CN117777576B - High-wear-resistance rubber runway and preparation method thereof - Google Patents
High-wear-resistance rubber runway and preparation method thereof Download PDFInfo
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- CN117777576B CN117777576B CN202410212459.1A CN202410212459A CN117777576B CN 117777576 B CN117777576 B CN 117777576B CN 202410212459 A CN202410212459 A CN 202410212459A CN 117777576 B CN117777576 B CN 117777576B
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000002135 nanosheet Substances 0.000 claims abstract description 44
- 229920003225 polyurethane elastomer Polymers 0.000 claims abstract description 34
- 239000002245 particle Substances 0.000 claims abstract description 16
- 229920002379 silicone rubber Polymers 0.000 claims abstract description 13
- 244000043261 Hevea brasiliensis Species 0.000 claims abstract description 12
- 229920003052 natural elastomer Polymers 0.000 claims abstract description 12
- 229920001194 natural rubber Polymers 0.000 claims abstract description 12
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 7
- 239000000049 pigment Substances 0.000 claims abstract description 7
- 239000004945 silicone rubber Substances 0.000 claims abstract description 6
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims description 50
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 40
- 238000002156 mixing Methods 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 22
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- 229940125904 compound 1 Drugs 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 15
- 239000004970 Chain extender Substances 0.000 claims description 14
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 14
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 12
- 239000011737 fluorine Substances 0.000 claims description 12
- 229910052731 fluorine Inorganic materials 0.000 claims description 12
- 229920000515 polycarbonate Polymers 0.000 claims description 12
- 239000004417 polycarbonate Substances 0.000 claims description 12
- 150000002009 diols Chemical class 0.000 claims description 11
- UBVMBXTYMSRUDX-UHFFFAOYSA-N n-prop-2-enyl-3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCNCC=C UBVMBXTYMSRUDX-UHFFFAOYSA-N 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 239000003921 oil Substances 0.000 claims description 10
- 238000009210 therapy by ultrasound Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- YMDMDDUYDDFCSX-UHFFFAOYSA-N 2,3-bis(trifluoromethyl)benzene-1,4-diamine Chemical compound NC1=CC=C(N)C(C(F)(F)F)=C1C(F)(F)F YMDMDDUYDDFCSX-UHFFFAOYSA-N 0.000 claims description 9
- ZDOWUKFHZLWXJA-UHFFFAOYSA-N 3-hydroxypropanoyl chloride Chemical compound OCCC(Cl)=O ZDOWUKFHZLWXJA-UHFFFAOYSA-N 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- JMTFLSQHQSFNTE-UHFFFAOYSA-N 1-dodecylimidazole Chemical compound CCCCCCCCCCCCN1C=CN=C1 JMTFLSQHQSFNTE-UHFFFAOYSA-N 0.000 claims description 7
- BZFKSWOGZQMOMO-UHFFFAOYSA-N 3-chloropropan-1-amine Chemical compound NCCCCl BZFKSWOGZQMOMO-UHFFFAOYSA-N 0.000 claims description 7
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 7
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 7
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 7
- -1 polytetrafluoroethylene Polymers 0.000 claims description 7
- 230000001276 controlling effect Effects 0.000 claims description 5
- 230000018044 dehydration Effects 0.000 claims description 5
- 238000006297 dehydration reaction Methods 0.000 claims description 5
- 238000007723 die pressing method Methods 0.000 claims description 5
- 239000012065 filter cake Substances 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- 238000007493 shaping process Methods 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 239000002064 nanoplatelet Substances 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 4
- 235000013799 ultramarine blue Nutrition 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- 235000010215 titanium dioxide Nutrition 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 abstract description 24
- 239000000463 material Substances 0.000 abstract description 6
- 229920002635 polyurethane Polymers 0.000 description 10
- 239000004814 polyurethane Substances 0.000 description 10
- 238000004132 cross linking Methods 0.000 description 7
- 150000001408 amides Chemical group 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 229920000728 polyester Polymers 0.000 description 6
- AUMBZPPBWALQRO-UHFFFAOYSA-L zinc;n,n-dibenzylcarbamodithioate Chemical compound [Zn+2].C=1C=CC=CC=1CN(C(=S)[S-])CC1=CC=CC=C1.C=1C=CC=CC=1CN(C(=S)[S-])CC1=CC=CC=C1 AUMBZPPBWALQRO-UHFFFAOYSA-L 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 125000003277 amino group Chemical group 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 230000001050 lubricating effect Effects 0.000 description 4
- 230000006835 compression Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229960005191 ferric oxide Drugs 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 229910018557 Si O Inorganic materials 0.000 description 2
- 229910002808 Si–O–Si Inorganic materials 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 150000001263 acyl chlorides Chemical group 0.000 description 2
- 238000007112 amidation reaction Methods 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 125000002883 imidazolyl group Chemical group 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical group 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- NBRHIIKTFSQOGZ-UHFFFAOYSA-N 1-tert-butylperoxy-2-propylbenzene Chemical compound C(C)(C)(C)OOC1=C(C=CC=C1)CCC NBRHIIKTFSQOGZ-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a high-wear-resistance rubber runway and a preparation method thereof. The runway comprises the following raw materials in parts by weight: 50-60 parts of rubber particles, 40-50 parts of natural rubber, 10-15 parts of silicone rubber, 8-12 parts of modified polyurethane rubber, 10-15 parts of modified MXene nano-sheets, 0.5-2 parts of pigment, 0.3-1 part of accelerator, 3-6 parts of vulcanizing agent and 0.2-1 part of antioxidant. The silicon rubber and the polyurethane rubber with excellent wear resistance are added into the rubber runway prepared by the invention to improve the wear resistance of the runway, and the polyurethane rubber is modified, so that the wear resistance of the runway is improved, and the water resistance and the heat resistance of a matrix are also improved; in addition, the lubricity of the rubber runway material is improved by adding the modified MXene nano-sheets, so that the wear resistance of the rubber runway is improved.
Description
Technical Field
The invention relates to the technical field of rubber runways, in particular to a high-wear-resistance rubber runway and a preparation method thereof.
Background
The rubber runway is an indispensable important facility in modern track and field fields, and has good elasticity, skid resistance, wear resistance and shock absorption compared with the traditional soil runway, and the field is easy to care, bright in color and beautiful and tidy. The particles for paving the runway generally consist of natural rubber, rubber particles, auxiliary additives and other materials, and the particles have poor wear resistance, are easy to wear in the use process, and greatly reduce the service life of the particles, so that the functional modification on the wear resistance of the runway particles is imperative. Furthermore, since most runways are laid outdoors, they are susceptible to environmental factors such as: the precipitation in summer and rainy season is large, and accumulated water can soak the runway to damage the inside of the runway, so that the service life of the runway is reduced.
Therefore, researchers have been required to develop a rubber track that has both high wear resistance and excellent water resistance.
Disclosure of Invention
In order to solve the technical problems, the invention provides a high-wear-resistance rubber runway and a preparation method thereof.
The aim of the invention can be achieved by the following technical scheme:
The high wear-resistant rubber runway comprises the following raw materials in parts by weight: 50-60 parts of rubber particles, 40-50 parts of natural rubber, 10-15 parts of silicone rubber, 8-12 parts of modified polyurethane rubber, 10-15 parts of modified MXene nano-sheets, 0.5-2 parts of pigment, 0.3-1 part of accelerator, 3-6 parts of vulcanizing agent and 0.2-1 part of antioxidant;
the pigment is one of iron oxide red, oxidation iron violet, ultramarine blue and titanium white;
the modified polyurethane rubber is prepared by the following steps:
Step A1, adding 2, 3-bis (trifluoromethyl) benzene-1, 4-diamine into a flask containing dimethylacetamide, stirring and mixing uniformly, cooling the mixed solution to 0 ℃ in a water bath, adding triethylamine into the flask, stirring and mixing uniformly, slowly adding 3-hydroxy propionyl chloride under the condition of low temperature stirring, transferring the flask into an oil bath, heating to 40-60 ℃, maintaining the temperature for reaction for 4 hours, adding the mixture into deionized water at 10 ℃ after the reaction is finished, washing a filter cake with deionized water at 80-90 ℃ after vacuum suction filtration, and vacuum drying for 8 hours at 100 ℃ to obtain a fluorine-containing chain extender;
in the step A1, an acyl chloride group on 3-hydroxy propionyl chloride and an amino group of 2, 3-bis (trifluoromethyl) benzene-1, 4-diamine fan are subjected to amidation reaction to form an amide structure, and the amide structure can be introduced into polyurethane rubber to improve the strength and wear resistance of the polyurethane rubber, because the amide group is grafted on a molecular chain of polyurethane, the intramolecular and intermolecular hydrogen bonds of the polyurethane can be enhanced, and the hydrogen bonds have a physical crosslinking effect, so that the polyurethane rubber has higher strength and wear resistance; in addition, fluorine atoms in the chain extender can migrate to the surface in the process of forming the matrix due to small radius, strong electronegativity and low surface energy, so that the hydrophobicity of the surface of the matrix is improved, permeation and corrosion of water molecules can be prevented to a certain extent, and the matrix has water resistance.
Further, the dosage ratio of the 2, 3-bis (trifluoromethyl) benzene-1, 4-diamine, dimethylacetamide, triethylamine, 3-hydroxy propionyl chloride and deionized water is 0.1 to 0.3mol:100-150mL:7-21mL:0.21-0.61mol:100mL.
Step A2, adding polycarbonate diol (PCDL 2000) into a reactor, placing the reactor in an oil bath at 100-120 ℃ under the vacuum degree of 0.67kPa for high-temperature dehydration for 1.5 hours, then reducing the system temperature to 40-60 ℃, adding isophorone diisocyanate, introducing nitrogen into the reactor, stirring for 10-20 minutes, heating to 80-90 ℃ and continuing stirring for 1-2 hours to obtain a prepolymer;
In the step A2, polycarbonate diol is used as polyalcohol to synthesize polyester polyurethane, and a large number of polar groups are contained in the polyester polyurethane, so that the polyester polyurethane has a more compact and stable structure, is difficult to penetrate water molecules, and further improves the water resistance of a matrix;
Further, the polycarbonate diol and isophorone diisocyanate are used in an amount ratio of 1mol:1.75-3.5mol.
Step A3, under the condition of nitrogen, adding a fluorine-containing chain extender, dibutyl tin dilaurate and N, N-dimethylacetamide into the prepolymer, stirring for 5-10min, adding 3- (N-allylamino) propyl trimethoxy silane, reacting for 30-60min at 40 ℃, transferring the mixture into a polytetrafluoroethylene container, and curing for 24h in a baking oven at 100 ℃ to obtain modified polyurethane rubber;
In the step A3, secondary amine in 3- (N-allylamino) propyl trimethoxy silane is utilized to react with terminal isocyanate, so that a siloxane structure is introduced, siloxane can react with water molecules in the air to generate silanol bonds, condensation reaction can be carried out between the silanol bonds to form a Si-O-Si cross-linked network, and the compact cross-linked structure can effectively prevent water molecules from entering a matrix, so that the water resistance of the matrix is further improved; because the bond energy of Si-O is higher than that of C-O and C-C, the formed cross-linked network increases the interaction between molecular chains and improves the heat resistance of the matrix; in addition, free double bonds in 3- (N-allylamino) propyl trimethoxy silane can be polymerized with double bonds in a rubber molecular chain under the subsequent high temperature condition, so that the crosslinking density of the matrix is further improved.
Further, the ratio of the fluorine-containing chain extender, dibutyl tin dilaurate, N-dimethylacetamide, 3- (N-allylamino) propyl trimethoxysilane and the polycarbonate diol in the step A1 is 1.75 to 3.5mol:0.21-0.42g:10-20mL:0.1-0.15mL:1mol.
The modified MXene nano-sheet is prepared by the following steps:
Step B1, under the condition of nitrogen, adding 3-chloropropylamine and 1-dodecyl imidazole into a reactor, uniformly stirring and mixing, heating to 60 ℃, stirring for 24 hours, cooling to room temperature, and washing with anhydrous diethyl ether for three times to obtain a compound 1;
further, the molar ratio of 3-chloropropylamine to 1-dodecyl imidazole is 1:1.
Step B2, adding the MXene nano-sheets into a reactor containing deionized water, carrying out ultrasonic treatment for 30min, stirring for 20min at a rotating speed of 300rpm, adjusting the pH of the mixed solution to 8.5, adding the compound 1, carrying out water bath ultrasonic treatment for 30min, then reacting for 10-12h under the condition of nitrogen, wherein the reaction temperature is 75-85 ℃, the rotating speed is 300rpm, cooling to room temperature after the reaction is finished, and carrying out ultrasonic stirring for 30min to obtain the modified MXene nano-sheets;
In the step B2, the amino group in the compound 1 and the carboxyl group on the surface of the MXene nano-sheet generate an amide bond through an amide reaction, so that the modification of the MXene nano-sheet is realized; meanwhile, the positively charged imidazole structure of the compound 1 can also generate electrostatic action with the negatively charged MXene nano-sheets to be adsorbed on the surfaces of the MXene nano-sheets to realize modification. The modified MXene nano-sheet has excellent dispersibility, because the compound 1 on the surface of the nano-sheet disturbs the MXene lamellar structure, so that the disorder is increased; the dispersibility is improved, the physical crosslinking point is increased, and the friction between the rubber molecular chain and the rubber molecular chain is reduced; in addition, the lubricating layer formed on the surface of the MXene nano-sheet by the compound 1 is equivalent to coating a layer of lubricating layer on the surface of the rubber matrix, so that the direct contact between the rubber and the friction surface is reduced, the friction coefficient is reduced, and the wear resistance of the matrix is improved.
Further, the dose ratio of MXene nanoplatelets, deionized water and compound 1 was 0.1g:20mL:0.05-0.2g.
The preparation method of the high wear-resistant rubber runway comprises the following steps:
S1, weighing raw materials according to parts by weight, adding rubber particles, natural rubber, silicon rubber and modified polyurethane rubber into a mixing mill, mixing uniformly, and sequentially adding modified MXene nano-sheets, pigments, antioxidants and accelerators, mixing uniformly to obtain a rubber compound;
S2, transferring the rubber compound into an open mill, adding a vulcanizing agent, carrying out thin-pass 5-8 times, and then carrying out lower piece die pressing and shaping to obtain a blank;
And S3, placing the blank in a vulcanizing machine, controlling the vulcanizing temperature to be 165-185 ℃ and the vulcanizing time to be 2-3 hours, cooling, crushing by a crusher, and then paving, compacting and solidifying to obtain the high-wear-resistance rubber runway.
The invention has the beneficial effects that:
The silicon rubber and the polyurethane rubber with excellent wear resistance are added into the rubber runway prepared by the invention to improve the wear resistance of the runway, and the polyurethane rubber is modified, so that the wear resistance of the runway is improved, and the water resistance and the heat resistance of a matrix are also improved; in addition, the lubricity of the rubber runway material is improved by adding the modified MXene nano-sheets, so that the wear resistance of the rubber runway is improved.
In the modified polyurethane rubber, firstly, an amide structure is introduced into the polyurethane rubber to improve the strength and wear resistance of the polyurethane rubber by amidation reaction of an acyl chloride group on 3-hydroxy propionyl chloride and an amino group on 2, 3-bis (trifluoromethyl) benzene-1, 4-diamine, and the amide structure can strengthen hydrogen bonds in polyurethane molecules and among molecules after being grafted on the molecular chain of the polyurethane, and the hydrogen bonds play a physical crosslinking role, so that the polyurethane rubber has higher strength and wear resistance; in addition, fluorine atoms in the chain extender can migrate to the surface in the process of forming the matrix due to small radius, strong electronegativity and low surface energy, so that the hydrophobicity of the surface of the matrix is improved, permeation and corrosion of water molecules can be prevented to a certain extent, and the matrix has water resistance. And secondly, the polyester polyurethane is synthesized by taking the polycarbonate dihydric alcohol as the polyalcohol, and a large number of polar groups are contained in the polyester polyurethane, so that the polyester polyurethane has a more compact and stable structure, is difficult to penetrate water molecules, and further improves the water resistance of the matrix. Finally, secondary amine in 3- (N-allylamino) propyl trimethoxy silane is utilized to react with terminal isocyanate, so that a siloxane structure is introduced, siloxane can react with water molecules in the air to generate silanol bonds, condensation reaction can be carried out between the silanol bonds to form a Si-O-Si cross-linked network, and the compact cross-linked structure can effectively prevent the water molecules from entering a matrix, so that the water resistance of the matrix is further improved; because the bond energy of Si-O is higher than that of C-O and C-C, the formed cross-linked network increases the interaction between molecular chains and improves the heat resistance of the matrix; in addition, free double bonds in 3- (N-allylamino) propyl trimethoxy silane can be polymerized with double bonds in a rubber molecular chain under the subsequent high temperature condition, so that the crosslinking density of the matrix is further improved.
In the modified MXene nano-sheet, firstly, an amide bond is generated by utilizing an amide reaction between an amino group in the compound 1 and a carboxyl group on the surface of the MXene nano-sheet, so that the modification of the MXene nano-sheet is realized; meanwhile, the positively charged imidazole structure of the compound 1 can also generate electrostatic action with the negatively charged MXene nano-sheets to be adsorbed on the surfaces of the MXene nano-sheets to realize modification. Secondly, the modified MXene nano-sheet has excellent dispersibility, because the compound 1 on the surface of the nano-sheet disturbs the MXene lamellar structure, so that the disorder is increased; the dispersibility is improved, and the friction between the rubber molecular chain and the physical crosslinking point is reduced by increasing the physical crosslinking point. Finally, the lubricating layer formed on the surface of the MXene nano-sheet by the compound 1 is equivalent to coating a layer of lubricating layer on the surface of the rubber matrix, so that the direct contact between the rubber and the friction surface is reduced, the friction coefficient is reduced, and the wear resistance of the matrix is improved; in addition, the long-chain hydrophobic alkyl structure on the surface of the nano sheet endows the matrix with certain hydrophobicity, so that the water resistance of the matrix is further improved.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
1) The modified polyurethane rubber is prepared by the following steps:
Step A1, adding 0.1mol of 2, 3-bis (trifluoromethyl) benzene-1, 4-diamine into a flask containing 100mL of dimethylacetamide, stirring and mixing uniformly, cooling the mixed solution to 0 ℃ in a water bath, adding 7mL of triethylamine into the flask, stirring and mixing uniformly, slowly adding 0.21mol of 3-hydroxy propionyl chloride under the condition of low temperature stirring, transferring the flask into an oil bath, heating to 40 ℃, maintaining the temperature for reaction for 4 hours, adding the mixture into 100mL of deionized water at 10 ℃ after the reaction is finished, washing a filter cake with 80 ℃ of deionized water after vacuum suction filtration, and drying in vacuum at 100 ℃ for 8 hours to obtain the fluorine-containing chain extender;
Step A2, adding 1mol of polycarbonate diol (PCDL 2000) into a reactor, placing the reactor in an oil bath at 100 ℃ under the vacuum degree of 0.67kPa for high-temperature dehydration for 1.5 hours, then reducing the system temperature to 40 ℃, adding 1.75mol of isophorone diisocyanate, introducing nitrogen into the reactor, stirring for 10 minutes, and then heating to 80 ℃ for continuing stirring for 1 hour to obtain a prepolymer;
And A3, adding 1.75mol of fluorine-containing chain extender, 0.21g of dibutyltin dilaurate and 10mL of N, N-dimethylacetamide into the prepolymer under the condition of nitrogen, stirring for 5min, adding 0.1mL of 3- (N-allylamino) propyl trimethoxysilane, reacting at 40 ℃ for 30min, transferring the mixture into a polytetrafluoroethylene container, and curing in a baking oven at 100 ℃ for 24h to obtain the modified polyurethane rubber.
2) The modified MXene nano-sheet is prepared by the following steps:
step B1, under the condition of nitrogen, adding 1mol of 3-chloropropylamine and 1mol of 1-dodecyl imidazole into a reactor, stirring and mixing uniformly, heating to 60 ℃, stirring for 24 hours, cooling to room temperature, and washing with anhydrous diethyl ether for three times to obtain a compound 1;
And B2, adding 0.1g of MXene nano-sheets into a reactor containing 20mL of deionized water, carrying out ultrasonic treatment for 30min, stirring for 20min at a rotating speed of 300rpm, regulating the pH of the mixed solution to 8.5, adding 0.05g of compound 1, carrying out water bath ultrasonic treatment for 30min, reacting for 10h under the condition of nitrogen, wherein the reaction temperature is 75 ℃, the rotating speed is 300rpm, cooling to room temperature after the reaction is finished, and carrying out ultrasonic stirring for 30min to obtain the modified MXene nano-sheets.
Example 2
1) The modified polyurethane rubber is prepared by the following steps:
step A1, adding 0.2mol of 2, 3-bis (trifluoromethyl) benzene-1, 4-diamine into a flask containing 120mL of dimethylacetamide, stirring and mixing uniformly, cooling the mixed solution to 0 ℃ in a water bath, adding 14mL of triethylamine into the flask, stirring and mixing uniformly, slowly adding 0.41mol of 3-hydroxy propionyl chloride under the condition of low temperature stirring, transferring the flask into an oil bath, heating to 50 ℃, maintaining the temperature for reaction for 4 hours, adding the mixture into 100mL of deionized water at 10 ℃ after the reaction is finished, washing a filter cake with deionized water at 85 ℃ after vacuum suction filtration, and drying in vacuum at 100 ℃ for 8 hours to obtain the fluorine-containing chain extender;
Step A2, adding 1mol of polycarbonate diol (PCDL 2000) into a reactor, placing the reactor in an oil bath at 110 ℃ under the vacuum degree of 0.67kPa for high-temperature dehydration for 1.5 hours, then reducing the system temperature to 50 ℃, adding 2.3mol of isophorone diisocyanate, introducing nitrogen into the reactor, stirring for 15 minutes, and then heating to 85 ℃ for continuing stirring for 1.5 hours to obtain a prepolymer;
And A3, adding 2.3mol of fluorine-containing chain extender, 0.32g of dibutyltin dilaurate and 15mL of N, N-dimethylacetamide into the prepolymer under the condition of nitrogen, stirring for 10min, adding 0.12mL of 3- (N-allylamino) propyl trimethoxysilane, reacting at 40 ℃ for 45min, transferring the mixture into a polytetrafluoroethylene container, and curing in a baking oven at 100 ℃ for 24h to obtain the modified polyurethane rubber.
2) The modified MXene nano-sheet is prepared by the following steps:
step B1, under the condition of nitrogen, adding 1mol of 3-chloropropylamine and 1mol of 1-dodecyl imidazole into a reactor, stirring and mixing uniformly, heating to 60 ℃, stirring for 24 hours, cooling to room temperature, and washing with anhydrous diethyl ether for three times to obtain a compound 1;
and B2, adding 0.1g of MXene nano-sheets into a reactor containing 20mL of deionized water, carrying out ultrasonic treatment for 30min, stirring for 20min at a rotating speed of 300rpm, regulating the pH of the mixed solution to 8.5, adding 0.1g of compound 1, carrying out water bath ultrasonic treatment for 30min, reacting for 11h under the condition of nitrogen, wherein the reaction temperature is 80 ℃, the rotating speed is 300rpm, cooling to room temperature after the reaction is finished, and carrying out ultrasonic stirring for 30min to obtain the modified MXene nano-sheets.
Example 3
1) The modified polyurethane rubber is prepared by the following steps:
Step A1, adding 0.3mol of 2, 3-bis (trifluoromethyl) benzene-1, 4-diamine into a flask containing 150mL of dimethylacetamide, stirring and mixing uniformly, cooling the mixed solution to 0 ℃ in a water bath, adding 21mL of triethylamine into the flask, stirring and mixing uniformly, slowly adding 0.61mol of 3-hydroxy propionyl chloride under the condition of low temperature stirring, transferring the flask into an oil bath, heating to 60 ℃ to maintain the temperature for reaction for 4 hours, adding the mixture into 100mL of deionized water at 10 ℃ after the reaction is finished, washing a filter cake with 90 ℃ of deionized water after vacuum suction filtration, and drying in vacuum at 100 ℃ for 8 hours to obtain the fluorine-containing chain extender;
Step A2, adding 1mol of polycarbonate diol (PCDL 2000) into a reactor, placing the reactor in an oil bath at 120 ℃ under the vacuum degree of 0.67kPa for high-temperature dehydration for 1.5 hours, then reducing the system temperature to 60 ℃, adding 3.5mol of isophorone diisocyanate, introducing nitrogen into the reactor, stirring for 20 minutes, and then heating to 90 ℃ for continuous stirring for 2 hours to obtain a prepolymer;
And A3, adding 3.5mol of fluorine-containing chain extender, 0.42g of dibutyltin dilaurate and 20mL of N, N-dimethylacetamide into the prepolymer under the condition of nitrogen, stirring for 10min, adding 0.15mL of 3- (N-allylamino) propyl trimethoxysilane, reacting at 40 ℃ for 60min, transferring the mixture into a polytetrafluoroethylene container, and curing in a baking oven at 100 ℃ for 24h to obtain the modified polyurethane rubber.
2) The modified MXene nano-sheet is prepared by the following steps:
step B1, under the condition of nitrogen, adding 1mol of 3-chloropropylamine and 1mol of 1-dodecyl imidazole into a reactor, stirring and mixing uniformly, heating to 60 ℃, stirring for 24 hours, cooling to room temperature, and washing with anhydrous diethyl ether for three times to obtain a compound 1;
And B2, adding 0.1g of MXene nano-sheets into a reactor containing 20mL of deionized water, carrying out ultrasonic treatment for 30min, stirring for 20min at a rotating speed of 300rpm, regulating the pH of the mixed solution to 8.5, adding 0.2g of compound 1, carrying out water bath ultrasonic treatment for 30min, reacting for 12h under the condition of nitrogen, wherein the reaction temperature is 85 ℃, the rotating speed is 300rpm, cooling to room temperature after the reaction is finished, and carrying out ultrasonic stirring for 30min to obtain the modified MXene nano-sheets.
Example 4
The material of the high wear-resistant rubber runway comprises the following raw materials in parts by weight: 50 parts of rubber particles, 40 parts of natural rubber, 10 parts of silicone rubber, 8 parts of modified polyurethane rubber prepared in example 1, 10 parts of modified MXene nano-sheets prepared in example 1, 0.5 part of iron oxide red, 0.3 part of zinc dibenzyl dithiocarbamate, 3 parts of bis-tert-butyl peroxy-propyl benzene and 0.2 part of amine antioxidants; the preparation method comprises the following steps:
Step S1, weighing raw materials according to parts by weight, adding rubber particles, natural rubber, silicon rubber and the modified polyurethane rubber prepared in the embodiment 1 into a mixing mill for uniform mixing, and sequentially adding the modified MXene nano-sheet prepared in the embodiment 1, ferric oxide red, an amine antioxidant and zinc dibenzyl dithiocarbamate for uniform mixing to obtain a mixed rubber;
S2, transferring the rubber compound into an open mill, adding the bis-tert-butyl peroxy propyl benzo thin pass for 5 times, and then performing lower piece die pressing and shaping to obtain a blank;
And S3, placing the blank in a vulcanizing machine, controlling the vulcanizing temperature to be 165 ℃ and the vulcanizing time to be 2 hours, cooling, crushing by a crusher, and then paving, compacting and solidifying to obtain the high-wear-resistance rubber runway.
Example 5
The material of the high wear-resistant rubber runway comprises the following raw materials in parts by weight: 55 parts of rubber particles, 45 parts of natural rubber, 12 parts of silicone rubber, 10 parts of modified polyurethane rubber prepared in example 2, 12 parts of modified MXene nano-sheets prepared in example 2, iron violet parts of oxidation, 0.5 part of zinc dibenzyl dithiocarbamate, 4.5 parts of bis (tert-butyl) peroxy-propylbenzene and 0.6 part of amine antioxidants; the preparation method comprises the following steps:
Step S1, weighing raw materials according to parts by weight, adding rubber particles, natural rubber, silicon rubber and the modified polyurethane rubber prepared in the example 2 into a mixing mill for uniform mixing, and sequentially adding the modified MXene nano-sheet prepared in the example 2, oxidation iron violet, an amine antioxidant and zinc dibenzyl dithiocarbamate for uniform mixing to obtain a mixed rubber;
s2, transferring the rubber compound into an open mill, adding the bis-tert-butyl peroxy propyl benzo thin pass for 6 times, and then performing lower piece die pressing and shaping to obtain a blank;
and S3, placing the blank in a vulcanizing machine, controlling the vulcanizing temperature to 175 ℃ and the vulcanizing time to 2.5 hours, cooling, crushing by a crusher, and then paving, compacting and solidifying to obtain the high-wear-resistance rubber runway.
Example 6
The material of the high wear-resistant rubber runway comprises the following raw materials in parts by weight: 60 parts of rubber particles, 50 parts of natural rubber, 15 parts of silicone rubber, 12 parts of modified polyurethane rubber prepared in example 3, 15 parts of modified MXene nano-sheets prepared in example 3, 2 parts of ultramarine blue, 1 part of zinc dibenzyldithiocarbamate, 6 parts of bis-tert-butyl-peroxy-propyl benzene and 1 part of amine antioxidant; the preparation method comprises the following steps:
Step S1, weighing raw materials according to parts by weight, adding rubber particles, natural rubber, silicon rubber and the modified polyurethane rubber prepared in the example 3 into a mixing mill for uniform mixing, and sequentially adding the modified MXene nano-sheet prepared in the example 3, ultramarine blue, an amine antioxidant and zinc dibenzyl dithiocarbamate for uniform mixing to obtain a mixed rubber;
s2, transferring the rubber compound into an open mill, adding the bis-tert-butyl peroxy propyl benzo thin pass for 8 times, and then performing lower piece die pressing and shaping to obtain a blank;
And S3, placing the blank in a vulcanizing machine, controlling the vulcanizing temperature to be 185 ℃ and the vulcanizing time to be 3 hours, cooling, crushing by a crusher, and then paving, compacting and solidifying to obtain the high-wear-resistance rubber runway.
Comparative example 1
This comparative example is a rubber track, and differs from example 5 in that the modified polyurethane rubber is replaced with an equivalent amount of polyurethane rubber, and the remainder are the same.
Comparative example 2
This comparative example is a rubber track, and differs from example 5 in that the modified MXene nanoplatelets are replaced with the same amount of MXene nanoplatelets, the remainder being the same.
Performance tests were performed on the rubber runways prepared in examples 4-6 and comparative examples 1-2; abrasion resistance: the abrasion-resistant effect detection indexes mainly comprise Shore A hardness and compression recovery rate, the Shore A hardness is measured according to GB/T531-1999 standard, and the compression recovery rate is measured according to GB/T14833-93 standard; water resistance: cutting the rubber runway into 5cm multiplied by 5cm sample blocks, soaking in rainwater for 300h, and observing whether the appearance of the sample blocks is foamed or cracked. The test results are shown in table 1:
TABLE 1
As can be seen from Table 1, the rubber tracks of examples 4 to 6 of the present invention have a Shore A hardness of 73 to 76 degrees, a compression recovery of 99%, and exhibit excellent wear resistance; after the water resistance test, the runway sample block is not foamed and cracked, and has excellent water resistance.
The foregoing is merely illustrative and explanatory of the principles of the invention, as various modifications and additions may be made to the specific embodiments described, or similar alternatives may be made by those skilled in the art, without departing from the scope of the invention as defined by the principles of the invention.
Claims (8)
1. The high wear-resistant rubber runway is characterized by comprising the following raw materials in parts by weight: 50-60 parts of rubber particles, 40-50 parts of natural rubber, 10-15 parts of silicone rubber, 8-12 parts of modified polyurethane rubber, 10-15 parts of modified MXene nano-sheets, 0.5-2 parts of pigment, 0.3-1 part of accelerator, 3-6 parts of vulcanizing agent and 0.2-1 part of antioxidant;
the modified polyurethane rubber is prepared by the following steps:
Step A1, adding 2, 3-bis (trifluoromethyl) benzene-1, 4-diamine into a flask containing dimethylacetamide, stirring and mixing uniformly, cooling the mixed solution to 0 ℃ in a water bath, adding triethylamine into the flask, stirring and mixing uniformly, slowly adding 3-hydroxy propionyl chloride under the condition of low temperature stirring, transferring the flask into an oil bath, heating to 40-60 ℃, maintaining the temperature for reaction for 4 hours, adding the mixture into deionized water at 10 ℃ after the reaction is finished, washing a filter cake with deionized water at 80-90 ℃ after vacuum suction filtration, and vacuum drying for 8 hours at 100 ℃ to obtain a fluorine-containing chain extender;
step A2, adding polycarbonate diol into a reactor, placing the polycarbonate diol into an oil bath pot at 100-120 ℃ under the vacuum degree of 0.67kPa for high-temperature dehydration for 1.5 hours, then reducing the system temperature to 40-60 ℃, adding isophorone diisocyanate, introducing nitrogen into the reactor, stirring for 10-20 minutes, and then heating to 80-90 ℃ for continuous stirring for 1-2 hours to obtain a prepolymer;
Step A3, under the condition of nitrogen, adding a fluorine-containing chain extender, dibutyl tin dilaurate and N, N-dimethylacetamide into the prepolymer, stirring for 5-10min, adding 3- (N-allylamino) propyl trimethoxy silane, reacting for 30-60min at 40 ℃, transferring the mixture into a polytetrafluoroethylene container, and curing for 24h in a baking oven at 100 ℃ to obtain modified polyurethane rubber;
the modified MXene nano-sheet is prepared by the following steps:
Step B1, under the condition of nitrogen, adding 3-chloropropylamine and 1-dodecyl imidazole into a reactor, uniformly stirring and mixing, heating to 60 ℃, stirring for 24 hours, cooling to room temperature, and washing with anhydrous diethyl ether for three times to obtain a compound 1;
And B2, adding the MXene nano-sheets into a reactor containing deionized water, carrying out ultrasonic treatment for 30min, stirring for 20min at a rotating speed of 300rpm, regulating the pH of the mixed solution to 8.5, adding the compound 1, carrying out water bath ultrasonic treatment for 30min, then reacting for 10-12h under the condition of nitrogen, wherein the reaction temperature is 75-85 ℃, the rotating speed is 300rpm, cooling to room temperature after the reaction is finished, and carrying out ultrasonic stirring for 30min to obtain the modified MXene nano-sheets.
2. The high wear resistant rubber track according to claim 1, wherein the amount ratio of 2, 3-bis (trifluoromethyl) benzene-1, 4-diamine, dimethylacetamide, triethylamine, 3-hydroxypropionyl chloride and deionized water in step A1 is 0.1 to 0.3mol:100-150mL:7-21mL:0.21-0.61mol:100mL.
3. The high wear resistant rubber track according to claim 1, wherein the polycarbonate diol and isophorone diisocyanate are used in an amount ratio of 1mol:1.75-3.5mol.
4. The high wear resistant rubber track according to claim 1, wherein the ratio of the amount of fluorine-containing chain extender, dibutyltin dilaurate, N-dimethylacetamide, 3- (N-allylamino) propyltrimethoxysilane and polycarbonate diol in step A1 is 1.75 to 3.5mol:0.21-0.42g:10-20mL:0.1-0.15mL:1mol.
5. The high wear resistant rubber track according to claim 1, wherein the molar ratio of 3-chloropropylamine to 1-dodecylimidazole in step B1 is 1:1.
6. The high wear resistant rubber track according to claim 1, wherein the amount ratio of MXene nanoplatelets, deionized water and compound 1 in step B2 is 0.1g:20mL:0.05-0.2g.
7. The high wear resistant rubber track of claim 1 wherein said pigment is one of red iron oxide, iron violet oxide, ultramarine blue, titanium white.
8. The method for preparing a high wear-resistant rubber runway according to claim 1, comprising the following steps:
S1, weighing raw materials according to parts by weight, adding rubber particles, natural rubber, silicon rubber and modified polyurethane rubber into a mixing mill, mixing uniformly, and sequentially adding modified MXene nano-sheets, pigments, antioxidants and accelerators, mixing uniformly to obtain a rubber compound;
S2, transferring the rubber compound into an open mill, adding a vulcanizing agent, carrying out thin-pass 5-8 times, and then carrying out lower piece die pressing and shaping to obtain a blank;
And S3, placing the blank in a vulcanizing machine, controlling the vulcanizing temperature to be 165-185 ℃ and the vulcanizing time to be 2-3 hours, cooling, crushing by a crusher, and then paving, compacting and solidifying to obtain the high-wear-resistance rubber runway.
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| CN112608534A (en) * | 2020-12-15 | 2021-04-06 | 浙江奋飞橡塑制品有限公司 | Wear-resistant polyurethane rubber, preparation method thereof and application thereof in conveyor belt |
| CN114292515A (en) * | 2022-01-12 | 2022-04-08 | 安徽冠泓塑业有限公司 | High-wear-resistance and high-strength protective boot and preparation method thereof |
| CN117467204A (en) * | 2023-12-19 | 2024-01-30 | 太原工业学院 | MXene/rubber composite material with high wear resistance and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106496703A (en) * | 2016-10-08 | 2017-03-15 | 扬中市橡胶塑料厂有限公司 | A kind of high wearable rubber seal production method |
| CN112608534A (en) * | 2020-12-15 | 2021-04-06 | 浙江奋飞橡塑制品有限公司 | Wear-resistant polyurethane rubber, preparation method thereof and application thereof in conveyor belt |
| CN114292515A (en) * | 2022-01-12 | 2022-04-08 | 安徽冠泓塑业有限公司 | High-wear-resistance and high-strength protective boot and preparation method thereof |
| CN117467204A (en) * | 2023-12-19 | 2024-01-30 | 太原工业学院 | MXene/rubber composite material with high wear resistance and preparation method thereof |
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