CN109369993A - A kind of butadiene styrene rubber foaming material prescription of uniform in foaming - Google Patents

A kind of butadiene styrene rubber foaming material prescription of uniform in foaming Download PDF

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Publication number
CN109369993A
CN109369993A CN201811282419.5A CN201811282419A CN109369993A CN 109369993 A CN109369993 A CN 109369993A CN 201811282419 A CN201811282419 A CN 201811282419A CN 109369993 A CN109369993 A CN 109369993A
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CN
China
Prior art keywords
agent
foaming
parts
styrene rubber
blowing agent
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Pending
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CN201811282419.5A
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Chinese (zh)
Inventor
陈勇军
罗远芳
贾志欣
陈丽娟
毛晓琪
贾德民
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South China University of Technology SCUT
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South China University of Technology SCUT
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Priority to CN201811282419.5A priority Critical patent/CN109369993A/en
Publication of CN109369993A publication Critical patent/CN109369993A/en
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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
    • C08J9/06—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 by a chemical blowing agent
    • C08J9/10—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 by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
    • C08J9/102—Azo-compounds
    • C08J9/103—Azodicarbonamide
    • 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
    • C08J9/06—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 by a chemical blowing agent
    • C08J9/10—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 by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
    • C08J9/104—Hydrazines; Hydrazides; Semicarbazides; Semicarbazones; Hydrazones; Derivatives thereof
    • C08J9/105—Hydrazines; Hydrazides; Semicarbazides; Semicarbazones; Hydrazones; Derivatives thereof containing sulfur
    • 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
    • C08J9/06—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 by a chemical blowing agent
    • C08J9/10—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 by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
    • C08J9/107—Nitroso compounds
    • 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
    • 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/20—Ternary blends of expanding agents
    • 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
    • C08J2309/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08J2309/06—Copolymers with styrene
    • 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
    • C08J2491/00—Characterised by the use of oils, fats or waxes; Derivatives thereof
    • C08J2491/06—Waxes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02—Organic and inorganic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides

Abstract

The invention discloses a kind of butadiene styrene rubber foaming material prescription of uniform in foaming, which includes butadiene-styrene rubber, reinforcing filler, vulcanizing agent, composite foamable agent, plasticizer, activating agent and anti-aging agent.The composite foamable agent is the coordinated of blowing agent AC, blowing agent H, foaming agent OBSH.Inventive formulation includes consisting of ingredient: 100 parts of butadiene-styrene rubber, 15~35 parts of reinforcing fillers, 1.0~2.0 parts of vulcanizing agents, 10~30 parts of composite foamable agents, 10~15 parts of plasticizer, 10~20 portions of activating agents, 1~3 part of anti-aging agent, and wherein composite foamable agent is the mixture of blowing agent AC, blowing agent H, foaming agent OBSH arbitrary proportion.Has the characteristics of uniform in foaming, good mechanical properties by the butadiene styrene rubber foaming material of formula preparation of the invention.

Description

A kind of butadiene styrene rubber foaming material prescription of uniform in foaming
Technical field
The present invention relates to rubber expanded material fields, and in particular to a kind of butadiene styrene rubber foaming material of uniform in foaming is matched Side.
Background technique
Butadiene-styrene rubber is widely used in tire, adhesive tape, sebific duct, wire and cable, medical apparatus and each as a kind of general purpose rubber The fields such as the production of kind rubber product are the largest general purpose synthetic rubber kind, and realize the rubber of industrialized production earliest One of kind.But due to the limitation of general purpose rubber performance, butadiene-styrene rubber foam material field application also than relatively limited, Therefore how to improve formula, preparing high performance butadiene styrene rubber foaming material becomes the emphasis of research.
There is a kind of butadiene-styrene rubber microcellular foam material of disclosure of the invention and preparation method thereof (201610150936.1) proposition Using the method for supercritical foaming, supercritical fluid is carbon dioxide, the mixed gas of one or both of nitrogen gas, into Row foaming.The process conditions are harsh, and complicated for operation.The method to be foamed using foaming agent, simple process, mild condition. Most-often used organic foaming agent has azodicarbonamide (AC), N, N- dinitrosopentamethylene tetramine (H), 4,4 '-oxos Double benzene sulfonyl hydrazides (OBSH).Blowing agent AC is very widely used at present, have many advantages, such as it is non-toxic and tasteless non-discolouring, but there is also Obvious insufficient, the decomposition temperature of blowing agent AC is very high, by improving processing temperature or addition during producing foamed material Blowing promotor promotes foaming agent to decompose, and is in addition easy under the electrostatic interaction to reunite, and the foaming agent decomposition of reunion causes product Abscess aperture is larger, influences foaming quality.Blowing agent H is pollution-free, non-discolouring, but odorous, and decomposition rate is compared with AC at 165 DEG C Fastly, the gas permeability for decomposing generation is big, open-celled structure easy to form, and shrinkage is also larger when interior pressure becomes smaller.Foaming Agent OBSH is non-toxic and tasteless, and comprehensive performance is more excellent, uniform fine and closely woven foam structure easy to form, but gas forming amount is only blowing agent AC Half or so, and price is far more expensive than AC and H.
Therefore certain above-mentioned foaming agent, which is used alone, prepares butadiene styrene rubber foaming material, can all there is correspondence problem.
Summary of the invention
The purpose of the present invention is to provide a kind of butadiene styrene rubber foaming material prescriptions of uniform in foaming, it is intended to original foaming It is foamed jointly on the basis of agent using a variety of foaming agents, to reach mutual supplement with each other's advantages, prepares uniform in foaming, good mechanical performance Butadiene styrene rubber foaming material.
The purpose of the present invention is achieved through the following technical solutions.
A kind of butadiene styrene rubber foaming material prescription of uniform in foaming, comprises the following components in parts by weight:
The composite foamable agent is the mixture of blowing agent AC, blowing agent H and foaming agent OBSH.
Preferably, the reinforcing filler is one or more of carbon black, calcium carbonate and clay.
Preferably, the vulcanizing agent is one or both of sulphur and cumyl peroxide (DCP).
Preferably, blowing agent AC in the composite foamable agent, blowing agent H, foaming agent OBSH mass ratio be 1~5:1~ 5:1~5.Many experiments find that blowing agent AC, blowing agent H and foaming agent OBSH have synergistic effect, and three is used cooperatively can Improve the foaming quality and mechanical property of butadiene styrene rubber foaming material.
Preferably, the plasticizer is one or both of vaseline and paraffin oil.
Preferably, the activating agent is one or both of zinc oxide and stearic acid.
Preferably, the anti-aging agent is one or both of antioxidant MB and antioxidant D NP.
A kind of preparation of the butadiene styrene rubber foaming material of uniform in foaming described above includes the following steps:
It plasticates on the double roll mill 100 parts of packet roller butadiene-styrene rubber, then sequentially adds certain number vulcanizing agent, activity Agent, reinforcing filler and composite foamable agent and plasticizer are kneaded uniformly, and rubber compound is made in thin pass-out piece.Sizing material is in air drying It is placed some time under environment, back mixing, then sulfur foam forms, and butadiene styrene rubber foaming material is made.Vulcanization uses two sections of sulphur Change method, one step cure temperature are 160 DEG C, and post vulcanization temperature is 170 DEG C.
Compared with prior art, the present invention has the advantage that
1, has the spy of uniform in foaming, good mechanical properties by the butadiene styrene rubber foaming material of formula preparation of the invention Point.
2, inventive formulation preparation process flow is simple, can be mass-produced preparation, is conducive to realize industrialization.
Detailed description of the invention
Fig. 1 is the SEM photograph of styrene butadiene rubber sbr -111 prepared by embodiment 1.
Fig. 2 is the SEM photograph of styrene butadiene rubber sbr -211 prepared by embodiment 2.
Fig. 3 is the SEM photograph of styrene butadiene rubber sbr -221 prepared by embodiment 3.
Specific embodiment
Implementation of the invention is further described below in conjunction with example and attached drawing, but embodiments of the present invention are unlimited In this.
Part below is mass parts.
Embodiment 1:
It plasticates on the double roll mill 100 parts of packet roller butadiene-styrene rubber, then sequentially adds 1 part of DCP, 10 parts of zinc oxide, 10 Part stearic acid, 15 parts of carbon blacks, 1 part of antioxidant MB, and uniformly mixed foaming agent (by 3 parts of blowing agent ACs, 3 parts of blowing agent Hs and 3 parts of foaming agent OBSH compositions) and 10 parts of vaseline, it is kneaded uniformly, rubber compound is made in thin pass-out piece.Sizing material is in air drying environment Lower placement 8h, back mixing, then sulfur foam forms, and butadiene styrene rubber foaming material is made, and is labeled as SBR-111.Vulcanization uses two Section vulcanization, one step cure temperature are 160 DEG C, and post vulcanization temperature is 170 DEG C.
Embodiment 2:
Plasticate on the double roll mill 100 parts of packet roller butadiene-styrene rubber, then sequentially add 1.5 parts of DCP, 20 parts of zinc oxide, 20 parts of stearic acid, 35 parts of carbon blacks, 2 parts of antioxidant D NP, and uniformly mixed foaming agent is (by 6 parts of blowing agent ACs, 3 parts of foaming agents H and 3 part of foaming agent OBSH composition) and 10 parts of vaseline, it is kneaded uniformly, rubber compound is made in thin pass-out piece.Sizing material is in air drying 8h is placed under environment, back mixing, then sulfur foam forms, and butadiene styrene rubber foaming material SBR-211 is made.Vulcanization uses two sections of sulphur Change method, one step cure temperature are 160 DEG C, and post vulcanization temperature is 170 DEG C.
Embodiment 3:
It plasticates on the double roll mill 100 parts of packet roller butadiene-styrene rubber, then sequentially adds 1 part of DCP, 15 parts of zinc oxide, 15 Part stearic acid, 25 parts of carbon blacks, 3 parts of antioxidant D NP, and uniformly mixed foaming agent is (by 6 parts of blowing agent ACs, 6 parts of blowing agent Hs Formed with 3 parts of foaming agent OBSH) and 15 parts of vaseline, it is kneaded uniformly, rubber compound is made in thin pass-out piece.Sizing material is in air drying ring 8h is placed under border, back mixing, then sulfur foam forms, and butadiene styrene rubber foaming material SBR-221 is made.Vulcanization is using two sections of vulcanizations Method, one step cure temperature are 160 DEG C, and post vulcanization temperature is 170 DEG C.
Embodiment 4:
It is tested according to the apparent density of GB/T 6343-2009 standard test SBR-111, SBR-211, SBR-221.
According to the shore hardness of GB4493-84 standard test SBR-111, SBR-211, SBR-221.
According to the tensile strength and extension at break of GB/T 6344-2008 standard test SBR-111, SBR-211, SBR-221 Rate.
The physical mechanical property of different foaming systems is as shown in table 1.
Table 2
As shown in Table 1, butadiene styrene rubber foaming foaming materials produced by the present invention uniformly, good mechanical properties.
Above said content is only the basic explanation under present inventive concept, and is appointed made by technical solution according to the present invention What equivalent transformation, is within the scope of protection of the invention.

Claims (7)

1. a kind of butadiene styrene rubber foaming material prescription of uniform in foaming, which is characterized in that comprise the following components in parts by weight:
The composite foamable agent is the mixture of blowing agent AC, blowing agent H and foaming agent OBSH.
2. formula according to claim 1, which is characterized in that the reinforcing filler is in carbon black, calcium carbonate and clay It is one or more of.
3. formula according to claim 1, which is characterized in that the vulcanizing agent is in sulphur and cumyl peroxide It is one or two kinds of.
4. formula according to claim 1, which is characterized in that blowing agent AC, blowing agent H, hair in the composite foamable agent The mass ratio of infusion OBSH is 1~5:1~5:1~5.
5. formula according to claim 1, which is characterized in that the plasticizer be one of vaseline and paraffin oil or Two kinds.
6. formula according to claim 1, which is characterized in that the activating agent be one of zinc oxide and stearic acid or Two kinds.
7. formula according to claim 1, which is characterized in that the anti-aging agent is in antioxidant MB and antioxidant D NP It is one or two kinds of.
CN201811282419.5A 2018-10-31 2018-10-31 A kind of butadiene styrene rubber foaming material prescription of uniform in foaming Pending CN109369993A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115141433A (en) * 2022-07-19 2022-10-04 宁波拓普集团股份有限公司 Environment-friendly sealing element and preparation method thereof

Citations (3)

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Publication number Priority date Publication date Assignee Title
CN102775652A (en) * 2012-08-16 2012-11-14 株洲时代新材料科技股份有限公司 Thermoplastic elastomer micropore foaming material and preparation method thereof
CN107245195A (en) * 2017-05-31 2017-10-13 广东工业大学 A kind of foaming type electromagnetic screen rubber and its preparation method and application
CN108084509A (en) * 2016-11-22 2018-05-29 沈阳赛亚橡胶制品有限公司 A kind of Natural rubber foam material and preparation method thereof

Patent Citations (3)

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Publication number Priority date Publication date Assignee Title
CN102775652A (en) * 2012-08-16 2012-11-14 株洲时代新材料科技股份有限公司 Thermoplastic elastomer micropore foaming material and preparation method thereof
CN108084509A (en) * 2016-11-22 2018-05-29 沈阳赛亚橡胶制品有限公司 A kind of Natural rubber foam material and preparation method thereof
CN107245195A (en) * 2017-05-31 2017-10-13 广东工业大学 A kind of foaming type electromagnetic screen rubber and its preparation method and application

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115141433A (en) * 2022-07-19 2022-10-04 宁波拓普集团股份有限公司 Environment-friendly sealing element and preparation method thereof
CN115141433B (en) * 2022-07-19 2023-12-08 宁波拓普底盘系统有限公司 Environment-friendly sealing element and preparation method thereof

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Application publication date: 20190222