CN106280035A - The formula of high transparency rubber sole and preparation method - Google Patents

The formula of high transparency rubber sole and preparation method Download PDF

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Publication number
CN106280035A
CN106280035A CN201610757721.6A CN201610757721A CN106280035A CN 106280035 A CN106280035 A CN 106280035A CN 201610757721 A CN201610757721 A CN 201610757721A CN 106280035 A CN106280035 A CN 106280035A
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China
Prior art keywords
parts
rubber
high transparency
formula
sole
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Pending
Application number
CN201610757721.6A
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Chinese (zh)
Inventor
马小平
王昊
王一昊
王建森
黄伟良
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhejiang Rui Rui Rubber Polymer Materials Ltd By Share Ltd
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Zhejiang Rui Rui Rubber Polymer Materials Ltd By Share Ltd
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Application filed by Zhejiang Rui Rui Rubber Polymer Materials Ltd By Share Ltd filed Critical Zhejiang Rui Rui Rubber Polymer Materials Ltd By Share Ltd
Priority to CN201610757721.6A priority Critical patent/CN106280035A/en
Publication of CN106280035A publication Critical patent/CN106280035A/en
Pending legal-status Critical Current

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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
    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B13/00—Soles; Sole-and-heel integral units
    • A43B13/02—Soles; Sole-and-heel integral units characterised by the material
    • A43B13/04—Plastics, rubber or vulcanised fibre
    • 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
    • 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
    • C08L2201/00—Properties
    • C08L2201/10—Transparent films; Clear coatings; Transparent materials
    • 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
    • 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
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four 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)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)

Abstract

Disclosed by the invention is formula and the preparation method of a kind of high transparency rubber sole, its feature is made up of following raw material in parts by weight: solution polymerized butadiene styrene rubber 10～30 parts, butadiene rubber 20～60 parts, ethylene propylene diene rubber 30～70 parts, coupling agent 1.0～2.0 parts, antioxidant 0.5～2.0 parts, UV absorbent 0.5～2.0 parts, anhydrous White Carbon black 30.0～40.0 parts, activating agent 0.3～2.0 parts, tranquilizer 0.2～0.4 part, white oil 20.0～30.0 parts, vulcanizing agent 0.5～1.5 parts.Present invention discover that use ethylene propylene diene rubber can significantly improve, the anti-yellowing property of high transparency rubber sole, but owing to the half finished rubber cohesive of ethylene propylene diene rubber is poor, need and improve half finished rubber cohesive with butadiene rubber and butadiene-styrene rubber.Find to use ethylene propylene diene rubber simultaneously, the loading of white oil can be increased, enhance the transparency.

Description

The formula of high transparency rubber sole and preparation method
Technical field
The present invention relates to formula and the preparation method at high transparency rubber (being commonly called as glass cement) the big end, it is adaptable to cold glutinous motion Footwear and the production at the vulcanized rubber shoes big end.
Background technology
Cold glutinous sport shoes and the method producing employing molded vulcanization mostly at the vulcanized rubber shoes big end, and high transparency rubber sole (being commonly called as glass cement) uses transparent general purpose rubber to add anhydrous White Carbon black, vulcanizes with organic peroxide.And due to organic mistake Oxide to the instability of hot oxygen and general purpose rubber UV resistant is poor, simultaneously ultraviolet penetrate readily through high transparent rubber The reasons such as glue, cause high transparency rubber anti-yellowing property poor.Simultaneously high transparency rubber as to be fabricated to cold glutinous sport shoes or The vulcanized rubber shoes big end, it is necessary to meet the color inhibition requirement at the big end.General shoe sole requires that color inhibition reaches more than 4 grades (HG/ T3689-2014 standard testing), and high transparency rubber can only achieve 2～3 grades.
Summary of the invention
It is an object of the present invention to provide a kind of color inhibition to reach more than 4 grades (UV fluorescent tube method × 6 hour) high transparency rubber and (be commonly called as Glass cement) rubber compounding and preparation method thereof at the big end.
In order to achieve the above object, the technical scheme is that formula and the preparation of a kind of high transparency rubber sole is provided Method, its feature is made up of following raw material in parts by weight: solution polymerized butadiene styrene rubber 10～30 parts, butadiene rubber 20～60 parts, Ethylene propylene diene rubber 30～70 parts, coupling agent 1.0～2.0 parts, antioxidant 0.5～2.0 parts, UV absorbent 0.5～2.0 Part, anhydrous White Carbon black 30.0～40.0 parts, activating agent 0.3～2.0 parts, tranquilizer 0.2～0.4 part, white oil 20.0～30.0 parts, Vulcanizing agent 0.5～1.5 parts.
Further, described solution polymerized butadiene styrene rubber is Japan Asahi Chemical Industry Asaprene 303.
Described butadiene rubber is Qilu Petrochemical BR9000.
Described ethylene propylene diene rubber is Mitsui 4045M.
Described coupling agent is vinyl three (b-methoxy ethoxy) silane, Chinese name silane coupling A 172.
Described antioxidant is 2,6-di-tert-butyl-4-methy phenol, Chinese name antioxidant BHT.
Described UV absorbent is Octabenzone, Chinese name UV-531.
Described anhydrous White Carbon black is day Bender mountain QS-20LS.
Described activating agent is stearic acid and Polyethylene Glycol and combinations thereof.
Described tranquilizer is Degussa sipemat 820A.
Described white oil is Maoming Petrochemical 10# white oil.
Described vulcanizing agent is 1,1-di-t-butyl peroxy-3, and 5,5-trimethyl-cyclohexanes are commonly called as vulcanizing agent 3M and 2,5- Dimethyl-2,5 pairs (t-butyl peroxy) hexane, is commonly called as vulcanizing agent double 25.
Present invention discover that use ethylene propylene diene rubber can significantly improve, the resistance to Huang at high transparency rubber (being commonly called as glass cement) the big end Degeneration energy.But owing to the half finished rubber cohesive of ethylene propylene diene rubber is poor, need and with butadiene rubber and butadiene-styrene rubber Improve half finished rubber cohesive.Find to use ethylene propylene diene rubber simultaneously, the loading of white oil can be increased, improve high transparency The transparency of rubber sole.Simultaneously antioxidant, UV absorbent, the Fruit variety of tranquilizer and ratio, saturating to height The anti-yellowing property impact at bright rubber (being commonly called as glass cement) the big end is greatly.
Detailed description of the invention
The formula of a kind of high transparency rubber sole and preparation method, raw material composition the most in parts by weight: solution polymerized butylbenzene Rubber 10～30 parts, butadiene rubber 20～60 parts, ethylene propylene diene rubber 30～70 parts, coupling agent 1.0～2.0 parts, antioxidant 0.5 ～2.0 parts, UV absorbent 0.5～2.0 parts, anhydrous White Carbon black 30.0～40.0 parts, activating agent 0.3～2.0 parts, tranquilizer 0.2～0.4 part, white oil 20.0～30.0 parts, vulcanizing agent 0.5～1.5 parts.
Described solution polymerized butadiene styrene rubber is Japan Asahi Chemical Industry Asaprene 303.
Described butadiene rubber is Qilu Petrochemical BR9000.
Described ethylene propylene diene rubber is Mitsui 4045M.
Described coupling agent is vinyl three (b-methoxy ethoxy) silane, and Chinese name silane coupling A 172, for upper Hai Ruihuan industry and trade is supplied.
Described antioxidant is 2,6-di-tert-butyl-4-methy phenol, Chinese name antioxidant BHT, for Shanghai Hua Yi group Hua Yuan Chemical Co., Ltd. supplies.
Described UV absorbent is Octabenzone, Chinese name UV-531.
Described anhydrous White Carbon black is day Bender mountain QS-20LS.
Described activating agent is stearic acid and Polyethylene Glycol and combinations thereof, and stearic acid is that production and supply are contained in sky, Fujian, poly- The petrochemical iy produced supply of ethylene glycol Hai'an.
Described tranquilizer is Degussa sipemat 820A.
Described white oil is Maoming Petrochemical 10# color inhibition white oil.
Described vulcanizing agent is 1,1-di-t-butyl peroxy-3, and 5,5-trimethyl-cyclohexanes are commonly called as vulcanizing agent 3M and 2, 5-dimethyl-2,5 pairs of (t-butyl peroxy) hexanes, it is commonly called as vulcanizing agent double 25, for the supply of Dongguan Yue Bang scientific & technical corporation.
1. embodiment 1
It is made up of following raw material in parts by weight: solution polymerized butadiene styrene rubber 303 10 parts；Butadiene rubber BR9000 20 parts；Ternary EP rubbers 4045M 70.0 parts；Coupling agent A172 2.0 parts；Stearic acid 0.3 part；Polyethylene Glycol PEG4000 1.0 parts；Antioxygen Agent BHT 1.5 parts；UV absorbent 2.0 parts；White Carbon black QS-20LS 35 parts；10# white oil 25 parts；Tranquilizer 820A 1.5 Part；Vulcanizing agent 3M 0.3 part；Double 25 0.8 parts of vulcanizing agent.
The preparation of above-mentioned composition uses banbury one section mixing, and mill two-stage nitration adds the method for sulfur. and its concrete steps are such as Under:
Banbury one section is mixing: add solution polymerized butadiene styrene rubber and butadiene rubber, 30s after the most load weighted ethylene-propylene-diene monomer glue laminated is soft The while of rear 3/4 anhydrous White Carbon black and coupling agent, add antioxidant, activating agent, UV absorbent, tranquilizer, white after 120s Oil and remaining 1/4 anhydrous White Carbon black, binder removal after 240s.Putting into mill to refine, after about 5 minutes, bottom sheet is parked again.Wherein banbury Dump temperature controls≤120 DEG C, mill temperature control≤60 DEG C.
In order to make filler have more preferable dispersibility and the more preferable contractility of rubber molecule, one section of elastomeric compound needs to park Within at least 12 hours, (typically requiring between 12 hours to three months) just can add vulcanizing agent.
Mill two-stage nitration adds sulfur: will add after soft for one section of mixing glue laminated under after vulcanizing agent 3M and double 25,180 seconds of vulcanizing agent Sheet is parked.Crossing range request to be uniformly dispersed, mill mixer roller temperature controls at 40～60 DEG C.
2. embodiment 2
It is made up of following raw material in parts by weight: solution polymerized butadiene styrene rubber 303 10 parts；Butadiene rubber BR9000 50 parts；Ternary EP rubbers 4045M 40.0 parts；Coupling agent A172 1.05 parts；Stearic acid 0.2 part；Polyethylene Glycol PEG4000 1.0 parts；Antioxygen Agent BHT 2.5 parts；UV absorbent 2.0 parts；White Carbon black QS-20LS 30 parts；10# white oil 12 parts；Tranquilizer 820A 1.0 Part；Vulcanizing agent 3M 0.1 part；Double 25 0.6 parts of vulcanizing agent.
Remarks: preparation method is same as in Example 1.

Claims (13)

1. the formula of high transparency rubber sole, it is characterised in that: it is made up of following raw material in parts by weight: solution polymerized butadiene styrene rubber 10～30 parts, butadiene rubber 20～60 parts, ethylene propylene diene rubber 30～70 parts, coupling agent 1.0～2.0 parts, antioxidant 0.5～ 2.0 parts, UV absorbent 0.5～2.0 parts, anhydrous White Carbon black 30.0～40.0 parts, activating agent 0.3～2.0 parts, tranquilizer 0.2～0.4 part, white oil 20.0～30.0 parts, vulcanizing agent 0.5～1.5 parts.
The formula of high transparency rubber sole the most according to claim 1, it is characterised in that: described solution polymerized butadiene styrene rubber is day This Asahi Chemical Industry Asaprene 303.
The formula of high transparency rubber sole the most according to claim 1, it is characterised in that: described butadiene rubber is Shandong stone Change BR9000.
The formula of high transparency rubber sole the most according to claim 1, it is characterised in that: described ethylene propylene diene rubber is day These three well 4045M.
The formula of high transparency rubber sole the most according to claim 1, it is characterised in that: described coupling agent is vinyl three (b-methoxy ethoxy) silane.
The formula of high transparency rubber sole the most according to claim 1, it is characterised in that: described antioxidant is 2,6-bis-uncle Butyl-4-methylphenol.
The formula of high transparency rubber sole the most according to claim 1, it is characterised in that: described UV absorbent is 2- Hydroxyl-4-oxy-octyl benzophenone.
The formula of high transparency rubber sole the most according to claim 1, it is characterised in that: described anhydrous White Carbon black is Japan Moral mountain QS-20LS.
The formula of high transparency rubber sole the most according to claim 1, it is characterised in that: described activating agent be stearic acid and Polyethylene Glycol and combinations thereof.
The formula of high transparency rubber sole the most according to claim 1, it is characterised in that: described tranquilizer is Degussa sipemat 820A。
The formula of 11. high transparency rubber soles according to claim 1, it is characterised in that: described white oil is Maoming Petrochemical 10# white oil.
The formula of 12. high transparency rubber soles according to claim 1, it is characterised in that: described vulcanizing agent is 1,1-bis- T-butylperoxy-3,5,5-trimethyl-cyclohexane and 2,5-dimethyl-2,5 pairs (t-butyl peroxy) hexane.
The preparation method of 13. high transparency rubber soles according to claim 1, it is characterised in that it specifically comprises the following steps that
Banbury one section is mixing: add solution polymerized butadiene styrene rubber and butadiene rubber, 30s after the most load weighted ethylene-propylene-diene monomer glue laminated is soft After be simultaneously introduced 3/4 anhydrous White Carbon black and coupling agent, add antioxidant, activating agent, UV absorbent, stable after 120s Agent, white oil and remaining 1/4 White Carbon black, binder removal after 240s, put into mill and refine, and after about 5 minutes, bottom sheet is parked, wherein banbury Dump temperature controls≤120 DEG C, and mill temperature controls≤60 DEG C；
Mill two-stage nitration adds sulfur: adding vulcanizing agent after soft for one section of mixing glue laminated, after 180 seconds, bottom sheet is parked, and crosses range request dispersion Uniformly, mill mixer roller temperature controls at 40～60 DEG C.
CN201610757721.6A 2016-08-30 2016-08-30 The formula of high transparency rubber sole and preparation method Pending CN106280035A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107793602A (en) * 2017-12-07 2018-03-13 福建省安源橡胶科技有限公司 High-strength transparence glass rubber and its manufacture craft
CN109971078A (en) * 2019-04-28 2019-07-05 南通江中光电有限公司 A kind of formula of escalator handrail
CN110041626A (en) * 2019-04-28 2019-07-23 南通江中光电有限公司 A kind of preparation method of the formula of escalator handrail
CN110305366A (en) * 2019-07-29 2019-10-08 山东省临沂市三丰化工有限公司 A kind of antioxidative stabilizer composition and modified butadiene rubber
CN110343340A (en) * 2019-06-30 2019-10-18 瑞声科技(新加坡)有限公司 A kind of light transmission rubber composition, preparation method and the application in electro-acoustic element

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101774246A (en) * 2010-01-26 2010-07-14 宝宏(扬州)制鞋有限公司 Method for manufacturing sulfur bridge transparent rubber sole
CN103980575A (en) * 2014-05-29 2014-08-13 南京东亚橡塑制品有限公司 Transparent rubber sole material and preparation method thereof
CN104312014A (en) * 2014-09-29 2015-01-28 青岛高远光电测控技术有限公司 High-performance automobile sealing strip
CN105670130A (en) * 2016-01-21 2016-06-15 永嘉县伟诚橡胶工贸有限公司 Rubber comprehensive accelerator and method for preparing same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101774246A (en) * 2010-01-26 2010-07-14 宝宏(扬州)制鞋有限公司 Method for manufacturing sulfur bridge transparent rubber sole
CN103980575A (en) * 2014-05-29 2014-08-13 南京东亚橡塑制品有限公司 Transparent rubber sole material and preparation method thereof
CN104312014A (en) * 2014-09-29 2015-01-28 青岛高远光电测控技术有限公司 High-performance automobile sealing strip
CN105670130A (en) * 2016-01-21 2016-06-15 永嘉县伟诚橡胶工贸有限公司 Rubber comprehensive accelerator and method for preparing same

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107793602A (en) * 2017-12-07 2018-03-13 福建省安源橡胶科技有限公司 High-strength transparence glass rubber and its manufacture craft
CN109971078A (en) * 2019-04-28 2019-07-05 南通江中光电有限公司 A kind of formula of escalator handrail
CN110041626A (en) * 2019-04-28 2019-07-23 南通江中光电有限公司 A kind of preparation method of the formula of escalator handrail
CN110343340A (en) * 2019-06-30 2019-10-18 瑞声科技(新加坡)有限公司 A kind of light transmission rubber composition, preparation method and the application in electro-acoustic element
CN110343340B (en) * 2019-06-30 2022-04-22 瑞声科技(新加坡)有限公司 Light-transmitting rubber composition, preparation method and application in electroacoustic device
CN110305366A (en) * 2019-07-29 2019-10-08 山东省临沂市三丰化工有限公司 A kind of antioxidative stabilizer composition and modified butadiene rubber
CN110305366B (en) * 2019-07-29 2021-03-12 山东省临沂市三丰化工有限公司 Antioxidant stabilizer composition and modified butadiene rubber

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