolymer EP rubber master batch.The content of each material as mentioned before, does not repeat them here.In one embodiment of the invention, the order of addition(of ingredients) preparing terpolymer EP rubber master batch is: part stearic acid → 1/2, EPDM → 1/2 part zinc oxide → carbon black → anti-aging agent → coupling agent → ATH and MDH, is more specifically: part stearic acid → 1/2, EPDM → 1/2 part zinc oxide → carbon black N330 → antioxidant 4010NA → silane coupling agent → ATH and MDH.As preferably, by the stearic acid of terpolymer EP rubber, carbon black, aluminium hydroxide, magnesium hydroxide, 1/2 quality and mixing temperature≤110 DEG C of the zinc oxide of 1/2 quality, be more preferably 80 DEG C ~ 105 DEG C.The described mixing time is preferably 5min ~ 10min, is more preferably 6min ~ 8min.
In internal rubber mixer, the embodiment of the present invention adopts the stearic acid of chloroprene rubber, magnesium oxide, zinc borate, calcium carbonate, antimonous oxide and 1/2 quality mixing, prepares chloroprene rubber master batch.The content of each material as mentioned before, does not repeat them here.In one embodiment of the invention, the order of addition(of ingredients) preparing chloroprene rubber master batch is: CR → magnesium oxide → 1/2 part stearic acid → ZB, CaCO
3and Sb
2o
3.Wherein, the material before arrow first adds, and add after the material after arrow, the rest may be inferred.As preferably, by temperature≤90 DEG C mixing for the stearic acid of chloroprene rubber, magnesium oxide, zinc borate, calcium carbonate, antimonous oxide and 1/2 quality, be more preferably 70 DEG C ~ 85 DEG C.The described mixing time is preferably 5min ~ 10min, is more preferably 6min ~ 8min.
After obtaining terpolymer EP rubber master batch and chloroprene rubber master batch, the embodiment of the present invention prepares EPDM/CR rubber unvulcanizate on opening rubber mixing machine.The embodiment of the present invention, by mixing for the zinc oxide of described terpolymer EP rubber master batch, described chloroprene rubber master batch, sulphur, vulcanization accelerator, whipping agent and 1/2 quality, obtains sizing material.
In some embodiments of the invention, on opening rubber mixing machine, by the zinc oxide of described terpolymer EP rubber master batch, described chloroprene rubber master batch, sulphur, vulcanization accelerator, whipping agent and 1/2 quality, and other rubber ingredients are as antiradiation agent and/or water-resisting agent, carry out mixing, obtain sizing material.The content of each material as mentioned before, does not repeat them here.In an embodiment of the present invention, the order of addition(of ingredients) of preparation EPDM/CR rubber unvulcanizate is: EPDM master batch, CR master batch → anti-irradiation agent → water-resisting agent → 1/2 part zinc oxide → sulphur → promotor → whipping agent, is more specifically: EPDM master batch, CR master batch → anti-irradiation agent → water-resisting agent → 1/2 part zinc oxide → sulphur → promotor ETU → altax → Vulcanization accelerator TMTD → blowing agent AC.As preferably, by temperature≤70 DEG C mixing for the zinc oxide of described terpolymer EP rubber master batch, described chloroprene rubber master batch, sulphur, vulcanization accelerator, whipping agent and 1/2 quality, be more preferably 60 DEG C ~ 70 DEG C.The described mixing time is preferably 5min ~ 10min, is more preferably 6min ~ 8min.In addition, the embodiment of the present invention can in the end thin-pass 6 times.
After obtaining sizing material, the embodiment of the present invention by sizing material slice, park.In embodiments of the present invention, slice after described sizing material thin-pass, thickness can be 0.8cm ~ 1cm.Then, the embodiment of the present invention is that under the weight of 5kg, normal temperature parks more than 8 hours in quality; Require the environment parked for directly shining without sunlight, humidity is moderate, dustless, ventilation condition is good.
Sizing material obtained in the previous step or pellet on vulcanizing press, are carried out sulfur foam, obtain environmental protection flame retardant bipeltate through shaping by the embodiment of the present invention.
In the present invention, the temperature of described sulfur foam is preferably 170 DEG C ~ 190 DEG C, is more preferably 175 DEG C ~ 185 DEG C.The pressure of described sulfur foam is preferably 10MPa ~ 12MPa; The time of described sulfur foam is preferably 10min ~ 15min.After sulfur foam terminates, the embodiment of the present invention cools 15min ~ 20min setting under room temperature (25 DEG C), makes the finished product.
After obtaining environmental protection flame retardant bipeltate, the present invention carries out performance test to it.The present invention, according to GB/T528-2009 " mensuration of vulcanized rubber or thermoplastic elastomer tensile stress-strain performance ", carries out stretching experiment test, and testing apparatus is the CMT6104 microcomputer controlled electronic universal testing machine that materiology company limited is newly thought carefully by Shenzhen.
The present invention is according to ASTMD1056-2007 " spongy or expanded rubber class flexible, porous material specification ", carry out compression experiment and density experiment test, testing apparatus is the CMT6104 microcomputer controlled electronic universal testing machine that materiology company limited is newly thought carefully by Shenzhen.
The present invention is according to GB/T10707-2008 " mensuration of rubber combustion performance ", carry out limiting oxygen index(LOI) experiment test, testing apparatus is the intelligent critical oxygen index tester of the TTech-GBT2406-1 of safe this Tyke (Suzhou) detecting instrument Science and Technology Ltd..
The present invention is according to GB/T10707-2008 " mensuration of rubber combustion performance ", carry out vertical combustion experiment test, testing apparatus is the horizontal vertical combustion test instrument of the TTech-GBT2408-002 of safe this Tyke (Suzhou) detecting instrument Science and Technology Ltd..
Result shows, the present invention is based on Ethylene Propylene Terpolymer flame retardant rubber foam material and EPDM/CR bipeltate that above-mentioned forming method prepares, have mechanical property and the flame retardant properties of higher cell density and excellence, its market has larger exploitation potential, has good industrial prospect.This environmental protection flame retardant of the present invention bipeltate both can be widely used in not high sports goods, all kinds of building and the industry such as refrigeration, air-conditioning of requirement for environmental conditions, can be widely used in again the field such as automobile component, medicine, military project apparatus higher to environmental requirement.
In addition, the preparation technology of environmental protection flame retardant bipeltate of the present invention is simple.
In order to understand the application further, below in conjunction with embodiment, environmental protection flame retardant bipeltate that the application provides and preparation method thereof is described particularly.
In following examples, each material number is mass fraction.In following examples and comparative example, EPDM used is the terpolymer EP rubber EP35 that Japan SYnthetic Rubber Co. Ltd produces; Chloroprene rubber is the chloroprene rubber CR126 that German bright Sheng group is produced; Carbon black is purchased from Shanxi Fu Li birch Chemical Co., Ltd.; The anti-irradiation agent UV-531 that anti-irradiation agent provides for Town in Shanghai brightness Chemical Co., Ltd.; The water-resisting agent potassium methyl silicate that water-resisting agent provides for the emerging Chemical Co., Ltd. of Jinan your writing; Silane resin acceptor kh-550 is purchased from Guangzhou Heng Yu Chemical Co., Ltd..
Embodiment 1
Material formula: EPDM80 part, CR20 part, 10 parts, zinc oxide, 4 parts, magnesium oxide, stearic acid 6 parts, carbon black N33020 part, fire retardant ATH10 part, fire retardant MDH10 part, fire brake ZB 10 parts, fire retardant CaCO
310 parts, fire retardant Sb
2o
310 parts, antioxidant 4010NA 1 part, anti-irradiation agent 10 parts, silane coupling agent 10 parts, water-resisting agent 10 parts, 1.4 parts, sulphur, promotor ETU1 part, altax 1.2 parts, Vulcanization accelerator TMTD 4 parts, blowing agent AC 9 parts.
Concrete preparation method is:
(1) in internal rubber mixer, terpolymer EP rubber master batch is prepared.Order of addition(of ingredients) is: part stearic acid → 1/2, EPDM → 1/2 part zinc oxide → carbon black N330 → antioxidant 4010NA → silane coupling agent → ATH and MDH.Temperature: 90 DEG C.Mixing time: 8min.
(2) in internal rubber mixer, chloroprene rubber master batch is prepared.Order of addition(of ingredients) is: CR → magnesium oxide → 1/2 part stearic acid → ZB, CaCO
3and Sb
2o
3.Temperature: 70 DEG C.Mixing time: 8min.
(3) on opening rubber mixing machine, preparation EPDM/CR rubber unvulcanizate.Order of addition(of ingredients) is: EPDM master batch, CR master batch → anti-irradiation agent → water-resisting agent → 1/2 part zinc oxide → sulphur → promotor ETU → altax → Vulcanization accelerator TMTD → blowing agent AC.Temperature: 60 DEG C.Mixing time: 8min.Last thin-pass 6 times, obtains sizing material.
(4) slice after sizing material thin-pass, thickness is 0.8 ~ 1.0cm.Be that under the weight of 5kg, normal temperature parks 12 hours in quality; Require the environment parked for directly shining without sunlight, humidity is moderate, dustless, ventilation condition is good.
(5) by shaping for pellet obtained in the previous step sulfur foam on vulcanizing press, its condition is: temperature is 180 ± 5 DEG C, and pressure is 10MPa, and the time is 10min.Then under room temperature (25 DEG C), cool 20min setting, make the finished product.
Embodiment 2
Material formula: EPDM70 part, CR30 part, 10 parts, zinc oxide, 4 parts, magnesium oxide, stearic acid 6 parts, carbon black N33020 part, fire retardant ATH10 part, fire retardant MDH10 part, fire brake ZB 10 parts, fire retardant CaCO
310 parts, fire retardant Sb
2o
310 parts, antioxidant 4010NA 1 part, anti-irradiation agent 10 parts, silane coupling agent 10 parts, water-resisting agent 10 parts, 1.4 parts, sulphur, promotor ETU1 part, altax 1.2 parts, Vulcanization accelerator TMTD 4 parts, blowing agent AC 9 parts.
Concrete preparation method is identical with the preparation method of above-described embodiment 1.
Embodiment 3
Material formula: EPDM70 part, CR30 part, 10 parts, zinc oxide, 4 parts, magnesium oxide, stearic acid 6 parts, carbon black N33020 part, fire retardant ATH15 part, fire retardant MDH15 part, fire brake ZB 15 parts, fire retardant CaCO
310 parts, fire retardant Sb
2o
310 parts, antioxidant 4010NA 1 part, anti-irradiation agent 10 parts, silane coupling agent 10 parts, water-resisting agent 10 parts, 1.4 parts, sulphur, promotor ETU1 part, altax 1.2 parts, Vulcanization accelerator TMTD 4 parts, blowing agent AC 9 parts.
Concrete preparation method is identical with the preparation method of above-described embodiment 1.
According to method mentioned above, the performance of embodiment 1 ~ 3 gained environmental protection flame retardant bipeltate is tested.Results of property is shown in Table 1, and table 1 is the performance test results of embodiment 1 ~ 3 gained environmental protection flame retardant bipeltate.
The performance test results of table 1 embodiment 1 ~ 3 gained environmental protection flame retardant bipeltate
| Embodiment 1 | Embodiment 2 | Embodiment 3 | |
| Tensile strength (MPa) | 3.50 | 3.20 | 3.80 |
| Elongation at break (%) | 190 | 220 | 210 |
| Compression line Young's modulus (MPa) | 5.6 | 5.0 | 5.4 |
| Density (g/cm 3) | 0.19 | 0.19 | 0.20 |
| Limiting oxygen index(LOI) (%) | 32 | 31 | 35 |
| Vertical combustion grade | V1 | V1 | V0 |
Comparative example 1
Material formula: EPDM100 part, 8 parts, zinc oxide, 4 parts, magnesium oxide, stearic acid 3 parts, carbon black N33020 part, fire retardant ATH100 part, fire retardant MDH50 part, antioxidant 4010NA 1 part, anti-irradiation agent 10 parts, silane coupling agent 10 parts, water-resisting agent 10 parts, 1.4 parts, sulphur, altax 1.2 parts, Vulcanization accelerator TMTD 4 parts, blowing agent AC 9 parts.
The order of addition(of ingredients) of concrete preparation method and step (1) in above-described embodiment 1 and step (3) ~ (5) and compounding conditions etc. are identical, do not add CR, obtained flame-retardant expanded rubber.
Comparative example 2
Material formula: EPDM100 part, 10 parts, zinc oxide, 4 parts, magnesium oxide, stearic acid 6 parts, carbon black N33020 part, fire retardant polynite (granularity is 1250 orders) 100 parts, fire retardant melamine cyanurate (MCA) 30 parts, antioxidant 4010NA 1 part, anti-irradiation agent 10 parts, silane coupling agent 10 parts, water-resisting agent 10 parts, 1.4 parts, sulphur, promotor ETU1 part, altax 1.2 parts, Vulcanization accelerator TMTD 4 parts, blowing agent AC 9 parts.
The order of addition(of ingredients) of concrete preparation method and step (1) in above-described embodiment 1 and step (3) ~ (5) and compounding conditions etc. are identical, do not add CR, obtained flame-retardant expanded rubber.
Comparative example 3
Material formula: EPDM70 part, CR30 part, 10 parts, zinc oxide, 4 parts, magnesium oxide, stearic acid 6 parts, carbon black N33020 part, antioxidant 4010NA 1 part, anti-irradiation agent 10 parts, silane coupling agent 10 parts, water-resisting agent 10 parts, 1.4 parts, sulphur, promotor ETU1 part, altax 1.2 parts, Vulcanization accelerator TMTD 4 parts, blowing agent AC 9 parts.
Concrete preparation method is identical with the preparation method of above-described embodiment 1, does not add fire retardant, obtained bipeltate.
Comparative example 4
Material formula: EPDM70 part, CR30 part, 10 parts, zinc oxide, 4 parts, magnesium oxide, stearic acid 6 parts, carbon black N33020 part, fire retardant ATH15 part, fire retardant MDH15 part, fire retardant Sb
2o
35 parts, antioxidant 4010NA 1 part, anti-irradiation agent 10 parts, silane coupling agent 10 parts, water-resisting agent 10 parts, 1.4 parts, sulphur, promotor ETU1 part, altax 1.2 parts, Vulcanization accelerator TMTD 4 parts, blowing agent AC 9 parts.
Concrete preparation method is identical with the preparation method of above-described embodiment 1, does not add ZB and CaCO
3, obtained flame-retardant expanded rubber.
Comparative example 5
Material formula: EPDM70 part, CR30 part, 10 parts, zinc oxide, 4 parts, magnesium oxide, stearic acid 6 parts, carbon black N33020 part, fire retardant MDH15 part, fire brake ZB 15 parts, fire retardant Sb
2o
310 parts, antioxidant 4010NA 1 part, anti-irradiation agent 10 parts, silane coupling agent 10 parts, water-resisting agent 10 parts, 1.4 parts, sulphur, promotor ETU1 part, altax 1.2 parts, Vulcanization accelerator TMTD 4 parts, blowing agent AC 9 parts.
Concrete preparation method is identical with the preparation method of above-described embodiment 1, has ZB, but does not have ATH and antimonous oxide, obtained flame-retardant expanded rubber.
Comparative example 6
Material formula: EPDM70 part, CR30 part, 10 parts, zinc oxide, 4 parts, magnesium oxide, stearic acid 6 parts, carbon black N33020 part, fire retardant ATH15 part, fire retardant MDH15 part, fire brake ZB 15 parts, antioxidant 4010NA 1 part, anti-irradiation agent 10 parts, silane coupling agent 10 parts, water-resisting agent 10 parts, 1.4 parts, sulphur, promotor ETU1 part, altax 1.2 parts, Vulcanization accelerator TMTD 4 parts, blowing agent AC 9 parts.
Concrete preparation method is identical with the preparation method of above-described embodiment 1, has ZB and ATH, but does not have antimonous oxide, obtained flame-retardant expanded rubber.
Comparative example 7
Material formula: EPDM70 part, CR30 part, 10 parts, zinc oxide, 4 parts, magnesium oxide, stearic acid 6 parts, carbon black N33020 part, fire retardant MDH15 part, fire brake ZB 15 parts, fire retardant Sb
2o
310 parts, antioxidant 4010NA 1 part, anti-irradiation agent 10 parts, silane coupling agent 10 parts, water-resisting agent 10 parts, 1.4 parts, sulphur, promotor ETU1 part, altax 1.2 parts, Vulcanization accelerator TMTD 4 parts, blowing agent AC 9 parts.
Concrete preparation method is identical with the preparation method of above-described embodiment 1, has ZB and antimonous oxide, but does not have ATH, obtained flame-retardant expanded rubber.
According to method mentioned above, the performance of comparative example 1 ~ 7 gained bipeltate is tested.Results of property is shown in Table 2, and table 2 is the performance test results of comparative example 1 ~ 7 gained bipeltate.
The performance test results of table 2 comparative example 1 ~ 7 gained bipeltate
By the comparison of above-described embodiment and comparative example, can find out, other flame resistant method is difficult to prepare the EPDM foam material with excellent mechanical performances and flame retardant properties simultaneously.Method of the present invention can the environmental protection flame retardant EPDM/CR bipeltate of simple, the excellent property of preparation technology, can solve that EPDM foam material flame retardant properties is poor, the not environmentally problem such as influenced with mechanical property.
Claims (10)
1. an environmental protection flame retardant bipeltate, is obtained through mixing and sulfur foam successively by mixture;
In mass fraction, described mixture comprises:
The terpolymer EP rubber of 60 ~ 100 parts;
The chloroprene rubber of x part, 0 < x < 40;
The zinc oxide of 5 ~ 10 parts;
The magnesium oxide of 3 ~ 4 parts;
The stearic acid of 4 ~ 6 parts;
The carbon black of 10 ~ 30 parts;
The aluminium hydroxide of 10 ~ 30 parts;
The magnesium hydroxide of 10 ~ 30 parts;
The zinc borate of 10 ~ 20 parts;
The calcium carbonate of 10 ~ 20 parts;
The antimonous oxide of 10 ~ 20 parts;
The sulphur of 1 ~ 2 part;
The vulcanization accelerator of 4 ~ 8 parts;
The whipping agent of 5 ~ 10 parts.
2. environmental protection flame retardant bipeltate according to claim 1, is characterized in that, described terpolymer EP rubber is made up of the material comprising ethene, propylene and ethylidene norbornene.
3. environmental protection flame retardant bipeltate according to claim 1, is characterized in that, described chloroprene rubber comprises the anti-form-1 of 80wt% ~ 90wt%, 1, the 2-sovprene of 4-sovprene and 1wt% ~ 2wt%.
4. environmental protection flame retardant bipeltate according to claim 1, is characterized in that, described vulcanization accelerator comprises the thiuram type accelerator of the Thiourea accelerator of 1 ~ 2 part, the thiazole accelerator of 1 ~ 2 part and 2 ~ 4 parts.
5. environmental protection flame retardant bipeltate according to claim 4, is characterized in that, described vulcanization accelerator comprises the curing two (thiocarbonyl group dimethylamine) of the ethylene thiocarbamide of 1 ~ 2 part, the dibenzothiazyl disulfide of 1 ~ 2 part and 2 ~ 4 parts.
6. the environmental protection flame retardant bipeltate according to any one of Claims 1 to 5, is characterized in that, described mixture also comprises the anti-aging agent of 1 ~ 2 part and the coupling agent of 5 ~ 10 parts.
7. environmental protection flame retardant bipeltate according to claim 6, is characterized in that, described mixture also comprises the antiradiation agent of 10 ~ 15 parts and the water-resisting agent of 5 ~ 10 parts.
8. a preparation method for environmental protection flame retardant bipeltate according to claim 1, comprises the following steps:
By the stearic acid of terpolymer EP rubber, carbon black, aluminium hydroxide, magnesium hydroxide, 1/2 quality and the zinc oxide of 1/2 quality mixing, obtain terpolymer EP rubber master batch;
By mixing for the stearic acid of chloroprene rubber, magnesium oxide, zinc borate, calcium carbonate, antimonous oxide and 1/2 quality, obtain chloroprene rubber master batch;
By mixing for the zinc oxide of described terpolymer EP rubber master batch, described chloroprene rubber master batch, sulphur, vulcanization accelerator, whipping agent and 1/2 quality, obtain sizing material;
Described rubber vulcanization is foamed, obtains environmental protection flame retardant bipeltate.
9. preparation method according to claim 8, is characterized in that, by the stearic acid of terpolymer EP rubber, carbon black, aluminium hydroxide, magnesium hydroxide, 1/2 quality and mixing temperature≤110 DEG C of the zinc oxide of 1/2 quality;
By temperature≤90 DEG C mixing for the stearic acid of chloroprene rubber, magnesium oxide, zinc borate, calcium carbonate, antimonous oxide and 1/2 quality;
By temperature≤70 DEG C mixing for the zinc oxide of described terpolymer EP rubber master batch, described chloroprene rubber master batch, sulphur, vulcanization accelerator, whipping agent and 1/2 quality.
10. preparation method according to claim 8 or claim 9, it is characterized in that, the temperature of described sulfur foam is 170 DEG C ~ 190 DEG C, and the pressure of described sulfur foam is 10MPa ~ 12MPa, and the time of described sulfur foam is 10min ~ 15min.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107200891A (en) * | 2017-05-09 | 2017-09-26 | 广西桂山特种橡胶制品有限公司 | A kind of fire retardant combination for neoprene |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3846371A (en) * | 1973-04-09 | 1974-11-05 | Du Pont | Masterbatching elastomer blends |
| EP0230564A1 (en) * | 1985-12-02 | 1987-08-05 | Bando Chemical Industries, Ltd. | Rubber Flooring |
| CN102504419A (en) * | 2011-11-07 | 2012-06-20 | 易宝(福建)高分子材料有限公司 | Ethylene propylene diene monomer and chloroprene rubber blended secondary closed pore foaming material and preparation method thereof |
| CN103613809A (en) * | 2013-11-21 | 2014-03-05 | 扬州动易运动用品有限公司 | Foamed rubber sealing material and manufacturing method thereof |
-
2015
- 2015-12-11 CN CN201510928825.4A patent/CN105330995B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3846371A (en) * | 1973-04-09 | 1974-11-05 | Du Pont | Masterbatching elastomer blends |
| EP0230564A1 (en) * | 1985-12-02 | 1987-08-05 | Bando Chemical Industries, Ltd. | Rubber Flooring |
| CN102504419A (en) * | 2011-11-07 | 2012-06-20 | 易宝(福建)高分子材料有限公司 | Ethylene propylene diene monomer and chloroprene rubber blended secondary closed pore foaming material and preparation method thereof |
| CN103613809A (en) * | 2013-11-21 | 2014-03-05 | 扬州动易运动用品有限公司 | Foamed rubber sealing material and manufacturing method thereof |
Cited By (12)
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|---|---|---|---|---|
| CN107200891A (en) * | 2017-05-09 | 2017-09-26 | 广西桂山特种橡胶制品有限公司 | A kind of fire retardant combination for neoprene |
| CN107652561A (en) * | 2017-10-03 | 2018-02-02 | 江苏联禹智能工程有限公司 | A kind of fire proofing material for fire engineering |
| CN107746509A (en) * | 2017-10-03 | 2018-03-02 | 江苏联禹智能工程有限公司 | A kind of preparation method of fire-proof board for fire engineering |
| CN108530765A (en) * | 2018-03-21 | 2018-09-14 | 安徽泰达汽车零部件有限公司 | A kind of high-foaming density rubber pipe |
| CN111303544A (en) * | 2020-04-14 | 2020-06-19 | 国光电器股份有限公司 | Flame-retardant high-damping rubber composition and preparation method and application thereof |
| CN111303544B (en) * | 2020-04-14 | 2022-06-21 | 国光电器股份有限公司 | Flame-retardant high-damping rubber composition and preparation method and application thereof |
| CN111423666A (en) * | 2020-05-27 | 2020-07-17 | 厦门麦丰密封件有限公司 | Ethylene propylene diene monomer rubber flushing valve diaphragm and preparation method thereof |
| CN111944246A (en) * | 2020-08-24 | 2020-11-17 | 四川远星橡胶有限责任公司 | High-temperature-resistant oil-resistant high-flame-retardant environment-friendly foaming adhesive mixture |
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