CN114525007A - Light anti-cracking rubber sole and preparation method thereof - Google Patents
Light anti-cracking rubber sole and preparation method thereof Download PDFInfo
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- CN114525007A CN114525007A CN202210071622.8A CN202210071622A CN114525007A CN 114525007 A CN114525007 A CN 114525007A CN 202210071622 A CN202210071622 A CN 202210071622A CN 114525007 A CN114525007 A CN 114525007A
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- rubber sole
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 89
- 239000005060 rubber Substances 0.000 title claims abstract description 78
- 238000005336 cracking Methods 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 9
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 33
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 33
- 239000003795 chemical substances by application Substances 0.000 claims description 24
- 239000004088 foaming agent Substances 0.000 claims description 23
- 239000011521 glass Substances 0.000 claims description 18
- 239000004005 microsphere Substances 0.000 claims description 18
- 238000006065 biodegradation reaction Methods 0.000 claims description 17
- 229920005604 random copolymer Polymers 0.000 claims description 15
- 238000001746 injection moulding Methods 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 12
- 239000000806 elastomer Substances 0.000 claims description 11
- 238000002844 melting Methods 0.000 claims description 10
- 230000008018 melting Effects 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 239000004611 light stabiliser Substances 0.000 claims description 9
- 239000004709 Chlorinated polyethylene Substances 0.000 claims description 8
- 238000003801 milling Methods 0.000 claims description 8
- 239000002480 mineral oil Substances 0.000 claims description 8
- 235000010446 mineral oil Nutrition 0.000 claims description 8
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 8
- 230000004048 modification Effects 0.000 claims description 7
- 238000012986 modification Methods 0.000 claims description 7
- 229920000098 polyolefin Polymers 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 238000003825 pressing Methods 0.000 claims description 6
- 230000001681 protective effect Effects 0.000 claims description 6
- NBOCQTNZUPTTEI-UHFFFAOYSA-N 4-[4-(hydrazinesulfonyl)phenoxy]benzenesulfonohydrazide Chemical compound C1=CC(S(=O)(=O)NN)=CC=C1OC1=CC=C(S(=O)(=O)NN)C=C1 NBOCQTNZUPTTEI-UHFFFAOYSA-N 0.000 claims description 3
- 239000008187 granular material Substances 0.000 claims description 3
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 claims description 3
- 239000003094 microcapsule Substances 0.000 claims description 3
- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 abstract description 7
- 239000006260 foam Substances 0.000 abstract description 6
- 238000011161 development Methods 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 230000000704 physical effect Effects 0.000 abstract description 3
- 239000011148 porous material Substances 0.000 abstract 1
- 235000013339 cereals Nutrition 0.000 description 9
- 230000015556 catabolic process Effects 0.000 description 7
- 238000006731 degradation reaction Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 5
- 238000011925 1,2-addition Methods 0.000 description 4
- 241000209094 Oryza Species 0.000 description 4
- 235000007164 Oryza sativa Nutrition 0.000 description 4
- 235000009566 rice Nutrition 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 238000005187 foaming Methods 0.000 description 3
- 244000005700 microbiome Species 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229920002725 thermoplastic elastomer Polymers 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 238000012644 addition polymerization Methods 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011115 styrene butadiene Substances 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- JMTMSDXUXJISAY-UHFFFAOYSA-N 2H-benzotriazol-4-ol Chemical compound OC1=CC=CC2=C1N=NN2 JMTMSDXUXJISAY-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003674 animal food additive Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003864 humus Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- NPZTUJOABDZTLV-UHFFFAOYSA-N hydroxybenzotriazole Substances O=C1C=CC=C2NNN=C12 NPZTUJOABDZTLV-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Classifications
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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
-
- 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
- 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
-
- 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
- C08J9/009—Use of pretreated compounding ingredients
-
- 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
- C08J9/0095—Mixtures of at least two compounding ingredients belonging to different one-dot groups
-
- 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
- C08J9/32—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof from compositions containing microballoons, e.g. syntactic foams
-
- 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
- C08J2203/22—Expandable microspheres, e.g. Expancel®
-
- 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
- C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2353/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes
-
- 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
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/26—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment
- C08J2423/28—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment by reaction with halogens or halogen-containing compounds
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2425/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2425/02—Homopolymers or copolymers of hydrocarbons
- C08J2425/04—Homopolymers or copolymers of styrene
- C08J2425/08—Copolymers of styrene
- C08J2425/10—Copolymers of styrene with conjugated dienes
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- 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
- C08J2453/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2453/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes
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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
- C08J2491/00—Characterised by the use of oils, fats or waxes; Derivatives thereof
- C08J2491/06—Waxes
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- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/28—Glass
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- 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
- C08K9/00—Use of pretreated ingredients
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
A light anti-cracking rubber sole and a preparation method thereof are disclosed, wherein the rubber sole is composed of the following raw materials: the light anti-cracking rubber sole has the advantages of uniform foam pores, small density, high wear resistance, skid resistance and other conventional physical property advantages, has the characteristics of good weather resistance, ozone cracking resistance and the like, has biodegradability, can relieve the environmental problem caused by white pollution, and accords with the development direction of the current new material.
Description
Technical Field
The invention belongs to the field of rubber sole preparation, and particularly relates to a lightweight anti-cracking rubber sole and a preparation method thereof.
Background
At present, TPR thermoplastic rubber soles have high density (0.9-1.1 g/cm)3) Poor yellowing resistance, easy cracking (especially on the raised part of the toe cap), and the like.
Chinese patent CN104356582B discloses a micro-crosslinked thermoplastic elastomer and a preparation method thereof, and the prepared micro-crosslinked thermoplastic elastomer has the characteristics of small density, high wear resistance, uniform cells and the like, and has the characteristics of good low-temperature flexibility and dimensional stability. But the vulcanization temperature is 174-175 ℃, the processing temperature is high, and the energy consumption is high; when the rubber is used as toe cap rubber bonded to a vamp, the toe cap has stress of bending, the weather resistance is poor, and the cracking phenomenon is easy to occur, so that the improvement is needed.
Disclosure of Invention
The object of the present invention is to overcome the drawbacks of the prior art and to provide a lightweight anti-cracking rubber sole, and another object is to provide a method for preparing the above rubber sole.
The invention adopts the following technical scheme:
a light anti-cracking rubber sole is composed of the following raw materials in parts by weight:
further, the terminal double bonds of the branches of the butadiene block of the partially hydrogenated styrene-butadiene block copolymer are all hydrogenated, and the double bonds in the main chain are not affected.
Further, the partially hydrogenated styrene-butadiene random copolymer is a product in which the terminal double bonds of the styrene-butadiene copolymer are all hydrogenated.
Further, the biodegradation agent is a polyolefin graft modification product.
Further, the hollow glass microspheres are micron-sized surface-modified hollow glass microspheres.
Further, the foaming agent is one or more of foaming agent AC, microcapsule foaming agent and OBSH foaming agent.
Further, the feed additive is composed of the following raw materials in parts by weight:
a preparation method of a light anti-cracking rubber sole comprises the following steps:
premixing styrene-butadiene block copolymer and partially hydrogenated styrene-butadiene random copolymer in required weight parts in a high-speed mixer for 3-10 minutes, then melting and extruding the premix through a double-screw extruder at the temperature of 140-;
step two, pouring the elastomer particles prepared in the step one, the partially hydrogenated styrene-butadiene block copolymer, the white mineral oil, the chlorinated polyethylene, the foaming agent, the light stabilizer, the zinc stearate, the wear-resisting agent, the biodegradation agent and the hollow glass microspheres into an internal mixer for mixing and banburying, and then carrying out open milling and granulation to obtain the light anti-cracking rubber granules;
and step three, pouring the light anti-cracking rubber granules into a sealed sole mold for injection molding to obtain the light anti-cracking rubber sole.
Further, the specific process of the second step is as follows: pouring the elastomer particles prepared in the step one, the partially hydrogenated styrene-butadiene block copolymer, the white mineral oil, the chlorinated polyethylene, the foaming agent, the light stabilizer, the zinc stearate, the wear-resisting agent, the biodegradation agent and the hollow glass microspheres into an internal mixer bin, dropping a pressing hammer, closing a protective door, and carrying out internal mixing, and carrying out first material turning when the temperature reaches 108 ℃; continuously banburying, and turning for the second time when the temperature reaches 113 ℃; continuously banburying, and turning for the third time when the temperature reaches 129 ℃; and banburying for 2min, and finally pouring, milling and granulating.
Further, the third step comprises the following specific steps: pouring the light anti-cracking rubber grains into a hopper of a disc injection molding machine, automatically feeding, mixing and melting by a screw, extruding into a sealed rubber sole mold for injection molding, cooling at the screw temperature of 135 ℃ plus 160 ℃, and opening the mold to obtain the light anti-cracking rubber sole.
As can be seen from the above description of the present invention, compared with the prior art, the beneficial effects of the present invention are:
firstly, the light anti-cracking rubber sole prepared by the invention has the advantages of uniform foam holes, small density, high wear resistance, skid resistance and other conventional physical properties, has the characteristics of good weather resistance, ozone crack resistance and the like, has biodegradability, can relieve the environmental problem caused by white pollution, and accords with the development direction of the current new material;
secondly, the foaming agent is limited to be matched with the hollow glass microspheres, so that the foamed cells of the rubber sole are uniform, and the density is controlled to be 0.5-0.7g/cm3And can keep better mechanical property; styrene-butadiene block copolymer, styrene-butadiene block copolymer and styrene-butadiene random copolymer are all non-crystalline polymers, and when a foaming agent is added, foam collapse and hole string are easy to occur, so that the phenomena of no foaming at a thin position and hollow inclusion at a thick position are formed, and the mechanical properties such as tear strength, bending resistance and the like are poor; the application of the invention limits the cooperation of the foaming agent and the hollow glass microspheres, the foaming rate is small, the hollow glass microspheres can bear certain foaming pressure, the supporting force of the wall of the foam hole is improved, the foamed foam holes are uniform, and better mechanical properties are kept;
thirdly, the partially hydrogenated styrene-butadiene block copolymer and the partially hydrogenated styrene-butadiene random copolymer with hydrogenated double bonds at the tail ends of branched chains are adopted, and the proportion of the two is specifically limited, so that the anti-cracking performance of the rubber sole is improved, and the problem of cracking of the toe cap of the rubber sole is solved; the wet-skid resistance and the processing performance of the material can be improved by the double bonds at the tail ends of the branched chains, but the material has high reaction activity and is easy to oxidize, so that the performance is reduced and even the cracking phenomenon is caused after the material is aged; according to the invention, double bonds at the tail ends of the branched chains are hydrogenated, so that the ozone aging resistance of the rubber sole is obviously improved, the problem of cracking of the toe cap of the rubber sole is solved, and meanwhile, the better wet skid resistance and the better processing performance are kept through formula regulation.
Detailed Description
The invention is further described below by means of specific embodiments.
A light anti-cracking rubber sole is composed of the following raw materials in parts by weight:
wherein, the partially hydrogenated styrene-butadiene block copolymer is a selective hydrogenation product of the styrene-butadiene block copolymer under the action of a special catalyst, the double bonds at the tail ends of the branched chains of the butadiene block of the partially hydrogenated styrene-butadiene block copolymer are completely hydrogenated, and the double bonds on the main chain are not influenced; 1,4 addition polymerization and 1,2 addition polymerization exist in the butadiene polymerization process, wherein the 1,2 addition polymerization can generate a branch-chain terminal double bond, and the double bond has high reactivity and is easy to oxidize; wherein 1,4 addition polymerization does not produce branched terminal double bonds. The 1,2 addition polymerization of the partially hydrogenated styrene-butadiene block copolymer accounts for 3 to 30 mass% of the polymerized portion of butadiene. The styrene content of the partially hydrogenated styrene-butadiene block copolymer is 15 to 55 percent (mass ratio); the oil content of the partially hydrogenated styrene-butadiene block copolymer is 0 to 50 percent (mass ratio).
The partially hydrogenated styrene-butadiene random copolymer is a product in which the terminal double bonds of the styrene-butadiene copolymer are all hydrogenated. The partially hydrogenated styrene-butadiene random copolymer is resin, commonly known as K gum and K resin. When butadiene is subjected to 1,2 addition polymerization, a terminal double bond is generated, and the double bond has high reactivity and is easily oxidized.
The foaming agent at least comprises one or more of foaming agent AC, microcapsule foaming agent and OBSH foaming agent.
The light stabilizer at least comprises one of benzophenone ultraviolet absorbent, benzotriazole ultraviolet absorbent, hindered phenol antioxidant and hydroxybenzotriazole antioxidant.
The biodegradation agent is a polyolefin graft modification product, so that the degradation speed of the polymer in an anaerobic environment is accelerated, and the rubber sole can be degraded by at least 90% after 90 days of anaerobic landfill; specifically, the biodegradation agent is prepared by injecting a polyolefin material into an anaerobic organic auxiliary agent, and in a landfill (refuse landfill and deep sea) filled with active anaerobic organisms, the biodegradation agent attracts natural microorganisms, generates enzymes, destroys rubber polymer structures, and the microorganisms obtain required energy by digesting rubber, accelerate the propagation speed of the microorganisms, increase the biodegradation rate, and finally reduce rubber products into organic rotting substances (organic humus).
The hollow glass microspheres are micron-sized surface-modified hollow glass microspheres, specifically, the hollow glass microspheres are hollow spherical powdery inorganic nonmetallic materials, have the particle size of 2-320 mu m, and have the characteristics of light specific weight, large volume, low thermal conductivity, high compressive strength, good fluidity and the like.
A preparation method of a light anti-cracking rubber sole comprises the following steps:
premixing styrene-butadiene block copolymer and partially hydrogenated styrene-butadiene random copolymer in required weight parts in a high-speed mixer for 3-10 minutes, then melting and extruding the premix through a double-screw extruder at the temperature of 140-;
step two, the following steps: pouring the elastomer particles prepared in the step one, the partially hydrogenated styrene-butadiene block copolymer, the white mineral oil, the chlorinated polyethylene, the foaming agent, the light stabilizer, the zinc stearate, the wear-resisting agent, the biodegradation agent and the hollow glass microspheres into an internal mixer bin, dropping a pressing hammer, closing a protective door, and carrying out internal mixing, and carrying out first material turning when the temperature reaches 108 ℃; continuously banburying, and turning for the second time when the temperature reaches 113 ℃; continuously banburying, and turning for the third time when the temperature reaches 129 ℃; banburying for 2min, and finally pouring, milling and granulating to obtain the light anti-cracking rubber grain rice;
and step three, pouring the light anti-cracking rubber grains into a hopper of a disc injection molding machine, automatically feeding, mixing and melting by a screw, extruding into a sealing rubber sole mold for injection molding, cooling at the screw temperature of 135 plus 160 ℃, and opening the mold to obtain the light anti-cracking rubber sole.
Example 1
A light anti-cracking rubber sole is composed of the following raw materials in parts by weight:
the biodegradation agent is a polyolefin graft modification product, the degradation speed of the polymer in an anaerobic environment is accelerated, and the light anti-cracking rubber sole can be degraded by 92 percent (mass ratio) after 90 days of anaerobic landfill. The degradation experiment is referred to GB/T33797, and the mass loss is calculated after 90 days of landfill.
A preparation method of a light anti-cracking rubber sole comprises the following steps:
premixing styrene-butadiene block copolymer and partially hydrogenated styrene-butadiene random copolymer in required weight parts in a high-speed mixer for 3 minutes, then carrying out melt extrusion on the premix through a double-screw extruder at the temperature of 140 ℃, cooling and granulating to obtain elastomer particles;
step two, the following steps: pouring the elastomer particles prepared in the step one, the partially hydrogenated styrene-butadiene block copolymer, the white mineral oil, the chlorinated polyethylene, the foaming agent, the light stabilizer, the zinc stearate, the wear-resisting agent, the biodegradation agent and the hollow glass microspheres into an internal mixer bin, dropping a pressing hammer, closing a protective door, and carrying out internal mixing, and carrying out first material turning when the temperature reaches 108 ℃; continuously banburying, and turning for the second time when the temperature reaches 113 ℃; continuously banburying, and turning for the third time when the temperature reaches 129 ℃; banburying for 2min, and finally pouring, milling and granulating to obtain the light anti-cracking rubber grain rice;
and step three, pouring the light anti-cracking rubber grains into a hopper of a disc injection molding machine, automatically feeding, mixing and melting by a screw, extruding into a sealing rubber sole mold for injection molding, cooling at the temperature of 135 ℃, and opening the mold to obtain the light anti-cracking rubber sole.
Example 2
A light anti-cracking rubber sole is composed of the following raw materials in parts by weight:
the biodegradation agent is a polyolefin graft modification product, the degradation speed of the polymer in an anaerobic environment is accelerated, and the degradation rate of the rubber sole exceeds 90 percent after 90 days of anaerobic landfill.
A preparation method of a light anti-cracking rubber sole comprises the following steps:
firstly, premixing the required parts by weight of styrene-butadiene block copolymer and partially hydrogenated styrene-butadiene random copolymer in a high-speed mixer for 10 minutes, then, melting and extruding the premix through a double-screw extruder at 180 ℃, cooling and granulating to obtain elastomer particles;
step two, the following steps: pouring the elastomer particles prepared in the step one, the partially hydrogenated styrene-butadiene block copolymer, the white mineral oil, the chlorinated polyethylene, the foaming agent, the light stabilizer, the zinc stearate, the wear-resisting agent, the biodegradation agent and the hollow glass microspheres into an internal mixer bin, dropping a pressing hammer, closing a protective door, and carrying out internal mixing, and carrying out first material turning when the temperature reaches 108 ℃; continuously banburying, and turning for the second time when the temperature reaches 113 ℃; continuously banburying, and turning for the third time when the temperature reaches 129 ℃; banburying for 2min, and finally pouring, milling and granulating to obtain the light anti-cracking rubber grain rice;
and step three, pouring the light anti-cracking rubber grains into a hopper of a disc injection molding machine, automatically feeding, mixing and melting by a screw, extruding into a sealing rubber sole mold for injection molding, cooling the screw at the temperature of 160 ℃, and opening the mold to obtain the light anti-cracking rubber sole.
Example 3
A light anti-cracking rubber sole is composed of the following raw materials in parts by weight:
the biodegradation agent is a polyolefin graft modification product, the degradation speed of the polymer in an anaerobic environment is accelerated, and the degradation rate of the rubber sole is 93% after 90 days of anaerobic landfill.
A preparation method of a light anti-cracking rubber sole comprises the following steps:
premixing styrene-butadiene block copolymer and partially hydrogenated styrene-butadiene random copolymer in required weight parts in a high-speed mixer for 7 minutes, then carrying out melt extrusion on the premix through a double-screw extruder at 160 ℃, cooling and granulating to obtain elastomer particles;
step two, the following steps: pouring the elastomer particles prepared in the step one, the partially hydrogenated styrene-butadiene block copolymer, the white mineral oil, the chlorinated polyethylene, the foaming agent, the light stabilizer, the zinc stearate, the wear-resisting agent, the biodegradation agent and the hollow glass microspheres into an internal mixer bin, dropping a pressing hammer, closing a protective door, and carrying out internal mixing, and carrying out first material turning when the temperature reaches 108 ℃; continuously banburying, and turning for the second time when the temperature reaches 113 ℃; continuously banburying, and turning for the third time when the temperature reaches 129 ℃; banburying for 2min, and finally pouring, milling and granulating to obtain the light anti-cracking rubber grain rice;
and step three, pouring the light anti-cracking rubber grains into a hopper of a disc injection molding machine, automatically feeding, mixing and melting by a screw, extruding into a sealing rubber sole mold for injection molding, cooling at the temperature of 150 ℃, and opening the mold to obtain the light anti-cracking rubber sole.
Comparative example 1
In this comparative example, a method for preparing a lightweight anti-cracking rubber sole was substantially the same as that of example 3, except that:
styrene-butadiene block copolymer 1475 instead of the partially hydrogenated styrene-butadiene block copolymer, styrene-butadiene random copolymer instead of the partially hydrogenated styrene-butadiene random copolymer.
Comparative example 2
A certain brand of commercially available product.
The light anti-cracking rubber soles prepared by the three embodiments and the rubber soles in the prior art are used as comparative examples to be correspondingly tested, and the following data are obtained:
wherein, DIN abrasion resistance is tested according to GB/T9867-2008; the yellowing resistance test is carried out according to HG/T3689 sunlight at 50 ℃ for 24 hours; the ozone resistance test adopts an ozone testing machine, the temperature is 50 ℃, the humidity is 65%, the ozone concentration is 50pphm, the time is 24 hours, the sample is installed by a stretching clamp, the length of the sample is stretched to 120%, and the phenomenon that the toe cap is stressed and stretched is simulated.
TABLE 1 data Performance Table for each example
In conclusion, the light anti-cracking rubber sole prepared by the invention has the advantages of uniform foam holes, small density, high wear resistance, skid resistance and other conventional physical properties, has the characteristics of good weather resistance, ozone crack resistance and the like, has biodegradability, can relieve the environmental problem caused by white pollution, and accords with the development direction of the current new material; and as can be seen from comparison of comparative example 1, comparative example 2 and example 3, the present application adopts a partially hydrogenated styrene-butadiene block copolymer and a partially hydrogenated styrene-butadiene random copolymer, in which the double bonds at the ends of the branches are hydrogenated, and specifically limits the ratio of the two, so as to improve the anti-cracking performance of the rubber sole and solve the problem of cracking of the toe cap of the rubber sole.
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims and their equivalents and modifications within the scope of the description.
Claims (10)
1. The utility model provides a light prevent split crack rubber sole which characterized in that: the composition is characterized by comprising the following raw materials in parts by weight:
2. the lightweight anti-cracking rubber shoe sole according to claim 1, characterized in that: the terminal double bonds of the branches of the butadiene block of the partially hydrogenated styrene-butadiene block copolymer are completely hydrogenated, and the double bonds on the main chain are not affected.
3. The lightweight anti-cracking rubber shoe sole according to claim 1, characterized in that: the partially hydrogenated styrene-butadiene random copolymer is a product in which the terminal double bonds of the styrene-butadiene copolymer are all hydrogenated.
4. The lightweight anti-cracking rubber shoe sole as set forth in claim 1, wherein: the biodegradation agent is a polyolefin graft modification product.
5. The lightweight anti-cracking rubber shoe sole according to claim 1, characterized in that: the hollow glass microspheres are micron-sized surface-modified hollow glass microspheres.
6. The lightweight crack-releasing rubber shoe sole according to claim 1, characterized in that: the foaming agent is one or more of foaming agent AC, microcapsule foaming agent and OBSH foaming agent.
7. The lightweight anti-cracking rubber shoe sole according to claim 1, characterized in that: the composition is characterized by comprising the following raw materials in parts by weight:
8. a preparation method of a light anti-cracking rubber sole is characterized by comprising the following steps: the method comprises the following steps:
premixing styrene-butadiene block copolymer and partially hydrogenated styrene-butadiene random copolymer in required weight parts in a high-speed mixer for 3-10 minutes, then melting and extruding the premix through a double-screw extruder at the temperature of 140-;
step two, pouring the elastomer particles prepared in the step one, the partially hydrogenated styrene-butadiene block copolymer, the white mineral oil, the chlorinated polyethylene, the foaming agent, the light stabilizer, the zinc stearate, the wear-resisting agent, the biodegradation agent and the hollow glass microspheres into an internal mixer for mixing and banburying, and then carrying out open milling and granulation to obtain the light anti-cracking rubber granules;
and step three, pouring the light anti-cracking rubber grains into a sealed sole mold for injection molding to obtain the light anti-cracking rubber sole.
9. The preparation method of the light anti-cracking rubber sole according to claim 8, characterized in that: the second step comprises the following specific procedures: pouring the elastomer particles prepared in the step one, the partially hydrogenated styrene-butadiene block copolymer, the white mineral oil, the chlorinated polyethylene, the foaming agent, the light stabilizer, the zinc stearate, the wear-resisting agent, the biodegradation agent and the hollow glass microspheres into an internal mixer bin, dropping a pressing hammer, closing a protective door, and carrying out internal mixing, and carrying out first material turning when the temperature reaches 108 ℃; continuously banburying, and turning for the second time when the temperature reaches 113 ℃; continuously banburying, and turning for the third time when the temperature reaches 129 ℃; and banburying for 2min, and finally pouring, open milling and granulating.
10. The preparation method of the light anti-cracking rubber sole according to claim 8, characterized in that: the third step comprises the following specific procedures: pouring the light anti-cracking rubber grains into a hopper of a disc injection molding machine, automatically feeding, mixing and melting by a screw, extruding into a sealed rubber sole mold for injection molding, cooling at the screw temperature of 135 ℃ plus 160 ℃, and opening the mold to obtain the light anti-cracking rubber sole.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210071622.8A CN114525007A (en) | 2022-01-21 | 2022-01-21 | Light anti-cracking rubber sole and preparation method thereof |
| PCT/CN2022/114835 WO2023138055A1 (en) | 2022-01-21 | 2022-08-25 | Light anti-cracking rubber sole and preparation method therefor |
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| CN202210071622.8A CN114525007A (en) | 2022-01-21 | 2022-01-21 | Light anti-cracking rubber sole and preparation method thereof |
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| WO2023138055A1 (en) * | 2022-01-21 | 2023-07-27 | 茂泰(福建)鞋材有限公司 | Light anti-cracking rubber sole and preparation method therefor |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102391606A (en) * | 2011-09-07 | 2012-03-28 | 安踏（中国）有限公司 | Elastomer composition for soles of sports shoes, and manufacturing method thereof |
| CN112225946A (en) * | 2020-10-15 | 2021-01-15 | 深圳市通产丽星股份有限公司 | Composite biodegradation accelerant and preparation method and application thereof |
| CN214730977U (en) * | 2021-05-22 | 2021-11-16 | 洛阳绿之汇塑料降解科技有限公司 | Express bag that possesses environmental protection degradation ability |
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| BRPI0700089B1 (en) * | 2007-01-11 | 2018-02-06 | Alpargatas S.A | POLYMERIC COMPOSITION, VULCANIZED FOAMED SIMILAR MICROPOROUS RUBBER AND FOAM FOOT SOLES SIMILAR MICROPOROUS RUBBER |
| CN104804358B (en) * | 2015-04-24 | 2018-03-30 | 茂泰(福建)鞋材有限公司 | A kind of ageing-resistant thermoplasticity sole of light weight and preparation method thereof |
| CN107793690A (en) * | 2017-11-09 | 2018-03-13 | 武汉理工大学 | A kind of ultralight SEBS is material modified and preparation method thereof |
| CN114525007A (en) * | 2022-01-21 | 2022-05-24 | 茂泰(福建)鞋材有限公司 | Light anti-cracking rubber sole and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102391606A (en) * | 2011-09-07 | 2012-03-28 | 安踏（中国）有限公司 | Elastomer composition for soles of sports shoes, and manufacturing method thereof |
| CN112225946A (en) * | 2020-10-15 | 2021-01-15 | 深圳市通产丽星股份有限公司 | Composite biodegradation accelerant and preparation method and application thereof |
| CN214730977U (en) * | 2021-05-22 | 2021-11-16 | 洛阳绿之汇塑料降解科技有限公司 | Express bag that possesses environmental protection degradation ability |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2023138055A1 (en) * | 2022-01-21 | 2023-07-27 | 茂泰(福建)鞋材有限公司 | Light anti-cracking rubber sole and preparation method therefor |
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