CN104403142B - A kind of environment protection modification natural rubber material - Google Patents

A kind of environment protection modification natural rubber material Download PDF

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Publication number
CN104403142B
CN104403142B CN201410725161.7A CN201410725161A CN104403142B CN 104403142 B CN104403142 B CN 104403142B CN 201410725161 A CN201410725161 A CN 201410725161A CN 104403142 B CN104403142 B CN 104403142B
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Prior art keywords
parts
natural rubber
environment protection
weight
concentration
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Expired - Fee Related
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CN201410725161.7A
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CN104403142A (en
Inventor
江功志
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Guangzhou Milesun Rubber Plastic Technology Co., Ltd.
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GUANGZHOU MILESUN RUBBER PLASTIC TECHNOLOGY Co Ltd
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Priority to CN201610426253.4A priority Critical patent/CN105860163A/en
Priority to CN201410725161.7A priority patent/CN104403142B/en
Publication of CN104403142A publication Critical patent/CN104403142A/en
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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
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/02—Copolymers with acrylonitrile
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C1/00—Treatment of rubber latex
    • C08C1/14—Coagulation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L7/00—Compositions of natural rubber
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • 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

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses a kind of environment protection modification natural rubber material, its raw material includes by weight: modified natural rubber 30 40 parts, nitrile rubber 30 40 parts, accelerant N cyclohexyl 2 benzothiazole sulfenamide 12 parts, fluorine-containing surfactant 35 parts, 13 parts of sulfur, captax 13 parts, diphenylguanidine S 24 parts, white carbon 30 40 parts, precipitated calcium carbonate 20 30 parts, super fine magnesium hydroxide 40 50 parts, aluminium triphosphate 8 13 parts, methyl-phosphoric acid dimethyl ester 5 10 parts, Calcium pyroborate 25 parts, antioxidant MB 12 parts, anti-aging agent RD 1.5 3 parts, naphthenic oil 12 parts, stearic acid 13 parts；In the present invention, above-mentioned environment protection modification natural rubber material, ageing-resistant performance is good, and permanent compression set is little, environmental protection, low cost.

Description

A kind of environment protection modification natural rubber material
Technical field
The present invention relates to technical field of rubber material, particularly relate to a kind of environment protection modification natural rubber Material.
Background technology
Elastomeric material and goods thereof are flourish at present, and it replaces the most rapidly steel, metal, water Mud and the natural polymer such as timber, cotton are widely used in the national warp such as industry, agricultural, military affairs Each department of Ji, natural rubber material is stored and during use by heat energy, machine long-term Tool energy, luminous energy and the effect of radiation energy, add oxygen, ozone, moisture and variable valency metal, metal Ion participate in chemical reaction, rubber sleeve material engender deliquescing tacky, hardening become fragile or The catabiosis of be full of cracks so that it is mechanical property degenerates and even loses its original performance and cause making Break down by process, and need to add synthetic material in preparation process, and synthetic material is past Toward containing the highest halogen, substantial amounts of toxic gas can be produced in combustion, cause ring The harm in border, forms grave danger to the life security of people, how to change natural rubber Property, a kind of ageing-resistant performance of preparation is good, and mechanical property is good, and the elastomeric material of environmental protection becomes mesh The front technical issues that need to address.
Summary of the invention
The present invention proposes a kind of environment protection modification natural rubber material, and ageing-resistant performance is good, forever Compression is little, environmental protection, low cost.
A kind of environment protection modification natural rubber material that the present invention proposes, its raw material includes by weight: Modified natural rubber 30-40 part, nitrile rubber 30-40 part, accelerant N-cyclohexyl-2-benzene And thiazolesulfenamide 1-2 part, fluorine-containing surfactant 3-5 part, sulfur 1-3 part, promote Agent M 1-3 part, diphenylguanidine S 2-4 part, white carbon 30-40 part, precipitated calcium carbonate 20-30 Part, super fine magnesium hydroxide 40-50 part, aluminium triphosphate 8-13 part, methyl-phosphoric acid dimethyl ester 5-10 part, Calcium pyroborate 2-5 part, antioxidant MB 1-2 part, anti-aging agent RD 1.5-3 part, Naphthenic oil 1-2 part, stearic acid 1-3 part；
Wherein modified natural rubber uses following technique to prepare: by weight by dilute for 0.1-0.5 part Earth elements is that 12-15wt% sulphuric acid is mixed homogeneously with 5-6 part concentration, then drops to concentration and is In 10-13wt% high wear-resistant carbon black suspension, dripping alkali liquor after mix homogeneously to system pH is 8-9, then stirring at normal temperature 1-2h, be subsequently adding natural rubber, to natural rubber in system Concentration is 15-20wt%, stirs, and then heating in water bath is to 70-80 DEG C of stirring 1-1.5h, Add flocculant to system and precipitate occurs, filter and remove moisture removal, with distilled water wash 2-4 time, Dehydration, is dried to obtain the modified natural rubber that water content is 0.3-0.6wt%, and baking temperature is 70-80℃。
Preferably, in above-mentioned environment protection modification natural rubber material, modified natural rubber, butyronitrile rubber The weight ratio of glue is 30-35:35-40.
Preferably, in above-mentioned environment protection modification natural rubber material, super fine magnesium hydroxide, trimerization phosphorus Acid aluminum, methyl-phosphoric acid dimethyl ester and the weight part ratio 40-45:8-10:8-10:2-4 of Calcium pyroborate.
Preferably, above-mentioned environment protection modification natural rubber material, its raw material includes by weight: change Property natural rubber 30-35 part, nitrile rubber 35-40 part, accelerant N-cyclohexyl-2-benzo Thiazolesulfenamide 1.5-1.8 part, fluorine-containing surfactant 3-4 part, sulfur 2-3 part, promote Agent M 2-3 part, diphenylguanidine S 2-3 part, white carbon 35-40 part, precipitated calcium carbonate 26-28 Part, super fine magnesium hydroxide 40-45 part, aluminium triphosphate 8-10 part, methyl-phosphoric acid dimethyl ester 8-10 part, Calcium pyroborate 2-4 part, antioxidant MB 1-2 part, anti-aging agent RD 1.5-3 part, Naphthenic oil 1-2 part, stearic acid 1-3 part.
Preferably, above-mentioned environment protection modification natural rubber material, its raw material includes by weight: change Property natural rubber 34 parts, nitrile rubber 38 parts, accelerant N-cyclohexyl-2-[4-morpholinodithio Sulfenamide 1.6 parts, fluorine-containing surfactant 3.6 parts, 2.4 parts of sulfur, captax 3 Part, diphenylguanidine S 2 parts, white carbon 38 parts, precipitated calcium carbonate 27 parts, ultra-fine hydrogen-oxygen 43 parts of magnesium of change, aluminium triphosphate 9 parts, methyl-phosphoric acid dimethyl ester 9 parts, Calcium pyroborate 3 parts, Antioxidant MB 1.3 parts, anti-aging agent RD 1.8 parts, naphthenic oil 1.4 parts, stearic acid 2.5 part.
Preferably, in above-mentioned environment protection modification natural rubber material, modified natural rubber uses as follows Prepared by technique: be 13.5wt% sulphuric acid by 0.4 part of rare earth element and 5.2 parts of concentration by weight Mix homogeneously, then dropping to concentration is in 12wt% high wear-resistant carbon black suspension, mix homogeneously Rear dropping alkali liquor to system pH is 8.4, and then stirring at normal temperature 1.5h is subsequently adding natural Rubber, is 18wt% to natural rubber concentration in system, stirs, then heating in water bath To 78 DEG C of stirring 1.2h, add flocculant to system and precipitate occur, filter and remove moisture removal, With distilled water wash 3 times, dehydration, it is dried to obtain the modified natural rubber that water content is 0.5wt% Glue, baking temperature is 74 DEG C.
In the present invention, using modified natural rubber with nitrile rubber as major ingredient, product can be strengthened Hot strength and tearing strength, reduce permanent deformation, and goods rubber is weather-proof, ageing-resistant performance pole For excellence and fire-retardant, wear-resisting, thermostability is also preferable, use sulfur as vulcanizing agent, promote Agent M, diphenylguanidine S, N cyclohexyl 2 benzothiazole sulfenamide as accelerator, and Using naphthenic oil as plasticizer, add fluorine-containing surfactant further, product machinery is strong Degree is greatly enhanced, and heat-resisting, ageing-resistant performance further enhances, and adds appropriate super fine magnesium hydroxide As acid absorbent, and jointly act on, not only with white carbon, precipitated calcium carbonate reinforcing filler Can reduce manufacturing cost, the resistance to ozone of goods, heat-resisting, fire resistance good, and permanent compression set is little, Antioxidant MB, anti-aging agent RD have preferably protection to heat, oxygen, ozone and poisonous metal Effect, antioxidant MB, anti-aging agent RD and super fine magnesium hydroxide, aluminium triphosphate, methyl Dimethyl phosphate, Calcium pyroborate act on jointly, and the heat-resisting and thermal stability of goods is preferable, use Life-span further enhances.
Detailed description of the invention
Embodiment 1
A kind of environment protection modification natural rubber material, its raw material includes by weight: modified natural rubber 34 parts of glue, nitrile rubber 38 parts, accelerant N-cyclohexyl-2-[4-morpholinodithio sulfenamide 1.6 parts, fluorine-containing surfactant 3.6 parts, 2.4 parts of sulfur, captax 3 parts, promote Agent DS 2 parts, white carbon 38 parts, precipitated calcium carbonate 27 parts, super fine magnesium hydroxide 43 parts, Aluminium triphosphate 9 parts, methyl-phosphoric acid dimethyl ester 9 parts, Calcium pyroborate 3 parts, antioxidant MB 1.3 Part, anti-aging agent RD 1.8 parts, naphthenic oil 1.4 parts, stearic acid 2.5 parts；
Wherein modified natural rubber uses following technique to prepare: by weight by 0.4 part of rare earth unit Element is that 13.5wt% sulphuric acid is mixed homogeneously with 5.2 parts of concentration, and then dropping to concentration is 12wt% In high wear-resistant carbon black suspension, dripping alkali liquor to system pH after mix homogeneously is 8.4, so Rear stirring at normal temperature 1.5h, is subsequently adding natural rubber, to natural rubber concentration in system is 18wt%, stirs, and then heating in water bath is to 78 DEG C of stirring 1.2h, adds flocculant to body There is precipitate in system, filters and removes moisture removal, with distilled water wash 3 times, dehydration, is dried to obtain Water content is the modified natural rubber of 0.5wt%, and baking temperature is 74 DEG C.
Embodiment 2
A kind of environment protection modification natural rubber material, its raw material includes by weight: modified natural rubber 30 parts of glue, nitrile rubber 40 parts, accelerant N-cyclohexyl-2-[4-morpholinodithio sulfenamide 1 part, fluorine-containing surfactant 5 parts, 1 part of sulfur, captax 3 parts, diphenylguanidine S 2 parts, white carbon 40 parts, precipitated calcium carbonate 20 parts, super fine magnesium hydroxide 50 parts, trimerization Aluminum phosphate 8 parts, methyl-phosphoric acid dimethyl ester 10 parts, Calcium pyroborate 2 parts, antioxidant MB 2 Part, anti-aging agent RD 1.5 parts, naphthenic oil 2 parts, stearic acid 1 part；
Wherein modified natural rubber uses following technique to prepare: by weight by 0.5 part of rare earth unit Element is that 15wt% sulphuric acid is mixed homogeneously with 5 parts of concentration, and then dropping to concentration is that 10wt% height is resistance to In mill white carbon black suspension, dripping alkali liquor to system pH after mix homogeneously is 9, then room temperature Stirring 1h, is subsequently adding natural rubber, is 20wt% to natural rubber concentration in system, Stirring, then heating in water bath is to 70 DEG C of stirring 1.5h, adds flocculant and occurs to system Precipitate, filters and removes moisture removal, with distilled water wash 2 times, dehydration, is dried to obtain water content For the modified natural rubber of 0.6wt%, baking temperature is 70 DEG C.
Embodiment 3
A kind of environment protection modification natural rubber material, its raw material includes by weight: modified natural rubber 40 parts of glue, nitrile rubber 30 parts, accelerant N-cyclohexyl-2-[4-morpholinodithio sulfenamide 2 parts, fluorine-containing surfactant 3 parts, 3 parts of sulfur, captax 1 part, diphenylguanidine S 4 parts, white carbon 30 parts, precipitated calcium carbonate 30 parts, super fine magnesium hydroxide 40 parts, trimerization Aluminum phosphate 13 parts, methyl-phosphoric acid dimethyl ester 5 parts, Calcium pyroborate 5 parts, antioxidant MB 1 Part, anti-aging agent RD 3 parts, naphthenic oil 1 part, stearic acid 3 parts；
Wherein modified natural rubber uses following technique to prepare: by weight by 0.1 part of rare earth unit Element is that 12wt% sulphuric acid is mixed homogeneously with 6 parts of concentration, and then dropping to concentration is that 13wt% height is resistance to In mill white carbon black suspension, dripping alkali liquor to system pH after mix homogeneously is 8, then room temperature Stirring 2h, is subsequently adding natural rubber, is 15wt% to natural rubber concentration in system, Stirring, then heating in water bath is to 80 DEG C of stirring 1h, adds flocculant to system and occurs sinking Shallow lake thing, filters and removes moisture removal, and with distilled water wash 4 times, dehydration, being dried to obtain water content is The modified natural rubber of 0.3wt%, baking temperature is 80 DEG C.
The above, the only present invention preferably detailed description of the invention, but the protection model of the present invention Enclosing and be not limited thereto, any those familiar with the art is in the skill that the invention discloses In the range of art, according to technical scheme and inventive concept equivalent in addition thereof or change Become, all should contain within protection scope of the present invention.

Claims (6)

1. an environment protection modification natural rubber material, it is characterised in that its raw material wraps by weight Include: modified natural rubber 30-40 part, nitrile rubber 30-40 part, accelerant N-cyclohexyl-2- Benzothiazole sulfenamide 1-2 part, fluorine-containing surfactant 3-5 part, sulfur 1-3 part, promote Enter agent M 1-3 part, diphenylguanidine S 2-4 part, white carbon 30-40 part, precipitated calcium carbonate 20-30 part, super fine magnesium hydroxide 40-50 part, aluminium triphosphate 8-13 part, methyl acid phosphate two Methyl ester 5-10 part, Calcium pyroborate 2-5 part, antioxidant MB 1-2 part, anti-aging agent RD 1.5-3 Part, naphthenic oil 1-2 part, stearic acid 1-3 part；
Wherein modified natural rubber uses following technique to prepare: by weight by dilute for 0.1-0.5 part Earth elements is that 12-15wt% sulphuric acid is mixed homogeneously with 5-6 part concentration, then drops to concentration and is In 10-13wt% high wear-resistant carbon black suspension, dripping alkali liquor after mix homogeneously to system pH is 8-9, then stirring at normal temperature 1-2h, be subsequently adding natural rubber, to natural rubber in system Concentration is 15-20wt%, stirs, and then heating in water bath is to 70-80 DEG C of stirring 1-1.5h, Add flocculant to system and precipitate occurs, filter and remove moisture removal, with distilled water wash 2-4 time, Dehydration, is dried to obtain the modified natural rubber that water content is 0.3-0.6wt%, and baking temperature is 70-80℃。
Environment protection modification natural rubber material the most according to claim 1, it is characterised in that Modified natural rubber, the weight ratio of nitrile rubber are 30-35:35-40.
Environment protection modification natural rubber material the most according to claim 1, it is characterised in that The weight part ratio of super fine magnesium hydroxide, aluminium triphosphate, methyl-phosphoric acid dimethyl ester and Calcium pyroborate 40-45:8-10:8-10:2-4.
4. according to the environment protection modification natural rubber material described in any one of claim 1-3, its Being characterised by, its raw material includes by weight: modified natural rubber 30-35 part, nitrile rubber 35-40 part, accelerant N-cyclohexyl-2-[4-morpholinodithio sulfenamide 1.5-1.8 part is fluorine-containing Surfactant 3-4 part, sulfur 2-3 part, captax 2-3 part, diphenylguanidine S 2-3 Part, white carbon 35-40 part, precipitated calcium carbonate 26-28 part, super fine magnesium hydroxide 40-45 part, Aluminium triphosphate 8-10 part, methyl-phosphoric acid dimethyl ester 8-10 part, Calcium pyroborate 2-4 part, anti-old Agent MB 1-2 part, anti-aging agent RD 1.5-3 part, naphthenic oil 1-2 part, stearic acid 1-3 Part.
Environment protection modification natural rubber material the most according to claim 4, it is characterised in that Its raw material includes by weight: modified natural rubber 34 parts, nitrile rubber 38 parts, accelerator N cyclohexyl 2 benzothiazole sulfenamide 1.6 parts, fluorine-containing surfactant 3.6 parts, sulfur Sulphur 2.4 parts, captax 3 parts, diphenylguanidine S 2 parts, white carbon 38 parts, lightweight Calcium carbonate 27 parts, super fine magnesium hydroxide 43 parts, aluminium triphosphate 9 parts, methyl acid phosphate diformazan Ester 9 parts, Calcium pyroborate 3 parts, antioxidant MB 1.3 parts, anti-aging agent RD 1.8 parts, ring Alkanes oil 1.4 parts, stearic acid 2.5 parts.
Environment protection modification natural rubber material the most according to claim 1, it is characterised in that change Property natural rubber use following technique to prepare: by weight by 0.4 part of rare earth element and 5.2 parts Concentration is 13.5wt% sulphuric acid mix homogeneously, and then dropping to concentration is 12wt% high wear-resistant carbon black In suspension, dripping alkali liquor to system pH after mix homogeneously is 8.4, then stirring at normal temperature 1.5h, is subsequently adding natural rubber, is 18wt% to natural rubber concentration in system, stirring Uniformly, then heating in water bath is to 78 DEG C of stirring 1.2h, adds flocculant and precipitation occurs to system Thing, filters and removes moisture removal, and with distilled water wash 3 times, dehydration, being dried to obtain water content is The modified natural rubber of 0.5wt%, baking temperature is 74 DEG C.
CN201410725161.7A 2014-12-04 2014-12-04 A kind of environment protection modification natural rubber material Expired - Fee Related CN104403142B (en)

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CN201610426253.4A CN105860163A (en) 2014-12-04 2014-12-04 Environment-friendly modified natural rubber material
CN201410725161.7A CN104403142B (en) 2014-12-04 2014-12-04 A kind of environment protection modification natural rubber material

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CN107286399A (en) * 2017-08-02 2017-10-24 合肥市大卓电力有限责任公司 A kind of environment-protective rubber material and preparation method thereof

Citations (2)

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Publication number Priority date Publication date Assignee Title
CN101631829A (en) * 2007-09-10 2010-01-20 住友橡胶工业株式会社 Vulcanized rubber composition, pneumatic tire, and their production methods
CN104119579A (en) * 2014-08-10 2014-10-29 宁国市宁盛橡塑制品有限公司 High-stability anti-tear rubber material

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Publication number Priority date Publication date Assignee Title
CN101724187B (en) * 2008-10-31 2011-08-31 中国石油化工股份有限公司 Rubber composition and preparation method thereof
JP2011099012A (en) * 2009-11-04 2011-05-19 Bridgestone Corp Rubber composition for tie rubber, and pneumatic tire using the same
CN101973446B (en) * 2010-07-29 2012-05-30 安徽中意胶带有限责任公司 Environmentally-friendly flame-retardant conveyor belt with steel cable core used for coal mines

Patent Citations (2)

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Publication number Priority date Publication date Assignee Title
CN101631829A (en) * 2007-09-10 2010-01-20 住友橡胶工业株式会社 Vulcanized rubber composition, pneumatic tire, and their production methods
CN104119579A (en) * 2014-08-10 2014-10-29 宁国市宁盛橡塑制品有限公司 High-stability anti-tear rubber material

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