CN117624909A - One-step modification method for leather scraps, composite material and application thereof - Google Patents
One-step modification method for leather scraps, composite material and application thereof Download PDFInfo
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- CN117624909A CN117624909A CN202311456881.3A CN202311456881A CN117624909A CN 117624909 A CN117624909 A CN 117624909A CN 202311456881 A CN202311456881 A CN 202311456881A CN 117624909 A CN117624909 A CN 117624909A
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- 239000010985 leather Substances 0.000 title claims abstract description 126
- 239000002131 composite material Substances 0.000 title claims abstract description 37
- 238000002715 modification method Methods 0.000 title claims abstract description 6
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- 239000005060 rubber Substances 0.000 claims abstract description 39
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 38
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 15
- 229920003048 styrene butadiene rubber Polymers 0.000 claims abstract description 13
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- 229920002857 polybutadiene Polymers 0.000 claims abstract description 12
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- 238000012986 modification Methods 0.000 claims description 12
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- 239000011651 chromium Substances 0.000 claims description 9
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- 230000008569 process Effects 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- 229910021485 fumed silica Inorganic materials 0.000 claims description 6
- 239000003607 modifier Substances 0.000 claims description 6
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 claims description 4
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 4
- 239000013543 active substance Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 claims description 3
- ZNRLMGFXSPUZNR-UHFFFAOYSA-N 2,2,4-trimethyl-1h-quinoline Chemical compound C1=CC=C2C(C)=CC(C)(C)NC2=C1 ZNRLMGFXSPUZNR-UHFFFAOYSA-N 0.000 claims description 3
- BUZICZZQJDLXJN-UHFFFAOYSA-N 3-azaniumyl-4-hydroxybutanoate Chemical compound OCC(N)CC(O)=O BUZICZZQJDLXJN-UHFFFAOYSA-N 0.000 claims description 3
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 235000021355 Stearic acid Nutrition 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- 239000004200 microcrystalline wax Substances 0.000 claims description 3
- 235000019808 microcrystalline wax Nutrition 0.000 claims description 3
- IUJLOAKJZQBENM-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-2-methylpropan-2-amine Chemical compound C1=CC=C2SC(SNC(C)(C)C)=NC2=C1 IUJLOAKJZQBENM-UHFFFAOYSA-N 0.000 claims description 3
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 239000008117 stearic acid Substances 0.000 claims description 3
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 claims description 3
- 229960002447 thiram Drugs 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 3
- WRXCBRHBHGNNQA-UHFFFAOYSA-N (2,4-dichlorobenzoyl) 2,4-dichlorobenzenecarboperoxoate Chemical compound ClC1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1Cl WRXCBRHBHGNNQA-UHFFFAOYSA-N 0.000 claims description 2
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 claims description 2
- -1 3, 5-di-tert-butyl-4-hydroxyphenyl Chemical group 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 238000010276 construction Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000012188 paraffin wax Substances 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 239000001993 wax Substances 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims 1
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- IPJGAEWUPXWFPL-UHFFFAOYSA-N 1-[3-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC(N2C(C=CC2=O)=O)=C1 IPJGAEWUPXWFPL-UHFFFAOYSA-N 0.000 description 1
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a one-step modification method of leather scraps, a composite material and application thereof. Firstly, utilizing a silane coupling agent, sodium hydroxide, urea and other compounds to modify and finely crush leather scraps to obtain modified fine leather scraps; mixing the rubber with styrene-butadiene rubber, isoprene rubber, butadiene rubber, vulcanizing agent, vulcanizing aid, anti-aging agent, reinforcing agent and the like according to a certain proportion; and then, vulcanizing and forming to obtain the modified fine leather scraps/rubber composite material. The composite material has excellent wear resistance, skid resistance, tear resistance and bending resistance, changes waste into valuable, realizes the recycling of waste leather waste, obviously reduces the production cost of the leather scrap modified composite material, saves resources, and has important significance for the green recycling development of the leather industry.
Description
Technical Field
The invention relates to the technical field of leather and solid waste treatment, in particular to a one-step modification method of leather scraps, a composite material and application thereof.
Background
China is a large tanning country, and a large amount of solid wastes are generated in the leather production process, and the solid wastes comprise the following three types: firstly, the waste materials, such as offal, gray skin sheets, scraps and the like, cut from the raw leather are free of chromium leather solid waste materials, secondly, the chromium leather solid waste materials generated by shaving, trimming and the like of blue leather are the waste materials remained after leather products are processed. The three types of solid waste have the annual output of millions of tons, and if the three types of solid waste are not well treated, resources are wasted and the environment is polluted, so that the resource utilization of waste leather scraps is an important topic of common attention at home and abroad. The recycling and high-quality recycling of leather waste are important measures for solving the serious waste pollution problem of the leather industry and realizing the recycling development of the leather industry.
The main component of leather scraps is leather collagen fibers, and the leather scraps have an internal (microcrack and fibrous sliding) and external (crack deflection and crack bridging) structure. Because of the unique multi-scale structure, the fine leather scraps show excellent mechanical properties, have higher strength and modulus, and are rubber reinforcing agents with better application prospects. There have been many studies and reports on the reuse of waste leather scraps. For example, chinese patent CN110607021A discloses a preparation method of leather scraps composite modified EVA foaming shoe material, and the leather scraps composite modified EVA foaming shoe material with performance comparable with that of common EVA shoe material and low cost is prepared by plasticizing the leather scraps. Chinese patent CN112048185 a discloses a leather scrap modified foaming midsole and a preparation method thereof, which improves the compatibility of leather waste and EVA by melt grafting modification, and obtains a leather scrap modified foaming material with excellent performance.
Comprehensive analysis shows that the existing preparation methods of the leather chip modified polymer composite material have the problems of high processing and production energy consumption, complex modification steps, poor compatibility of modified fine leather chips and a matrix material and the like.
Disclosure of Invention
One of the objects of the present invention is to provide a one-step modification method of leather scraps, comprising the steps of: and (3) uniformly mixing the leather scraps and the modifier, and placing the obtained mixture into a high-speed crusher to carry out modification and fine crushing simultaneously, so as to finally obtain the modified fine leather scraps.
Further, the leather scraps may be waste leather scraps containing chromium or waste leather scraps containing no chromium. The waste leather scraps are usually flaky scraps generated when leather is sliced into one or more layers by a leather slicing machine, or flaky scraps generated when leather is sliced into a specified standard thickness by a shaving machine, or waste remained after leather product processing.
Further, the modifier is at least one selected from silane coupling agent, sodium hydroxide and urea.
Further, the mass ratio of the leather scraps to the modifier is 3-1:1-3.
Further, the rotation speed of the high-speed crusher is 3000-6000rpm.
Further, the particle size of the prepared modified fine leather scraps is 40-400 meshes.
The second object of the invention is to provide a modified fine leather chip-based composite material, which comprises the following components in parts by weight:
styrene-butadiene rubber: 30-60 parts;
isoprene rubber: 10-30 parts of a lubricant;
butadiene rubber: 5-20 parts;
modified fine leather scraps: 10-200 parts of a lubricant;
vulcanizing agent: 1-5 parts;
vulcanization aid: 2-15 parts;
anti-aging agent: 1-3 parts;
reinforcing agent: 10-40 parts.
Further, the composite material comprises the following components in parts by weight:
styrene-butadiene rubber: 40-50 parts;
isoprene rubber: 15-25 parts of a lubricant;
butadiene rubber: 10-15 parts of a lubricant;
modified fine leather scraps: 50-150 parts;
vulcanizing agent: 2-4 parts;
vulcanization aid: 5-12 parts;
anti-aging agent: 0.5-2.5 parts;
reinforcing agent: 20-35 parts.
Further, the vulcanizing agent is at least one selected from sulfur, dicumyl peroxide (DCP), 2, 4-di-tert-butyl cumyl peroxide, 2, 4-dichloro benzoyl peroxide (bis-di-tetra), and 2, 5-dimethyl-2, 5-bis (tert-butyl peroxy) hexane (bis-di-penta).
Further, the vulcanization aid comprises an accelerator and an active agent. Wherein the accelerator is at least one selected from N-cyclohexyl-2-benzothiazole sulfenamide, N-tertiary butyl-2-benzothiazole sulfenamide, 2' -dibenzothiazyl disulfide, tetramethylthiuram monosulfide, 2-mercaptobenzothiazole and tetramethylthiuram disulfide, and the active agent is at least one selected from diethylene glycol, polyethylene glycol, zinc oxide, stearic acid and zinc stearate.
Further, the antioxidant is at least one selected from 2-mercaptobenzimidazole, 2, 4-trimethyl-1, 2-dihydroquinoline polymer, N- (1, 3-dimethylbutyl) -N '-phenyl-p-phenylenediamine, N' -m-phenylene-bismaleimide, tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, paraffin wax, microcrystalline wax and antifogging wax.
Further, the reinforcing agent is at least one selected from the group consisting of fumed silica, precipitated silica and carbon black.
The third object of the present invention is to provide a method for preparing the modified fine leather chips-based composite material, which mainly comprises the following steps: firstly, mixing the raw materials and mixing at normal temperature, and then, heating and vulcanizing the obtained rubber compound.
Further, the feeding method in the mixing process is as follows: firstly adding rubber (styrene-butadiene rubber, isoprene rubber and butadiene rubber), then adding modified fine leather scraps and mixing for a period of time, and then adding reinforcing agent, anti-aging agent, vulcanizing agent and vulcanizing auxiliary agent to continuously mix. In the process of preparing the rubber compound, the modified fine leather scraps are mixed with rubber preferentially, so that the uniform dispersion of the modified fine leather scraps in a rubber matrix can be better realized.
Further, the rubber compound vulcanizing temperature is 150-200 ℃.
The fourth object of the invention is to provide the application of the composite material based on the modified fine leather scraps in sole materials, automobile industry and building industry.
The invention firstly prepares the modified fine leather scraps by a one-step method, and then prepares the highly filled fine leather scraps modified composite material by mechanical blending, and the process solves the problems of high processing energy consumption, complex process and the like commonly existing in the leather scraps modification process in the prior art. The invention solves the technical problems of poor dispersibility and difficult uniform dispersion of waste leather scraps in a composite material matrix through modification and fine crushing, creatively constructs a chemical interface between the leather collagen fibers and a rubber molecular structure, promotes the uniform dispersion of the leather collagen fibers in rubber by utilizing the interaction of the leather collagen fibers and the rubber molecular structure, and can be used as a bracket in a rubber matrix by a three-dimensional collagen fiber network formed by the leather collagen fibers, and the stress transmission from the rubber matrix to the fiber network is promoted by the strong interface interaction between the fibers and the matrix, so that the leather scraps/rubber composite material with excellent performance is obtained. The detection result shows that the composite material prepared by the invention has excellent wear resistance, skid resistance, tear resistance and bending resistance, and the composite material has good comfort and high strength after being manufactured into soles. The invention not only realizes the recycling of leather waste, but also obviously reduces the production cost and saves resources, can be applied to various product application scenes, and is particularly suitable for sole materials.
Compared with the prior similar technology and products, the invention has the advantages that:
(1) Styrene-butadiene rubber, isoprene rubber and butadiene rubber are selected as matrixes, wherein the styrene-butadiene rubber has excellent elasticity, wear resistance and weather resistance, and the three rubbers have good compatibility, so that the composite material has good performances of elasticity, moisture resistance, slip resistance, wear resistance and the like;
(2) The silane coupling agent, sodium hydroxide, urea and the like are utilized to modify leather scraps, the dispersibility and interaction of the leather scraps in various rubber matrixes are improved through simple equipment and a relatively easy industrialization method, the high filling quantity of modified fine leather scraps is realized, and the mechanical properties of the composite material are enhanced through a three-dimensional network formed by the modified fine leather scraps;
(3) The whole process is simpler, and only one step is needed for modification of leather scraps or compounding of the leather scraps and a rubber matrix, so that the processing flow is greatly shortened, and the production cost is reduced;
(4) The method is expected to solve the problems of treatment and reutilization of leather waste, realizes high-quality recycling of the leather waste, protects the environment while changing waste into valuables, and accords with the double-carbon development directions of carbon peak and carbon neutralization.
Detailed Description
In order for those of ordinary skill in the art to fully understand the technical solutions and advantageous effects of the present invention, the following description will be given with reference to specific embodiments.
Example 1
A composite material based on modified fine leather scraps comprises the following components in percentage by weight:
styrene-butadiene rubber, chinese petrochemical, 40kg;
isoprene rubber, japanese rayleigh, 25kg;
butadiene rubber, solitary petrochemical seed, 10kg;
50kg of modified fine leather scraps;
vulcanizing agent, DCP, commercially available, 2kg;
vulcanization accelerators, N-cyclohexyl-2-benzothiazole sulfenamide, commercially available, 3kg;
vulcanizing activator, diethylene glycol, commercially available, 2kg
1.5kg of an anti-aging agent, 2-mercaptobenzimidazole;
reinforcing agent, fumed silica, commercially available, 20kg.
The first step adopts a one-step method to prepare the modified fine leather scraps. 60kg of chromium-containing waste leather and 20kg of silane coupling agent KH580 are put into a high-speed crusher at a rotation speed of 4000rpm for shearing crushing and modification, and modified fine leather scraps with a particle size of about 300 meshes are obtained.
And mixing in the second step. Adding the three rubber raw materials into an open mill, adding modified fine leather scraps, mixing for a period of time, and then adding a vulcanizing agent, a vulcanization aid, an anti-aging agent, a reinforcing agent and the like, and continuously mixing to obtain a rubber compound.
And thirdly, vulcanizing. The rubber compound was placed in a mold and hot-pressed vulcanized at 175℃into a sheet of 2mm thickness.
Comparative example 1
This comparative example is substantially the same as example 1 except that: in the first step, the silane coupling agent KH580 is not added, and the mixture is directly crushed and then mixed and vulcanized.
Comparative example 2
This comparative example is substantially the same as example 1 except that: in the first step, the silane coupling agent is not added for direct crushing, and in turn, the silane coupling agent, a vulcanizing agent, a vulcanization aid, an anti-aging agent, a reinforcing agent and the like are added together for mixing and vulcanizing.
Example 2
A composite material based on modified fine leather scraps comprises the following components in percentage by weight:
styrene-butadiene rubber, fujian petrochemical, 50kg;
isoprene rubber, petrified, 15kg;
butadiene rubber, korean LG,15kg;
150kg of modified fine leather scraps;
vulcanizing agent, bis-II, penta, commercially available, 4kg;
vulcanization accelerators, N-tert-butyl-2-benzothiazole sulfenamide, commercially available, 7kg;
vulcanizing activator, polyethylene glycol, commercially available, 5kg;
2, 4-trimethyl-1, 2-dihydroquinoline polymer, commercially available, 2.5kg;
reinforcing agent, fumed silica, commercially available, 35kg.
The first step adopts a one-step method to prepare the modified fine leather scraps. 150kg of raw leather (without chromium) and 75kg of silane coupling agent KH570 were put into a high-speed crusher at 6000rpm to perform shearing crushing and modification, thereby obtaining modified fine leather scraps with a particle size of about 400 meshes.
And mixing in the second step. Adding the three rubber raw materials into an open mill, adding modified fine leather scraps, mixing for a period of time, and then adding a vulcanizing agent, a vulcanization aid, an anti-aging agent, a reinforcing agent and the like, and continuously mixing to obtain a rubber compound.
And thirdly, vulcanizing. The rubber compound was placed in a mold and hot-pressed vulcanized at 150℃into a sheet of 2mm thickness.
Example 3
A composite material based on modified fine leather scraps comprises the following components in percentage by weight:
styrene-butadiene rubber, fujian petrochemical, 46kg;
isoprene rubber, petrified, 20kg;
butadiene rubber, korean LG,12kg;
70kg of modified fine leather scraps;
vulcanizing agent, double two, five, commercially available, 3kg;
vulcanization accelerators, 2' -dibenzothiazyl disulfide, commercially available, 5kg;
3kg of a vulcanization activator, zinc oxide, commercially available;
an anti-aging agent, N- (1, 3-dimethylbutyl) -N' -phenyl-p-phenylenediamine, commercially available, 2kg;
reinforcing agent, fumed silica, commercially available as 28kg.
The first step adopts a one-step method to prepare the modified fine leather scraps. 70kg of chromium-containing waste leather from trimming and 100kg of sodium hydroxide are put into a high-speed crusher at a rotating speed of 3000rpm for shearing crushing and modification, and modified fine leather scraps with a particle size of about 200 meshes are obtained.
And mixing in the second step. Adding the three rubber raw materials into an open mill, adding modified fine leather scraps, mixing for a period of time, and then adding a vulcanizing agent, a vulcanization aid, an anti-aging agent, a reinforcing agent and the like, and continuously mixing to obtain a rubber compound.
And thirdly, vulcanizing. The rubber compound was placed in a mold and hot-pressed vulcanized at 180℃into a sheet of 2mm thickness.
Example 4
A composite material based on modified fine leather scraps comprises the following components in percentage by weight:
styrene-butadiene rubber, fujian petrochemical, 48kg;
isoprene rubber, petrified, 18kg;
butadiene rubber, korean LG,11kg;
90kg of modified fine leather scraps;
3.5kg of vulcanizing agent, namely double II, five, which is sold in the market;
a vulcanization accelerator, tetramethylthiuram monosulfide, commercially available at 5kg;
vulcanizing activator, stearic acid, commercially available, 5kg;
1.8kg of an anti-aging agent, commercially available N, N' -m-phenylene bismaleimide;
reinforcing agent, fumed silica, commercially available as 28kg.
The first step adopts a one-step method to prepare the modified fine leather scraps. 90kg of chromium-containing leather processing waste and 110kg of urea are put into a high-speed crusher at a rotation speed of 5000rpm for shearing crushing and modification, and modified fine leather scraps with a particle size of about 350 meshes are obtained.
And mixing in the second step. Adding the three rubber raw materials into an open mill, adding modified fine leather scraps, mixing for a period of time, and then adding a vulcanizing agent, a vulcanization aid, an anti-aging agent, a reinforcing agent and the like, and continuously mixing to obtain a rubber compound.
And thirdly, vulcanizing. The rubber compound was placed in a mold and hot-pressed vulcanized at 190℃into a sheet of 2mm thickness.
Example 5
A composite material based on modified fine leather scraps comprises the following components in percentage by weight:
styrene-butadiene rubber, 48kg of Chinese petrochemical industry;
isoprene rubber, petrified, 16kg;
butadiene rubber, korean LG,12kg;
60kg of modified fine leather scraps;
vulcanizing agent, two, four, commercially available, 2.8kg;
a vulcanization accelerator, tetramethylthiuram disulfide, commercially available, 5.5kg;
4.6kg of a vulcanization activator, zinc stearate, commercially available;
anti-aging agent, microcrystalline wax, commercially available, 1.9kg;
reinforcing agent, carbon black, commercially available at 28kg.
The first step adopts a one-step method to prepare the modified fine leather scraps. 60kg of waste leather containing chromium flakes, 50kg of silane coupling agent Si 69 and 30kg of urea are put into a high-speed crusher at a rotation speed of 4000rpm for shearing crushing and modification, and modified fine leather scraps with a particle size of about 300 meshes are obtained.
And mixing in the second step. Adding the three rubber raw materials into an open mill, adding modified fine leather scraps, mixing for a period of time, and then adding a vulcanizing agent, a vulcanization aid, an anti-aging agent, a reinforcing agent and the like, and continuously mixing to obtain a rubber compound.
And thirdly, vulcanizing. The rubber compound was placed in a mold and hot-pressed vulcanized at 182℃into a sheet of 2mm thickness.
To fully understand the properties of the composites made according to the present invention, the products of examples 1-5 and comparative examples 1-2 were tested, respectively, wherein the hardness, density, rebound, DIN abrasion, tensile strength properties and wet skid resistance were tested with reference to the standards GB/T39693.9, GB/T533, GB/T1681, GB/T9867, GB/T528-2009 and HG/T3780, respectively. The test results are shown in the following table:
table 1 comparison of test results for different samples
As can be seen from table 1, the composite material prepared by blending the modified fine leather chips and rubber and vulcanizing in example 1 has significantly improved rebound resilience, abrasion resistance, tensile strength and wet skid resistance as compared with the unmodified fine leather chips in comparative example 1; compared with the prior art method of crushing the leather waste and then mixing and modifying the crushed leather waste in comparative example 2, example 1 proposes a method of finely crushing the leather waste and simultaneously modifying the leather waste, then mixing the leather waste with rubber and vulcanizing the leather waste, wherein the rebound performance, abrasion resistance, tensile strength and wet skid resistance of the composite material prepared by the method are higher than those of the composite material prepared by the prior art method in comparative example 2.
In summary, the results of all examples and comparative examples of the present invention show that the rubber composite material prepared by modifying leather waste in a high-speed shearing crusher by a one-step method is excellent in rebound performance, abrasion resistance, tensile strength and wet skid resistance, and is expected to be applicable to sole materials, automobile industry and construction industry.
Claims (10)
1. A one-step modification method of leather scraps, which is characterized by comprising the following steps: and (3) uniformly mixing the leather scraps and the modifier, and placing the obtained mixture into a high-speed crusher to carry out modification and fine crushing simultaneously, so as to finally obtain the modified fine leather scraps.
2. The method of claim 1, wherein: the leather scraps are at least one selected from chromium-containing waste leather scraps and chromium-free waste leather scraps, and the modifier is at least one selected from silane coupling agents, sodium hydroxide and urea.
3. The method of claim 1, wherein: the mass ratio of the leather scraps to the modifier is 3-1:1-3, the rotating speed of the high-speed crusher is 3000-6000rpm, and the particle size of the prepared modified fine leather scraps is 40-400 meshes.
4. The composite material based on the modified fine leather scraps is characterized by comprising the following components in parts by weight:
styrene-butadiene rubber: 30-60 parts;
isoprene rubber: 10-30 parts of a lubricant;
butadiene rubber: 5-20 parts;
modified fine leather crumb made according to any one of claims 1 to 3: 10-200 parts of a lubricant;
vulcanizing agent: 1-5 parts;
vulcanization aid: 2-15 parts;
anti-aging agent: 1-3 parts;
reinforcing agent: 10-40 parts.
5. The composite material according to claim 4, wherein the composite material comprises the following components in parts by weight:
styrene-butadiene rubber: 40-50 parts;
isoprene rubber: 15-25 parts of a lubricant;
butadiene rubber: 10-15 parts of a lubricant;
modified fine leather scraps: 50-150 parts;
vulcanizing agent: 2-4 parts;
vulcanization aid: 5-12 parts;
anti-aging agent: 0.5-2.5 parts;
reinforcing agent: 20-35 parts.
6. The composite material of claim 4 or 5, wherein: the vulcanizing agent is at least one selected from sulfur, dicumyl peroxide, 2, 4-di-tert-butyl cumyl peroxide, 2, 4-dichloro benzoyl peroxide and 2, 5-dimethyl-2, 5-bis (tert-butyl peroxy) hexane; the vulcanization aid comprises an accelerator and an active agent, wherein the accelerator is at least one selected from N-cyclohexyl-2-benzothiazole sulfenamide, N-tertiary butyl-2-benzothiazole sulfenamide, 2' -dibenzothiazyl disulfide, tetramethylthiuram monosulfide, 2-mercaptobenzothiazole and tetramethylthiuram disulfide, and the active agent is at least one selected from diethylene glycol, polyethylene glycol, zinc oxide, stearic acid and zinc stearate; the anti-aging agent is at least one selected from 2-mercaptobenzimidazole, 2, 4-trimethyl-1, 2-dihydroquinoline polymer, N- (1, 3-dimethylbutyl) -N '-phenyl-p-phenylenediamine, N' -m-phenylene bismaleimide, pentaerythritol tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], paraffin wax, microcrystalline wax and antifogging wax; the reinforcing agent is at least one selected from the group consisting of fumed silica, precipitated silica and carbon black.
7. A method for preparing a modified fine leather crumb based composite according to any one of claims 4 to 6, characterized in that it comprises the following steps: firstly, mixing the raw materials and mixing at normal temperature, and then, heating and vulcanizing the obtained rubber compound.
8. The method of claim 7, wherein: the feeding method in the mixing process is as follows: firstly adding rubber, then adding modified fine leather scraps to carry out mixing, and then adding reinforcing agent, anti-aging agent, vulcanizing agent and vulcanizing aid to continue mixing.
9. The method of claim 7, wherein: the curing temperature of the rubber compound is 150-200 ℃.
10. Use of the modified fine leather crumb based composite according to any one of claims 4 to 6 in sole materials, automotive industry, construction industry.
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