CN112300565A - Wear-resistant polyurethane tire for forklift and preparation method thereof - Google Patents
Wear-resistant polyurethane tire for forklift and preparation method thereof Download PDFInfo
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- CN112300565A CN112300565A CN202011242058.9A CN202011242058A CN112300565A CN 112300565 A CN112300565 A CN 112300565A CN 202011242058 A CN202011242058 A CN 202011242058A CN 112300565 A CN112300565 A CN 112300565A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/143—Halogen containing compounds
- C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5003—Polyethers having heteroatoms other than oxygen having halogens
- C08G18/5006—Polyethers having heteroatoms other than oxygen having halogens having chlorine and/or bromine atoms
- C08G18/5009—Polyethers having heteroatoms other than oxygen having halogens having chlorine and/or bromine atoms having chlorine atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
- C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2639—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing elements other than oxygen, nitrogen or sulfur
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0014—Use of organic additives
- C08J9/0042—Use of organic additives containing silicon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0066—Use of inorganic compounding ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/08—Polyurethanes from polyethers
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Abstract
The invention discloses a wear-resistant polyurethane tire for a forklift, which comprises the following raw materials in parts by weight: 40-70 parts of chlorine-containing polyether polyol, 8-15 parts of toluene diisocyanate, 2-5 parts of antimony trioxide, 1-3 parts of chain extender, 1-3 parts of foaming agent, 1-3 parts of coupling agent and 1-3 parts of cross-linking agent; the invention also discloses a preparation method of the tire. According to the invention, chlorine-containing polyether polyol reacts with isocyanate, chlorine atoms of halogen flame-retardant elements are combined on a polyurethane molecular chain, so that chlorine radicals are separated out from a polyurethane tire in a friction heated state, the chlorine radicals can capture combustible active hydroxyl groups, meanwhile, the chlorine radicals are combined with hydrogen radicals to generate hydrogen chloride, the hydrogen chloride reacts with antimony trioxide to generate antimony trichloride, the formation of combustible substances can be prevented, and the heat resistance of the tire during friction is improved due to the synergistic effect of a halogen flame retardant and an antimony flame retardant, so that the wear resistance is greatly improved, and the service life of the tire is prolonged.
Description
Technical Field
The invention belongs to the technical field of tires, and relates to a wear-resistant polyurethane tire for a forklift and a preparation method thereof.
Background
Polyurethane rubber has excellent physical and mechanical properties and chemical resistance, and is widely used for manufacturing tires of various loading vehicles and engineering vehicles. The most needed in practical use of tires is wear resistance, and the problem to be solved is to improve the wear resistance of the tires.
The traditional preparation method is to directly add the flame-retardant material as an additive, so that the flame-retardant effect of the tire is greatly improved, the heat resistance of the tire during friction is improved, and the wear resistance is improved.
Disclosure of Invention
The invention aims to provide a wear-resistant polyurethane tire for a forklift and a preparation method thereof, wherein chlorine-containing polyether polyol is reacted with isocyanate in the preparation process of the wear-resistant polyurethane tire, and chlorine atoms serving as halogen flame-retardant elements are combined on a polyurethane molecular chain, so that chlorine radicals can be separated out from the polyurethane tire in a friction heated state, the chlorine radicals can capture combustible active hydroxyl groups, the chlorine radicals are combined with hydrogen radicals to generate hydrogen chloride, the hydrogen chloride is reacted with antimony trioxide to generate antimony trichloride, and the formation of combustible substances in combustion gas phase can also be prevented, and the heat resistance of the tire during friction can be improved due to the synergistic effect of the halogen flame retardant and the antimony flame retardant, so that the wear resistance is greatly improved, and the service life of the tire is prolonged.
The purpose of the invention can be realized by the following technical scheme:
the wear-resistant polyurethane tire for the forklift comprises the following raw materials in parts by weight:
40-70 parts of chlorine-containing polyether polyol, 8-15 parts of toluene diisocyanate, 2-5 parts of antimony trioxide, 1-3 parts of chain extender, 1-3 parts of foaming agent, 1-3 parts of coupling agent and 1-3 parts of cross-linking agent;
the wear-resistant polyurethane tire for the forklift is prepared by the following steps:
step S1, carrying out dehydration reaction on the chlorine-containing polyether polyol, controlling the dehydration reaction temperature to be 120 ℃ and the reaction time to be 5 hours; then adding toluene diisocyanate to carry out mixed reaction at 85 ℃ for 3 hours to prepare a prepolymer;
step S2, adding antimony trioxide, a chain extender, a foaming agent, a coupling agent and a crosslinking agent into a stirrer, stirring for 1 hour at room temperature, wherein the stirring speed is 120rpm, and preparing auxiliary materials;
and S3, respectively putting the prepolymer prepared in the step S1 and the auxiliary materials prepared in the step S2 into a casting machine, casting the prepolymer and the auxiliary materials into a tire casting mold for casting molding, demolding to obtain a semi-finished product, polishing the casting seam of the semi-finished product smoothly by using a tire polisher, and vulcanizing at 150 ℃ for 8 hours to obtain the wear-resistant polyurethane tire for the forklift.
Further, the specific preparation process of the chlorine-containing polyether polyol is as follows:
step A1, heating dichlorobutylene glycol to 120 ℃ under the protection of nitrogen, adding boron trifluoride diethyl etherate serving as a catalyst, stirring for 10 minutes, dropwise adding epichlorohydrin, keeping the temperature of the material at 120 ℃ during dropwise adding, and keeping the temperature for 1 hour to obtain an intermediate 1;
step A2, dissolving the intermediate 1 prepared in the step A1 in toluene, slowly adding a sodium hydroxide solution dropwise, standing for layering after the addition is finished, removing a water layer, repeatedly washing the water layer with deionized water until the water layer is neutral, and then evaporating to remove the toluene to obtain an intermediate 2;
step A3, dissolving the intermediate 2 prepared in the step A2 in a mixed solvent of water and methanol, adding nitric acid, heating to 70 ℃, stirring for reaction for 2 hours, adding calcium hydroxide for neutralization, filtering to remove precipitates and unreacted calcium hydroxide, finally evaporating the solvent to dryness to obtain chlorine-containing polyether polyol, carrying out ring opening reaction on-OH of dichlorobutenediol and epoxy groups in epoxy chloropropane in the synthetic route to generate a compound with a terminal group of chlorinated hydroxyl, removing hydrogen chloride from the chlorinated hydroxyl under the action of sodium hydroxide to form epoxy groups, and finally carrying out hydrolysis to obtain the chlorine-containing flame-retardant polyether polyol. Meanwhile, chlorine radicals are combined with hydrogen radicals to generate hydrogen chloride, the hydrogen chloride reacts with antimony trioxide to generate antimony trichloride, the formation of combustible substances in combustion gas phase can be prevented, and the heat resistance of the tire during friction can be improved due to the synergistic effect of the halogen flame retardant and the antimony flame retardant, so that the wear resistance is greatly improved, and the service life of the tire is prolonged.
Further, in the step S2, the chain extender is a mixture prepared by mixing ethylene glycol and 1, 4-butanediol at a mass ratio of 1:1, the blowing agent is chlorofluorocarbon, the coupling agent is a silane coupling agent, and the crosslinking agent is a mixture prepared by mixing ethylene glycol and 1, 4-butanediol at a mass ratio of 1: 1.
Further, the mol ratio of the dichlorobutylene glycol and the epichlorohydrin in the step A1 is 2:1, and 0.008-0.01 mol of boron trifluoride diethyl ether is added into each mol of dichlorobutylene glycol.
Further, the using amount ratio of the intermediate 1, the toluene and the sodium hydroxide solution in the step A2 is 10g:100mL:40mL, and the mass fraction of the sodium hydroxide solution is 50%.
Further, the intermediate 2 and the mixed solvent of water and methanol in the step A3 are mixed at a ratio of 5g to 100mL, the mixed solvent is prepared by mixing water and methanol at a volume ratio of 7:1, the mass fraction of the nitric acid is 65%, and 1g of nitric acid and 1g of calcium hydroxide are added into 100mL of the mixed solvent of water and methanol.
The specific preparation method of the wear-resistant polyurethane tire for the forklift comprises the following steps:
step S1, carrying out dehydration reaction on the chlorine-containing polyether polyol, controlling the dehydration reaction temperature to be 120 ℃ and the reaction time to be 5 hours; then adding toluene diisocyanate to carry out mixed reaction at 85 ℃ for 3 hours to prepare a prepolymer;
step S2, adding antimony trioxide, a chain extender, a foaming agent, a coupling agent and a crosslinking agent into a stirrer, stirring for 1 hour at room temperature, wherein the stirring speed is 120rpm, and preparing auxiliary materials;
and S3, respectively putting the prepolymer prepared in the step S1 and the auxiliary materials prepared in the step S2 into a casting machine, casting the prepolymer and the auxiliary materials into a tire casting mold for casting molding, demolding to obtain a semi-finished product, polishing the casting seam of the semi-finished product smoothly by using a tire polisher, and vulcanizing at 150 ℃ for 8 hours to obtain the wear-resistant polyurethane tire for the forklift.
The invention has the beneficial effects that: according to the invention, chlorine-containing polyether polyol reacts with isocyanate, chlorine atoms of halogen flame-retardant elements are combined on a polyurethane molecular chain, so that chlorine radicals are separated out from a polyurethane tire in a friction heated state, the chlorine radicals can capture flammable active hydroxyl groups, meanwhile, the chlorine radicals are combined with hydrogen radicals to generate hydrogen chloride, the hydrogen chloride reacts with antimony trioxide to generate antimony trichloride, and the formation of flammable substances in combustion gas phase can also be prevented, and the heat resistance of the tire during friction can be improved due to the synergistic effect of the halogen flame retardant and the antimony flame retardant, so that the wear resistance is greatly improved, and the service life of the tire is prolonged.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the 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.
Example 1:
the specific preparation process of the chlorine-containing polyether polyol is as follows:
step A1, heating dichlorobutenediol to 120 ℃ under the protection of nitrogen, adding boron trifluoride diethyl etherate serving as a catalyst, stirring for 10 minutes, then dropwise adding epoxy chloropropane, keeping the material temperature at 120 ℃ during dropwise adding, and keeping the temperature for 1 hour to prepare an intermediate 1, wherein the molar ratio of the dichlorobutenediol to the epoxy chloropropane is 2:1, and 0.008-0.01 mol of boron trifluoride diethyl etherate is added into each mol of dichlorobutenediol;
step A2, dissolving the intermediate 1 prepared in the step A1 in toluene, slowly adding a sodium hydroxide solution dropwise, standing for layering after dropwise adding, removing a water layer, repeatedly washing the water layer with deionized water until the water layer is neutral, and then evaporating to remove the toluene to obtain an intermediate 2, wherein the using ratio of the intermediate 1, the toluene and the sodium hydroxide solution is 10g:100mL:40mL, and the mass fraction of the sodium hydroxide solution is 50%;
step A3, dissolving the intermediate 2 prepared in the step A2 in a mixed solvent of water and methanol, adding nitric acid, heating to 70 ℃, stirring for reacting for 2 hours, adding calcium hydroxide for neutralization, filtering to remove precipitates and unreacted calcium hydroxide, and finally evaporating the solvent to obtain the chlorine-containing polyether polyol, wherein the using amount ratio of the intermediate 2 and the mixed solvent of water and methanol is 5g:100mL, the water and the methanol are mixed in a volume ratio of 7:1 to prepare the mixed solvent, the mass fraction of the nitric acid is 65%, and 1g of nitric acid and 1g of calcium hydroxide are added in each 100mL of the mixed solvent of water and methanol.
Example 2
A wear-resistant polyurethane tire for a forklift is prepared from the following raw materials in parts by weight: 40 parts of chlorine-containing polyether polyol, 8 parts of toluene diisocyanate, 2 parts of antimony trioxide, 2 parts of ethylene glycol, 1 part of chlorofluorocarbon, 1 part of silane coupling agent and 1 part of 1, 4-butanediol;
the specific preparation method of the wear-resistant polyurethane tire for the forklift comprises the following steps:
step S1, performing a dehydration reaction on the chlorine-containing polyether polyol prepared in example 1, controlling the dehydration reaction temperature at 120 ℃ and the reaction time at 5 hours; then adding toluene diisocyanate to carry out mixed reaction at 85 ℃ for 3 hours to prepare a prepolymer;
step S2, adding antimony trioxide, ethylene glycol, chlorofluorocarbon, silane coupling agent and 1, 4-butanediol into a stirrer, stirring for 1 hour at room temperature at the stirring speed of 120rpm to prepare auxiliary materials;
and S3, respectively putting the prepolymer prepared in the step S1 and the auxiliary materials prepared in the step S2 into a casting machine, casting the prepolymer and the auxiliary materials into a tire casting mold for casting molding, demolding to obtain a semi-finished product, polishing the casting seam of the semi-finished product smoothly by using a tire polisher, and vulcanizing at 150 ℃ for 8 hours to obtain the wear-resistant polyurethane tire for the forklift.
Example 3:
a wear-resistant polyurethane tire for a forklift is prepared from the following raw materials in parts by weight: 50 parts of chlorine-containing polyether polyol, 12 parts of toluene diisocyanate, 3.5 parts of antimony trioxide, 2 parts of 1, 4-butanediol, 2 parts of chlorofluorocarbon, 2 parts of silane coupling agent, and 2 parts of ethylene glycol and 1, 3-propylene glycol are mixed according to the mass ratio of 1:1 to prepare 2 parts of mixed crosslinking agent;
the specific preparation method of the wear-resistant polyurethane tire for the forklift comprises the following steps:
step S1, performing a dehydration reaction on the chlorine-containing polyether polyol prepared in example 1, controlling the dehydration reaction temperature at 120 ℃ and the reaction time at 5 hours; then adding toluene diisocyanate to carry out mixed reaction at 85 ℃ for 3 hours to prepare a prepolymer;
step S2, mixing antimony trioxide, 1, 4-butanediol, chlorofluorocarbon, silane coupling agent, ethylene glycol and 1, 3-propanediol in a mass ratio of 1:1 to prepare a mixed crosslinking agent, adding the mixed crosslinking agent into a stirrer, stirring for 1 hour at room temperature at a stirring speed of 120rpm to prepare auxiliary materials;
and S3, respectively putting the prepolymer prepared in the step S1 and the auxiliary materials prepared in the step S2 into a casting machine, casting the prepolymer and the auxiliary materials into a tire casting mold for casting molding, demolding to obtain a semi-finished product, polishing the casting seam of the semi-finished product smoothly by using a tire polisher, and vulcanizing at 150 ℃ for 8 hours to obtain the wear-resistant polyurethane tire for the forklift.
Example 4
A wear-resistant polyurethane tire for a forklift is prepared from the following raw materials in parts by weight: 70 parts of chlorine-containing polyether polyol, 15 parts of toluene diisocyanate, 5 parts of antimony trioxide, 3 parts of ethylene glycol, 3 parts of chlorofluorocarbon, 3 parts of alkane coupling agent and 3 parts of 1, 6-butanediol;
the specific preparation method of the wear-resistant polyurethane tire for the forklift comprises the following steps:
step S1, performing a dehydration reaction on the chlorine-containing polyether polyol prepared in example 1, controlling the dehydration reaction temperature at 120 ℃ and the reaction time at 5 hours; then adding toluene diisocyanate to carry out mixed reaction at 85 ℃ for 3 hours to prepare a prepolymer;
step S2, adding antimony trioxide, ethylene glycol, chlorofluorocarbon, alkane coupling agent and 1, 6-butanediol into a stirrer, stirring for 1 hour at room temperature, wherein the stirring speed is 120rpm, and preparing auxiliary materials;
and S3, respectively putting the prepolymer prepared in the step S1 and the auxiliary materials prepared in the step S2 into a casting machine, casting the prepolymer and the auxiliary materials into a tire casting mold for casting molding, demolding to obtain a semi-finished product, polishing the casting seam of the semi-finished product smoothly by using a tire polisher, and vulcanizing at 150 ℃ for 8 hours to obtain the wear-resistant polyurethane tire for the forklift.
Comparative example 1
The chlorine-containing polyether polyol of example 2 was replaced by a polyacrylate polyol.
Comparative example 2
The antimony trioxide in example 2 was replaced by the additive flame retardant aluminum hydroxide.
The following performance tests were performed on the polyurethane tires obtained in examples 2, 3, 4 and comparative examples 1, 2:
the polyurethane tires obtained in examples 2, 3 and 4 and comparative examples 1 and 2 were subjected to flame retardancy tests including an oxygen index test specified in national standard GB/T10707 and a vertical burning method specified in UL-94; the polyurethane tires obtained in examples 2, 3 and 4 and comparative examples 1 and 2 were subjected to friction with a grinding wheel at a certain inclination angle and under a certain load according to the national standard GB/T1689-1998 using an Akron abrasion tester, and the wear volume of the tire was determined for a certain mileage, the test data being shown in the following table:
| example 2 | Example 3 | Example 4 | Comparative example 1 | Comparative example 2 | |
| Oxygen index/% | 35 | 36 | 38 | 28 | 27 |
| Vertical combustion class | Class V-0 | Class V-0 | Class V-0 | Class V-1 | Class V-1 |
| Akron abrasion loss/cm3 | 0.26 | 0.27 | 0.28 | 0.34 | 0.36 |
As can be seen from the table, the oxygen indexes of the polyurethane tires prepared in examples 2, 3 and 4 are between 35% and 38%, which are all obviously higher than the oxygen indexes of the polyurethane tires prepared in comparative examples 1 and 2, and the higher the oxygen index of the polyurethane tires prepared in examples is, the better the flame retardant performance is, and the vertical burning grades of the polyurethane tires prepared in examples 2, 3 and 4 are V-0 grade, which is lower than the vertical burning grades of the polyurethane tires prepared in comparative examples 1 and 2, which indicates that the flame retardant performance of the polyurethane tires prepared in examples is better than that of the comparative examples; secondly, the akron wear loss of the polyurethane tires prepared in examples 2, 3 and 4 is lower than that of the polyurethane tires prepared in comparative examples 1 and 2, and it can be known that the wear resistance of the polyurethane tires prepared in examples 2, 3 and 4 is higher than that of the polyurethane tires prepared in comparative examples, and the performance tests show that the synergistic effect of the halogen flame retardant and the antimony flame retardant can improve the flame retardant effect of the tires, so that the heat resistance of the tires during friction is improved, the wear resistance of the tires is greatly improved, and the service life of the tires is prolonged.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims (10)
1. The wear-resistant polyurethane tire for the forklift is characterized by comprising the following raw materials in parts by weight: 40-70 parts of chlorine-containing polyether polyol, 8-15 parts of toluene diisocyanate, 2-5 parts of antimony trioxide, 1-3 parts of chain extender, 1-3 parts of foaming agent, 1-3 parts of coupling agent and 1-3 parts of cross-linking agent;
the wear-resistant polyurethane tire for the forklift is prepared by the following steps:
step S1, carrying out dehydration reaction on the chlorine-containing polyether polyol, controlling the dehydration reaction temperature to be 120 ℃ and the reaction time to be 5 hours; then adding toluene diisocyanate to carry out mixed reaction at 85 ℃ for 3 hours to prepare a prepolymer;
step S2, adding antimony trioxide, a chain extender, a foaming agent, a coupling agent and a crosslinking agent into a stirrer, stirring for 1 hour at room temperature, wherein the stirring speed is 120rpm, and preparing auxiliary materials;
and S3, respectively putting the prepolymer prepared in the step S1 and the auxiliary materials prepared in the step S2 into a casting machine, casting the prepolymer and the auxiliary materials into a tire casting mold for casting molding, demolding to obtain a semi-finished product, polishing the casting seam of the semi-finished product smoothly by using a tire polisher, and vulcanizing at 150 ℃ for 8 hours to obtain the wear-resistant polyurethane tire for the forklift.
2. The abrasion-resistant polyurethane tire for forklift trucks according to claim 1, wherein: the chain extender is one or two of ethylene glycol and 1, 4-butanediol mixed according to any proportion.
3. The abrasion-resistant polyurethane tire for forklift trucks according to claim 1, wherein: the foaming agent is chlorofluorocarbon.
4. The abrasion-resistant polyurethane tire for forklift trucks according to claim 1, wherein: the coupling agent is a silane coupling agent.
5. The abrasion-resistant polyurethane tire for forklift trucks according to claim 1, wherein: the cross-linking agent is one or more of ethylene glycol, 1, 4-butanediol, 1, 3-propanediol and 1, 6-butanediol which are mixed according to any proportion.
6. The abrasion-resistant polyurethane tire for forklift trucks according to claim 1, wherein: the specific preparation process of the chlorine-containing polyether polyol is as follows:
step A1, heating dichlorobutylene glycol to 120 ℃ under the protection of nitrogen, adding boron trifluoride diethyl etherate serving as a catalyst, stirring for 10 minutes, dropwise adding epichlorohydrin, keeping the temperature of the material at 120 ℃ during dropwise adding, and keeping the temperature for 1 hour to obtain an intermediate 1;
step A2, dissolving the intermediate 1 prepared in the step A1 in toluene, slowly adding a sodium hydroxide solution dropwise, standing for layering after the addition is finished, removing a water layer, repeatedly washing the water layer with deionized water until the water layer is neutral, and then evaporating to remove the toluene to obtain an intermediate 2;
step A3, dissolving the intermediate 2 prepared in the step A2 in a mixed solvent of water and methanol, adding nitric acid, heating to 70 ℃, stirring for reacting for 2 hours, then adding calcium hydroxide for neutralizing, removing precipitates and unreacted calcium hydroxide through filtration, and finally evaporating the solvent to obtain the chlorine-containing polyether polyol.
7. The abrasion-resistant polyurethane tire for forklift trucks according to claim 6, wherein: the mol ratio of the dichlorobutylene glycol to the epichlorohydrin in the step A1 is 2:1, and 0.008-0.01 mol of boron trifluoride diethyl etherate is added into each mol of dichlorobutylene glycol.
8. The abrasion-resistant polyurethane tire for forklift trucks according to claim 6, wherein: the dosage ratio of the intermediate 1, the toluene and the sodium hydroxide solution in the step A2 is 10g:100mL:40mL, and the mass fraction of the sodium hydroxide solution is 50%.
9. The abrasion-resistant polyurethane tire for forklift trucks according to claim 6, wherein: and B, mixing the intermediate 2 and the mixed solvent of water and methanol in the step A3 at a dosage ratio of 5g to 100mL, mixing the water and the methanol at a volume ratio of 7 to 1 to prepare the mixed solvent, wherein the mass fraction of the nitric acid is 65%, and adding 1g of nitric acid and 1g of calcium hydroxide into each 100mL of the mixed solvent of water and methanol.
10. The method for preparing the wear-resistant polyurethane tire for the forklift as claimed in claim 1, wherein the method comprises the following steps: the preparation method comprises the following preparation steps:
step S1, carrying out dehydration reaction on the chlorine-containing polyether polyol, controlling the dehydration reaction temperature to be 120 ℃ and the reaction time to be 5 hours; then adding toluene diisocyanate to carry out mixed reaction at 85 ℃ for 3 hours to prepare a prepolymer;
step S2, adding antimony trioxide, a chain extender, a foaming agent, a coupling agent and a crosslinking agent into a stirrer, stirring for 1 hour at room temperature, wherein the stirring speed is 120rpm, and preparing auxiliary materials;
and S3, respectively putting the prepolymer prepared in the step S1 and the auxiliary materials prepared in the step S2 into a casting machine, casting the prepolymer and the auxiliary materials into a tire casting mold for casting molding, demolding to obtain a semi-finished product, polishing the casting seam of the semi-finished product smoothly by using a tire polisher, and vulcanizing at 150 ℃ for 8 hours to obtain the wear-resistant polyurethane tire for the forklift.
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Citations (4)
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|---|---|---|---|---|
| GB1371488A (en) * | 1972-05-15 | 1974-10-23 | Solvay | Halogen-containing polyether-polyols and polyurethane forams produced therefrom |
| US20050164010A1 (en) * | 2004-01-27 | 2005-07-28 | Solvay Solexis S.P.A. | Polyurethanes |
| CN105504260A (en) * | 2015-12-18 | 2016-04-20 | 山东蓝星东大化工有限责任公司 | Hard-foam flame-retardant polyether glycol and preparation method thereof |
| CN108659212A (en) * | 2016-12-18 | 2018-10-16 | 苏州大学 | A kind of preparation method of polyether diatomic alcohol containing fluorine |
-
2020
- 2020-11-09 CN CN202011242058.9A patent/CN112300565B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1371488A (en) * | 1972-05-15 | 1974-10-23 | Solvay | Halogen-containing polyether-polyols and polyurethane forams produced therefrom |
| US20050164010A1 (en) * | 2004-01-27 | 2005-07-28 | Solvay Solexis S.P.A. | Polyurethanes |
| CN105504260A (en) * | 2015-12-18 | 2016-04-20 | 山东蓝星东大化工有限责任公司 | Hard-foam flame-retardant polyether glycol and preparation method thereof |
| CN108659212A (en) * | 2016-12-18 | 2018-10-16 | 苏州大学 | A kind of preparation method of polyether diatomic alcohol containing fluorine |
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