CN110903558A - Water-absorbing rubber composite material and preparation method thereof - Google Patents
Water-absorbing rubber composite material and preparation method thereof Download PDFInfo
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- CN110903558A CN110903558A CN201911258297.0A CN201911258297A CN110903558A CN 110903558 A CN110903558 A CN 110903558A CN 201911258297 A CN201911258297 A CN 201911258297A CN 110903558 A CN110903558 A CN 110903558A
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 85
- 239000005060 rubber Substances 0.000 title claims abstract description 85
- 239000002131 composite material Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000004073 vulcanization Methods 0.000 claims abstract description 43
- 229920005989 resin Polymers 0.000 claims abstract description 35
- 239000011347 resin Substances 0.000 claims abstract description 35
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 28
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 15
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 15
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000008117 stearic acid Substances 0.000 claims abstract description 15
- 239000000945 filler Substances 0.000 claims abstract description 14
- 239000012744 reinforcing agent Substances 0.000 claims abstract description 13
- 230000003712 anti-aging effect Effects 0.000 claims abstract description 11
- 239000011787 zinc oxide Substances 0.000 claims abstract description 11
- 239000000049 pigment Substances 0.000 claims abstract description 10
- 239000002250 absorbent Substances 0.000 claims description 33
- 239000012752 auxiliary agent Substances 0.000 claims description 29
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 21
- 239000006229 carbon black Substances 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 17
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 16
- 239000000194 fatty acid Substances 0.000 claims description 16
- 229930195729 fatty acid Natural products 0.000 claims description 16
- -1 glycerin fatty acid ester Chemical class 0.000 claims description 16
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 13
- 238000007599 discharging Methods 0.000 claims description 13
- 229910000278 bentonite Inorganic materials 0.000 claims description 12
- 239000000440 bentonite Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 10
- 244000043261 Hevea brasiliensis Species 0.000 claims description 9
- 229920003052 natural elastomer Polymers 0.000 claims description 9
- 229920001194 natural rubber Polymers 0.000 claims description 9
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 8
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims description 8
- 238000010074 rubber mixing Methods 0.000 claims description 8
- 239000004636 vulcanized rubber Substances 0.000 claims description 8
- 229920000181 Ethylene propylene rubber Polymers 0.000 claims description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 7
- 239000004094 surface-active agent Substances 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims description 4
- 229920002126 Acrylic acid copolymer Polymers 0.000 claims description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 4
- 229930006000 Sucrose Natural products 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 229920006322 acrylamide copolymer Polymers 0.000 claims description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 4
- 235000011187 glycerol Nutrition 0.000 claims description 4
- 229920002401 polyacrylamide Polymers 0.000 claims description 4
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 4
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 4
- 239000005720 sucrose Substances 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 239000011593 sulfur Substances 0.000 claims description 4
- 238000004806 packaging method and process Methods 0.000 claims description 3
- 150000002978 peroxides Chemical class 0.000 claims description 3
- 229920002635 polyurethane Polymers 0.000 claims description 3
- 239000004814 polyurethane Substances 0.000 claims description 3
- 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 claims description 2
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- 150000004996 alkyl benzenes Chemical class 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- 229940077388 benzenesulfonate Drugs 0.000 claims description 2
- 238000007723 die pressing method Methods 0.000 claims description 2
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 2
- 150000003557 thiazoles Chemical class 0.000 claims description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 2
- 150000002191 fatty alcohols Chemical class 0.000 claims 2
- 238000000034 method Methods 0.000 claims 1
- 238000000465 moulding Methods 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 58
- 238000010521 absorption reaction Methods 0.000 description 43
- 230000000052 comparative effect Effects 0.000 description 15
- 229940092782 bentonite Drugs 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- ONCZQWJXONKSMM-UHFFFAOYSA-N dialuminum;disodium;oxygen(2-);silicon(4+);hydrate Chemical compound O.[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Na+].[Na+].[Al+3].[Al+3].[Si+4].[Si+4].[Si+4].[Si+4] ONCZQWJXONKSMM-UHFFFAOYSA-N 0.000 description 6
- 238000003825 pressing Methods 0.000 description 6
- 230000032683 aging Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 4
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical group C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 230000002265 prevention Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 229910000280 sodium bentonite Inorganic materials 0.000 description 3
- 229940080314 sodium bentonite Drugs 0.000 description 3
- 239000000126 substance Substances 0.000 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 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 2
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 2
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 description 2
- OUBMGJOQLXMSNT-UHFFFAOYSA-N N-isopropyl-N'-phenyl-p-phenylenediamine Chemical compound C1=CC(NC(C)C)=CC=C1NC1=CC=CC=C1 OUBMGJOQLXMSNT-UHFFFAOYSA-N 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 2
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 206010020751 Hypersensitivity Diseases 0.000 description 1
- 239000008118 PEG 6000 Substances 0.000 description 1
- 239000005662 Paraffin oil Substances 0.000 description 1
- 229920002535 Polyethylene Glycol 1500 Polymers 0.000 description 1
- 229920002560 Polyethylene Glycol 3000 Polymers 0.000 description 1
- 229920001030 Polyethylene Glycol 4000 Polymers 0.000 description 1
- 229920002584 Polyethylene Glycol 6000 Polymers 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 208000026935 allergic disease Diseases 0.000 description 1
- 230000007815 allergy Effects 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229910000281 calcium bentonite Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 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
- 238000007654 immersion Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000012856 weighed raw material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Sealing Material Composition (AREA)
Abstract
The invention belongs to the field of composite materials, and particularly relates to a water-absorbing rubber composite material and a preparation method thereof, wherein the water-absorbing rubber composite material comprises the following components: the waterproof and water-stop plugging agent is prepared from 100 parts by mass of raw rubber, 10-60 parts by mass of water-absorbing resin, 1-45 parts by mass of water-absorbing auxiliary, 0-6 parts by mass of zinc oxide, 0-2.5 parts by mass of stearic acid, 0.5-3 parts by mass of vulcanizing agent, 1-5 parts by mass of vulcanization accelerator, 0.5-3 parts by mass of anti-aging agent, 10-50 parts by mass of reinforcing agent, 5-40 parts by mass of filler, 5-30 parts by mass of softener and 3-5 parts by mass of pigment through final vulcanization molding in a double-roll open mill mixing mode.
Description
Technical Field
The invention belongs to the field of composite materials, and particularly relates to a water-absorbing rubber composite material and a preparation method thereof.
Background
The water-absorbing rubber composite material is prepared by mixing and vulcanizing water-absorbing resin or water-absorbing polyurethane prepolymer material and the like with rubber. Because the water-absorbing agent has certain water absorption multiplying power and can absorb water repeatedly, the water-absorbing agent can be used for the water prevention, water stopping and leakage stopping of civil and architectural engineering such as railways, highways, urban subways, house construction and the like, and the sealing of water pipe joints and other related fields. The general processing method of the water-absorbing rubber is that the weighed raw materials are put into an internal mixer for mixing, and after the raw materials are vulcanized by an open mill, the raw materials are extruded and molded by an extruder, and then the raw materials are vulcanized and molded by an oven. The size of the composite material can be designed into different thicknesses and widths according to requirements.
The water absorption rate of the water-absorbent rubber depends on the content of the water-absorbent resin, the vulcanization degree, and the influence of the reinforcing filler system. At the same time, the rate of absorption of water by the article is also affected by its size, the thicker the article, the longer it takes for the water to reach saturation. In actual production, however, the water-absorbing polyurethane prepolymer material can cause allergy of workers in a workshop and has great influence on human bodies; the water-absorbent rubber composite material has little influence on human bodies due to the adoption of the water-absorbent resin. However, the current water-absorbing rubber materials adopting water-absorbing resin have the problem that the water-absorbing rubber materials are difficult to quickly reach the water-absorbing equilibrium state for thick products (generally about 10mm in size), so the water-absorbing effect is not ideal. In order to improve the problem of the water absorption rate of the water-absorbent rubber composite material of a thick product, a water-absorbent aid is often added, but the traditional aid has a single function and is difficult to meet the requirements of the water-absorbent rubber composite material.
Disclosure of Invention
In order to overcome the technical defects, the invention provides a water-absorbing rubber composite material and a preparation method thereof, the water-absorbing rubber composite material mainly comprises raw rubber, water-absorbing resin, a water-absorbing auxiliary agent and the like, and is finally vulcanized and formed by adopting a double-roller open mill mixing mode.
The technical scheme of the invention is as follows:
the water-absorbing rubber composite material comprises the following components in parts by mass:
preferably, the raw rubber is one of ethylene propylene rubber, natural rubber and styrene butadiene rubber.
Further preferably, the ethylene-propylene rubber is a non-oil-extended ethylene-propylene rubber, such as 6950C ethylene-propylene-diene monomer rubber; the natural rubber is a natural rubber standard rubber.
More preferably, the mass fraction of the third monomer in the non-oil-extended ethylene propylene rubber is more than 8%, the Mooney viscosity is 60-70, the content of the third monomer is high, the high vulcanization speed of the rubber compound can be ensured, and the production efficiency is improved; the natural rubber standard rubber is SCR5, so that the quality of the natural rubber is ensured, and the aging resistance of the natural rubber is improved.
Preferably, the water-absorbing resin is one of polyacrylate, polyacrylamide, polyvinyl alcohol and acrylic acid/acrylamide copolymer, the adopted water-absorbing resin has no influence on human body, and is harmless, but is not limited to the above, and other high water-absorbing resins can also be used.
Further preferably, the water-absorbent resin is a polyacrylamide water-absorbent resin.
Preferably, the mesh number of the water-absorbent resin is 200-300 meshes, the mesh number is too small, the water absorption rate is small, the water absorption multiplying power is small, and the strength is low; too large mesh, easy agglomeration, difficult dispersion and low strength.
Preferably, the water absorption auxiliary agent comprises, by mass, 15-40 parts of white carbon black, 5-30 parts of bentonite, 5-30 parts of hydrophilic lipophilic compatibilizer, 2-10 parts of surfactant and 1-5 parts of separant.
Preferably, the white carbon black is precipitated white carbon black, and the white carbon black is filled into the mixture as a matrix, so that the mechanical property of the water-absorbing rubber composite material is improved. The precipitated white carbon black is cheap and easy to obtain and has good processing performance.
Preferably, the mesh number of the precipitated silica is 100 meshes to 500 meshes. If the mesh number is too large, the dispersibility of the white carbon black is not good, and if the mesh number is too small, the reinforcing property of the white carbon black is low.
Preferably, the bentonite is one or two of sodium bentonite and calcium bentonite, and the function of the bentonite can improve the water absorption performance of the water-absorbing rubber.
Preferably, the mesh number of the bentonite is 800-2000 meshes.
Preferably, the hydrophilic lipophilic compatibilizer is one or more of glycerin fatty acid ester, sucrose fatty acid ester, sorbitan fatty acid ester, propylene glycol fatty acid ester, nonylphenol polyethylene glycol ether polyurethane, linear alkyl benzene sulfonate, fatty alcohol-polyoxyethylene ether sodium sulfate and fatty alcohol-polyoxyethylene ether ammonium sulfate. The hydrophilic and oleophilic compatibilizer can improve the binding force of the water-absorbent resin to rubber, increase the compatibility of hydrophilic substances and a rubber matrix, and simultaneously reduce the precipitation of the water-absorbent rubber after water absorption.
Preferably, the surfactant is one or a mixture of polyethylene glycol and stearic acid. The function of the rubber compound can improve the vulcanization speed of the rubber compound and the production efficiency.
Preferably, the polyethylene glycol is one of PEG1500, PEG2000, PEG3000, PEG4000, PEG 6000.
Preferably, the separant is one or a mixture of ultrafine talcum powder and zinc stearate, and the separant can improve the dispersibility of the water absorption aid.
Preferably, the mesh number of the superfine talcum powder is 1000 meshes to 3000 meshes. The price is increased due to too large mesh number; too small a mesh size does not serve as a discrete barrier.
The concrete preparation method of the water absorption auxiliary agent comprises the following steps: placing the hydrophilic oleophylic compatibilizer in an oven to be dried for 1-2 hours at the temperature of 20-30 ℃, taking the white carbon black, the bentonite, the surfactant, the separant and the dried hydrophilic oleophylic compatibilizer according to the formula ratio, sending the components into a high-speed mixer to be mixed and stirred for 3-8 s, controlling the stirring speed of the mixer to be 15000-25000r/min, and discharging to obtain the special multifunctional water-absorbing auxiliary agent for the nonpolar water-absorbing rubber.
By adopting the water absorption auxiliary agent, the water absorption rate of the water absorption rubber is improved, the addition amount of the water absorption resin can be reduced to a certain extent, the mechanical property of the water absorption rubber is effectively improved, the compatibility of the water absorption resin and a base material is increased, the dispersion of the water absorption resin is promoted, the precipitation of the water absorption resin is reduced, the viscosity of a composite material system is reduced, the fluidity is improved, the processing property of the composite material is improved, and the white carbon black is used as a base to be filled into a mixture, so that the mechanical property of the water absorption rubber composite material is improved.
Preferably, the vulcanizing agent is sulfur and/or peroxide vulcanizing agent, wherein the peroxide vulcanizing agent is dicumyl peroxide (DCP), the vulcanizing accelerator corresponding to the vulcanizing agent is one or more of thiazoles, sulfenamides, thiurams, triallyl isocyanurate (TAIC), 1,3, 5-triallyl cyanurate and N, N '-m-phenylene bismaleimide, and commonly used auxiliaries for improving the vulcanizing efficiency of the vulcanizing agent are 2,2' -dithiodibenzothiazole (accelerator DM) and N-cyclohexyl-2-benzothiazole sulfenamide (accelerator CZ), and the vulcanizing accelerator can shorten the vulcanizing time, improve the production efficiency and improve the mechanical properties of the rubber composite material.
Preferably, the zinc oxide is zinc oxide powder with the zinc content of more than 99.5 percent, and the zinc oxide is compounded with stearic acid to be used as a vulcanization activation system, so that vulcanization is promoted, and the strength performance of the composite material is improved.
Preferably, the anti-aging agent comprises all auxiliary agents for improving the aging performance of the rubber, wherein one or more of phenolic or amine anti-aging agents are preferably used in a composite manner. Such as: one or a mixture of two of 2,2, 4-trimethyl-1, 2-dihydroquinoline polymer (antioxidant RD) and N-isopropyl-N' -phenyl-p-phenylenediamine (antioxidant 4010NA) is selected, and the antioxidant can delay the aging of rubber materials and prolong the service life.
Preferably, the reinforcing agent is one or more of white carbon black, N85 and kaolin, and the reinforcing agent can improve the mechanical property of the composite material and ensure that the material has use value.
Preferably, the filler is one or a mixture of calcium carbonate and talcum powder, and the proper addition of the filler can reduce the cost of the rubber compound.
Preferably, the softener is one or a mixture of two of paraffin oil and naphthenic oil, and the proper addition of the softener can improve the processing performance, reduce the energy consumption and save the cost.
The pigments of the present invention are conventional in the art.
The concrete preparation method of the water-absorbing rubber composite material comprises the following steps:
rubber mixing: plasticating raw rubber in a double-roller mixing mill for 1-1.5 minutes, sequentially adding zinc oxide, stearic acid, a vulcanization accelerator, an anti-aging agent and a pigment, sequentially adding a left cutter and a right cutter for three times, sequentially adding a reinforcing agent, a softener, a filler, a water-absorbing auxiliary agent and water-absorbing resin, sequentially adding a left cutter and a right cutter for three times, finally adding a vulcanizing agent, sequentially adding a left cutter and a right cutter for three times, performing triangular packaging for five times, and discharging sheets to obtain rubber compound;
and (3) vulcanization: the mix was left for 16-24 hours, and conventional vulcanization conditions were set: the pressure is 10-15MPa, the vulcanization temperature is 160-180 ℃, the vulcanization time is 5-15min, and the vulcanized rubber is prepared by die pressing.
The raw rubber adopts the non-oil-filled ethylene propylene rubber or the natural rubber standard rubber as the matrix of the water-absorbing rubber composite material, and can endow good vulcanization speed and basic physical and mechanical properties; the water-absorbing resin with 200-mesh and 300-mesh and the water-absorbing auxiliary agent are selected as main auxiliary materials, the water-absorbing resin can endow the rubber with certain water-absorbing multiplying power, the water-absorbing auxiliary agent can play a role in reinforcement, can reduce the viscosity of rubber materials, improve the processability, increase the water-absorbing rate and other performances, and meanwhile, the proper amount of filler and softener added into the rubber can improve the processability and reduce the production cost to a certain extent.
The water-absorbing rubber composite material provided by the invention has good water absorption multiplying power and water absorption rate and excellent repeated water-soaking experimental performance. Under the conditions of room temperature and distilled water, the water absorption volume expansion ratio can reach more than 420%, the aging resistance is excellent, in addition, the tensile strength of the composite material is higher than 6MPa, and the composite material is very suitable for being applied to the related fields of water prevention, water stopping and leakage stopping of civil and architectural engineering such as railways, highways, urban subways, house construction and the like, water pipe joint sealing and the like.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. In the embodiment, the water absorption auxiliary agent is prepared by the application number 2019109473272 patent application, the mesh number of the water absorption resin is 200-300 meshes, the ethylene propylene rubber is 6950C ethylene propylene diene monomer rubber, and the natural rubber standard rubber is SCR 5.
Example 1
A water-absorbing rubber composite material comprises the following components in parts by mass:
the preparation method comprises the following specific steps:
preparation of water absorption auxiliary agent: firstly, placing glycerin fatty acid ester in an oven at 20 ℃ for 2 hours, then sending 375g of white carbon black, 750g of bentonite, 1500250 g of PEG, 125g of superfine talcum powder and 1000g of baked glycerin fatty acid ester into a high-speed mixer for mixing and stirring for 8s, controlling the stirring speed of a stirrer to be 15000r/min, and then discharging to obtain a water absorption auxiliary agent for later use;
rubber mixing: plasticating raw rubber in a double-roller mixing mill for 1.5 minutes, then sequentially adding zinc oxide, stearic acid, a vulcanization accelerator, an anti-aging agent and a pigment, sequentially adding a left cutter and a right cutter for three times, then sequentially adding a reinforcing agent, a softener, a filling agent, a water-absorbing auxiliary agent and polyacrylamide water-absorbing resin, sequentially adding the left cutter and the right cutter for three times, finally adding a vulcanizing agent, performing three times on the left cutter and the right cutter, performing triangular wrapping for five times, and discharging sheets to obtain rubber compound;
and (3) vulcanization: the mix was left for 24 hours, and conventional vulcanization conditions were set: the pressure is 10MPa, the vulcanization temperature is 170 ℃, the time is 10min, and the vulcanized rubber is prepared by mould pressing.
Example 2
A water-absorbing rubber composite material comprises the following components in parts by mass:
the preparation method comprises the following specific steps:
preparation of water absorption auxiliary agent: placing propylene glycol fatty acid ester in an oven at 25 ℃ for 1 hour, feeding 625g of white carbon black, 500g of bentonite PEG 4000200 g, 100g of superfine talcum powder and 625g of baked propylene glycol fatty acid ester into a high-speed mixer, mixing and stirring for 3s, controlling the stirring speed of the stirrer to be 25000r/min, and discharging to obtain the water absorption auxiliary agent for later use.
Rubber mixing: plasticating raw rubber in a double-roller mixing mill for 1.5 minutes, sequentially adding zinc oxide, stearic acid, a vulcanization accelerator, an anti-aging agent and a pigment, sequentially adding a left cutter and a right cutter for three times, sequentially adding a reinforcing agent, a softener, a filling agent, a water-absorbing auxiliary agent and polyvinyl alcohol water-absorbent resin, sequentially adding the reinforcing agent, the softener, the filling agent, the water-absorbing auxiliary agent and the polyvinyl alcohol water-absorbent resin, sequentially adding the left cutter and the right cutter for three times, finally adding a vulcanizing agent, performing three times on the;
and (3) vulcanization: the mix was left for 24 hours, and conventional vulcanization conditions were set: the pressure is 15MPa, the vulcanization temperature is 180 ℃, the time is 5min, and the vulcanized rubber is prepared by mould pressing.
Example 3
A water-absorbing rubber composite material comprises the following components in parts by mass:
the preparation method comprises the following specific steps:
preparation of water absorption auxiliary agent: placing sucrose fatty acid ester in an oven at 25 ℃ for 1.5 hours, feeding 1000g of white carbon black, 125g of bentonite, 600050 g of PEG, 60g of superfine talcum powder and 375g of baked sucrose fatty acid ester into a high-speed mixer, mixing and stirring for 5s, controlling the stirring speed of the stirrer to be 20000r/min, and discharging to obtain a multifunctional water absorption auxiliary agent for later use;
rubber mixing: plasticating raw rubber in a double-roller mixing mill for 1.5 minutes, then sequentially adding zinc oxide, stearic acid, a vulcanization accelerator, an anti-aging agent and a pigment, sequentially adding a left cutter and a right cutter for three times, then sequentially adding a reinforcing agent, a softener, a filling agent, a water-absorbing auxiliary agent and acrylic acid/acrylamide copolymer water-absorbing resin, sequentially adding the left cutter and the right cutter for three times, finally adding a vulcanizing agent, performing triangular wrapping for five times by the left cutter and the right cutter for three times, and discharging sheets to obtain rubber compound;
and (3) vulcanization: the mix was left for 24 hours, and conventional vulcanization conditions were set: the pressure is 15MPa, the vulcanization temperature is 180 ℃, the time is 5min, and the vulcanized rubber is prepared by mould pressing.
Example 4
A water-absorbing rubber composite material comprises the following components in parts by mass:
the preparation method comprises the following specific steps:
preparation of water absorption auxiliary agent: placing sorbitan fatty acid ester in an oven at 25 ℃ for 1.5 hours, feeding 750g of white carbon black, 375g of bentonite, 200g of stearic acid, 80g of superfine talcum powder and 250g of baked sorbitan fatty acid ester into a high-speed mixer, mixing and stirring for 5s, controlling the stirring speed of the stirrer to be 20000r/min, and discharging to obtain a water absorption auxiliary agent for later use;
rubber mixing: plasticating raw rubber in a double-roller mixing mill for 1.5 minutes, sequentially adding zinc oxide, stearic acid, an anti-aging agent and a pigment, sequentially adding a left cutter and a right cutter for three times, sequentially adding a reinforcing agent, a softening agent, a filling agent, a water absorption auxiliary agent and polyvinyl alcohol water-absorbent resin, sequentially adding the left cutter and the right cutter for three times, finally adding a vulcanizing agent DCP and a TAIC, sequentially adding the left cutter and the right cutter for three times, performing triangular packaging for five times, and discharging sheets to obtain rubber compound;
and (3) vulcanization: the mix was left for 24 hours, and conventional vulcanization conditions were set: the pressure is 15MPa, the vulcanization temperature is 180 ℃, the time is 5min, and the vulcanized rubber is prepared by mould pressing.
Comparative example 1
A water-absorbing rubber composite material comprises the following components in parts by mass:
the preparation method comprises the following specific steps:
rubber mixing: plasticating raw rubber in a double-roller mixing mill for 1.5 minutes, sequentially adding zinc oxide, stearic acid, a vulcanization accelerator, an anti-aging agent and a pigment, sequentially adding a left cutter and a right cutter for three times, sequentially adding a reinforcing agent, a softener, a filling agent, a water-absorbing auxiliary agent and polyvinyl alcohol water-absorbent resin, sequentially adding the reinforcing agent, the softener, the filling agent, the water-absorbing auxiliary agent and the polyvinyl alcohol water-absorbent resin, sequentially adding the left cutter and the right cutter for three times, finally adding a vulcanizing agent, performing three times on the;
and (3) vulcanization: the mix was left for 24 hours, and conventional vulcanization conditions were set: the pressure is 15MPa, the vulcanization temperature is 180 ℃, the time is 5min, and the vulcanized rubber is prepared by mould pressing.
Comparative example 2
A water-absorbing rubber composite material comprises the following components in parts by mass:
rubber mixing: plasticating raw rubber in a double-roller mixing mill for 1.5 minutes, then sequentially adding zinc oxide, stearic acid, a vulcanization accelerator, an anti-aging agent and a pigment, sequentially adding a left cutter and a right cutter for three times, then sequentially adding a reinforcing agent, a softener, a filling agent, a water-absorbing auxiliary agent and acrylic acid/acrylamide copolymer water-absorbing resin, sequentially adding the left cutter and the right cutter for three times, finally adding a vulcanizing agent, performing triangular wrapping for five times by the left cutter and the right cutter for three times, and discharging sheets to obtain rubber compound;
and (3) vulcanization: the mix was left for 24 hours, and conventional vulcanization conditions were set: the pressure is 15MPa, the vulcanization temperature is 180 ℃, the time is 5min, and the vulcanized rubber is prepared by mould pressing.
Comparative example 3
Weighing the following components in parts by mass: 95 parts of nitrile butadiene rubber, 5 parts of calcium oxide, 1.2 parts of stearic acid, 1.5 parts of sulfur, 0.8 part of accelerator DM, 26 parts of white carbon black, 25 parts of modified bentonite water-absorbent resin and 20 parts of polysiloxane-polyurethane copolymer;
the preparation method of the water-absorbent resin comprises the following steps: and drying the sodium bentonite to constant weight, and roasting the dried sodium bentonite in a resistance furnace at 200 ℃ for 68min to obtain the modified sodium bentonite. Adding acrylic acid into modified sodium bentonite, adding a sodium hydroxide solution while stirring, adding N, N-methylene bisacrylamide, uniformly stirring, placing into a water bath, adding an ammonium persulfate solution, continuing to react to obtain a colloidal substance after the solution becomes thick, finally drying and shearing to obtain particles, wherein the content of the modified sodium bentonite is 12%, the content of the N, N-methylene bisacrylamide is 0.2%, the content of the ammonium persulfate is 0.3%, and the reaction temperature is 70 ℃ when the colloidal substance is reacted.
The processing method of the water-absorbing rubber comprises the following steps: plasticating the nitrile rubber on a plasticating machine for 38min, adding calcium oxide, stearic acid, white carbon black, bentonite water-absorbent resin and a compatibilizer, continuing to mix for 30min, adding sulfur and an accelerator DM for mixing, uniformly mixing, performing thin pass for five times, and then discharging and vulcanizing. Wherein the vulcanization process is carried out at 145 ℃ and under 8MPa for 40 min.
In order to verify the performance of the product, the tensile strength, the elongation at break and the hardness are tested:
the water-absorbent rubber composite materials obtained in examples 1 to 3 and comparative examples 1 to 3 were tested for tensile strength, elongation at break, hardness, and water-absorbing volume expansion ratio according to the national standard GB/T18173.3-2002.
The test results are shown in the following table
Comparative examples 1 and 2 are distinguished from the water-absorbent rubber composite material without the water-absorbent aid added in the present example, and comparative example 3 is the existing preparation process of the high-speed water-absorbent rubber composite material, and it can be seen from the data that the water absorption rate of the present example is more than 420%, and the water absorption rates of comparative examples 1 to 3 are obviously lower than that of the present example; the time required for the water absorption of the comparative examples 1-3 to reach the equilibrium is far longer than that of the examples, the Mooney viscosity in the example is obviously lower than that of the comparative examples 1-3, the viscosity of the composite material system is reduced, the fluidity is improved, and the processing performance of the composite material is improved; according to the water-absorbent rubber composite material provided by the invention, the white carbon black is used as the water-absorbent auxiliary agent matrix, so that the mechanical property of the composite material is improved, and the mechanical property of the embodiment is obviously better than that of the embodiment in comparison with the comparison ratios 1 and 2; the time required for the 2mm test piece and the 12.5mm test piece obtained in comparative examples 1 to 3 to reach the water absorption equilibrium is much longer than that of the examples; through repeated water immersion experiments, the water absorption rate of the embodiment is obviously higher than that of comparative examples 1-3, the tensile strength and the tensile rate of the comparative examples 1 and 2 are obviously inferior to those of the embodiment, the mechanical property of the comparative example 3 is equivalent to that of the embodiment, but the water absorption rate of the comparative example 3 is obviously lower than that of the embodiment and the comparative example 3, the preparation process is complex, and the operation is obviously difficult.
According to the test results, the water-absorbing rubber composite material provided by the invention has good water absorption multiplying power and water absorption rate and excellent repeated water-soaking experimental performance. Under the conditions of room temperature and distilled water, the water absorption volume expansion ratio can reach more than 420%, the aging resistance is excellent, in addition, the tensile strength of the composite material is higher than 6MPa, and the composite material is very suitable for being applied to the related fields of water prevention, water stopping and leakage stopping of civil and architectural engineering such as railways, highways, urban subways, house construction and the like, water pipe joint sealing and the like.
Claims (10)
1. The water-absorbing rubber composite material is characterized by comprising the following components in parts by mass:
2. the water-absorbent rubber composite material as claimed in claim 1, wherein the raw rubber is one of ethylene propylene rubber, natural rubber and styrene butadiene rubber.
3. The water-absorbent rubber composite material as claimed in claim 1, wherein the water-absorbent resin is one of polyacrylate, polyacrylamide, polyvinyl alcohol, and acrylic acid/acrylamide copolymer.
4. The water-absorbent rubber composite material as claimed in claim 1 or 3, wherein the mesh number of the water-absorbent resin is 200-300 meshes.
5. The water-absorbing rubber composite material as claimed in claim 1, wherein the water-absorbing auxiliary comprises the following components in parts by mass: 15-40 parts of white carbon black, 5-30 parts of bentonite, 5-30 parts of hydrophilic and oleophilic compatibilizer, 2-10 parts of surfactant and 1-5 parts of separant.
6. The water-absorbing rubber composite material as claimed in claim 5, wherein the hydrophilic and lipophilic compatibilizer is one or more of glycerin fatty acid ester, sucrose fatty acid ester, sorbitan fatty acid ester, propylene glycol fatty acid ester, nonylphenol polyethylene glycol ether polyurethane, linear alkyl benzene sulfonate, fatty alcohol polyoxyethylene ether sodium sulfate, and fatty alcohol polyoxyethylene ether ammonium sulfate.
7. The water-absorbent rubber composite material as claimed in claim 5, wherein the surfactant is one or a mixture of polyethylene glycol and stearic acid; the separant is one or a mixture of superfine talcum powder and zinc stearate.
8. The water-absorbing rubber composite material as claimed in claim 5, wherein the water-absorbing auxiliary is prepared by the following specific method: placing the hydrophilic oleophylic compatibilizer in an oven to be dried for 1-2 hours at the temperature of 20-30 ℃, taking the white carbon black, the bentonite, the surfactant, the separant and the dried hydrophilic oleophylic compatibilizer according to the formula ratio, sending the components into a high-speed mixer to be mixed and stirred for 3-8 s, controlling the stirring speed of the mixer to be 15000-25000r/min, and discharging to obtain the special multifunctional water-absorbing auxiliary agent for the water-absorbing rubber.
9. The water-absorbent rubber composite material according to claim 1, wherein the vulcanizing agent is sulfur and/or peroxide vulcanizing agent; the vulcanization accelerator is one or more of thiazoles, sulfenamides, thiurams, triallylisocyanurate, 1,3, 5-triallyl cyanurate and N, N' -m-phenylene bismaleimide.
10. The preparation method of the water-absorbing rubber composite material as claimed in claim 1, is characterized by comprising the following steps:
rubber mixing: plasticating raw rubber in a double-roller mixing mill for 1.0-1.5 minutes, sequentially adding zinc oxide, stearic acid, a vulcanization accelerator, an anti-aging agent and a pigment, sequentially adding a left cutter and a right cutter for three times, sequentially adding a reinforcing agent, a softener, a filler, a water-absorbing auxiliary agent and water-absorbing resin, sequentially adding the left cutter and the right cutter for three times, finally adding a vulcanizing agent, performing three times on the left cutter and the right cutter, performing triangular packaging for five times, and discharging sheets to obtain rubber compound;
and (3) vulcanization: the mix was left for 16-24 hours, and conventional vulcanization conditions were set: the pressure is 10-15MPa, the vulcanization temperature is 160-180 ℃, the vulcanization time is 5-15min, and the vulcanized rubber is prepared by die pressing.
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| CN110204834A (en) * | 2019-05-10 | 2019-09-06 | 重庆理工大学 | A kind of water swelling rubber and preparation method thereof |
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