CN116874714B - Polyurethane foaming tyre with low hysteresis loss and preparation method thereof - Google Patents

Polyurethane foaming tyre with low hysteresis loss and preparation method thereof Download PDF

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CN116874714B
CN116874714B CN202311152327.6A CN202311152327A CN116874714B CN 116874714 B CN116874714 B CN 116874714B CN 202311152327 A CN202311152327 A CN 202311152327A CN 116874714 B CN116874714 B CN 116874714B
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polyether polyol
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polyurethane foam
molecular weight
parts
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CN116874714A (en
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公维英
陈纪强
孙兆任
李剑锋
袁立云
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Shandong Inov New Material Co Ltd
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Shandong Inov New Material Co Ltd
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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
    • C08G18/487—Polyethers containing cyclic groups
    • C08G18/4883—Polyethers containing cyclic groups containing cyclic groups having at least one oxygen atom in the ring
    • 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
    • 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
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C08G18/4812—Mixtures of polyetherdiols with polyetherpolyols having at least three hydroxy groups
    • 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
    • C08G18/4829—Polyethers containing at least three hydroxy groups
    • 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
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • 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
    • C08G65/2603—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 oxygen
    • C08G65/2606—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 oxygen containing hydroxyl groups
    • C08G65/2609—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 oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
    • 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
    • C08G65/2642—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 characterised by the catalyst used
    • C08G65/2645—Metals or compounds thereof, e.g. salts
    • C08G65/2654—Aluminium or boron; Compounds thereof
    • 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
    • C08G2101/00—Manufacture of cellular products

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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
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  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention belongs to the technical field of polyurethane foam tires, and particularly relates to a low-hysteresis-loss polyurethane foam tire and a preparation method thereof. The method comprises the following steps: the low hysteresis loss polyurethane foam tire is prepared by reacting a component A and a component B according to the mass ratio of 100 (40-60); wherein the A component comprises high-functionality high-molecular-weight high-activity polyether polyol X, polytetrahydrofuran ether polyol, crosslinking agent, chain extender, catalyst, foam stabilizer, foaming agent, filler and filler, and the B component is 6-functionality polyether polyol Y modified isocyanate. According to the invention, the chemical crosslinking density in the polyurethane soft segment structure and the foam is improved by introducing non-traditional chemical structural raw materials and formula design, the prepared polyurethane foam tire has high supporting strength, low compression set and good rebound resilience, the industrial bottleneck problem that the foam tire cannot rebound or rebound slowly after loading is solved, and the wet heat aging resistance of the product can be effectively improved.

Description

Polyurethane foaming tyre with low hysteresis loss and preparation method thereof
Technical Field
The invention belongs to the technical field of polyurethane foam tires, and particularly relates to a low-hysteresis-loss polyurethane foam tire and a preparation method thereof.
Background
Tires are an indispensable component in transportation means, and are huge in consumption. The traditional tyre is produced by adopting rubber materials, and numerous procedures such as rubber mixing, rubberizing, molding, vulcanizing and the like are needed, so that the investment of manpower and equipment is large, the production and manufacturing process is complex, but the development of the rubber industry is early, the process is mature, and the traditional tyre always occupies the main position of the market. With the progress of various advanced technologies and materials, various novel tires are continuously developed and applied, and a certain application effect is achieved. The polyurethane tire has obvious advantages in the aspects of wear resistance, tearing resistance, cutting resistance, bearing performance and the like as a representative novel tire, has the characteristic of simple production process, has low cost and has very obvious advantages compared with the traditional tire. Polyurethane tires have a development history of decades, but are affected by various factors in application, so that certain defects exist in practical application, such as large heat generation and slow heat transfer in conventional polyurethane foam tires, the heat resistance of the materials is low, the compression set of the foam structure is relatively increased, and therefore, the polyurethane tires can only be suitable for low-speed equipment, and have limited bearing capacity, and cannot rebound completely or rebound slowly after long-term heavy pressure, so that the development of the polyurethane foam tires is restricted.
Patent CN111378273a discloses a low hysteresis loss high strength polyurethane elastomer and a preparation method thereof, which comprises the steps of synthesizing a surface treatment stock solution by polytetrahydrofuran glycol and 2, 4-toluene diisocyanate, diluting by a mixed solvent of ethyl acetate and cyclohexanone, and adding a chain extender to prepare an aramid fibrid surface treatment agent. And then carrying out surface treatment on the aramid fibrid, and mixing the mixture of the aramid fibrid, polytetrahydrofuran glycol and polyoxypropylene glycol with a prepolymer prepared from 2, 4-toluene diisocyanate to finally prepare the polyurethane elastomer, wherein the method cannot be used for polyurethane foaming tires.
Patent CN105153390a discloses an environment-friendly polyurethane foaming tyre composite material and a preparation method thereof. The composite material is prepared by mixing the component A and the component B according to the mass ratio of 100:85-105: the component A is prepared from polyether polyol, polymer polyol, chain extender, cross-linking agent, cell stabilizer, foaming agent and catalyst; the component B is a polyester polyol modified isocyanate component and is prepared from polyester polyol, isocyanate and a storage stabilizer. The prepared environment-friendly polyurethane foaming tire has good skinning property and bright surface while meeting the hardness. However, the polyurethane foaming tyre prepared by the method has larger permanent deformation of material compression caused by larger hysteresis loss, and is easy to deform under long-term heavy pressure.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the low hysteresis loss polyurethane foam tire, which can reduce the compression set of the foam tire, reduce internal heat generation, improve the humidity and heat aging resistance and rebound resilience of products and solve the technical bottleneck problem that the foam tire cannot rebound completely or rebound slowly after being loaded.
The invention also provides a preparation method thereof, which is suitable for mass production.
The low hysteresis loss polyurethane foaming tyre is prepared by reacting a component A and a component B according to the mass ratio of 100 (40-60); the component A comprises the following raw materials in parts by weight:
60-90 parts of polyether polyol X;
10-40 parts of polytetrahydrofuran ether polyol;
8-20 parts of cross-linking and chain extender;
0.5-1.5 parts of catalyst;
0.5-1.5 parts of foam stabilizer;
10-20 parts of foaming agent;
5-20 parts of filler;
the component B is polyether polyol Y modified isocyanate and consists of the following raw materials in parts by mass:
11-37 parts of polyether polyol Y;
57-87 parts of diphenylmethane diisocyanate;
2-6 parts of polymethylene polyphenyl isocyanate;
the polyether polyol X is a polyether polyol with the functionality of 5-8 and the number average molecular weight of 10000-20000g/mol, and the content of primary hydroxyl is more than or equal to 70%;
the polytetrahydrofuran ether polyol has the functionality of 2-3 and the number average molecular weight of 1000-3000 g/mol; preferably, one or a mixture of several of PTMG1000, PTMG1300, PTMG1500, PTMG1800, PTMG2000, PTMG3000 of Mitsubishi chemical in Japan is used.
The polyether polyol Y is a polyether polyol with the functionality of 6 and the number average molecular weight of 6000-12000 g/mol.
The polyether polyol X is prepared by ring-opening polymerization of propylene oxide at 30-100 ℃ by adding an initiator and a catalyst, wherein the initiator is small molecular alcohol, low molecular weight polyether polyol or a composite initiator consisting of the small molecular alcohol and the low molecular weight polyether polyol, and the catalyst is alkyl borane, boron salt or borate;
the small molecular alcohol is one or a mixture of more of pentaerythritol, xylitol, mannitol, sorbitol, inositol, dipentaerythritol, sucrose, alpha-methyl glucoside, benzene hexaphenol and 2,3,6,7,10, 11-hexahydroxy triphenyl;
the low molecular weight polyether polyol is prepared by polymerizing the low molecular weight polyether polyol with propylene oxide under the catalysis of KOH by using the small molecular weight alcohol as an initiator and carrying out neutralization, adsorption and dehydration, wherein the number average molecular weight is 1000-3000g/mol, and the water content is less than or equal to 0.02wt.%;
the mass ratio of the small molecular alcohol to the low molecular polyether polyol in the composite initiator is 1 (1-50);
preferably, the mass ratio of the initiator to the propylene oxide is 1 (10-30);
the alkyl borane, the boron salt or the borate catalyst is one or a mixture of more of triethyl borane, tributyl borane, tris (pentafluorophenyl) borane, triphenyl butyl borane, trimethoxyphenyl butyl boron, tetraethyl triphenyl butyl boron, tetraethyl sodium borate, triethyl boron phenyl lithium and triethyl boron phenyl tetramethyl ammonium salt, and the dosage of the alkyl borane, the boron salt or the borate catalyst is 30-200ppm of the total mass of the raw materials of the reaction system.
The crosslinking and chain extending agent is selected from INOVOL R403, INOVOL R405, INOVOL F414, glycerol, ethylene glycol, 1, 4-butanediol, diethylene glycol, triethylene glycol, 1, 6-hexanediol, cyclohexanediol, hydroquinone dihydroxyethyl ether (HQEE), methyl propylene glycol, resorcinol dihydroxyethyl ether (HER), 4-hydroxyethyl oxyethyl-1-hydroxyethyl benzene diether (HQEE-L), 1, 7-heptanediol, 1, 8-octanediol, 1, 9-nonanediol or 1, 10-decanediol; wherein: INOVOLR403, INOVOLR 405, inovoll F414, glycerol are cross-linkers, the remainder being chain extenders.
The mass ratio of the cross-linking agent to the chain extender is (0-5) to (10-30).
The catalyst is one or a mixture of two of tertiary amine catalysts and organic metal catalysts.
The tertiary amine catalyst is one or a mixture of a plurality of triethylenediamine solution A-33, bis (dimethylaminoethyl) ether solution A-1, tetramethyl-propylenediamine, tris (dimethylaminopropyl) hexahydrotriazine, dimethylacetamide, diethylacetamide, bis (dimethylamino) -2-propanol and amine delay catalyst.
The organic metal catalyst is preferably one or a mixture of several of dibutyl tin dilaurate T-12, stannous octoate T-9, dibutyl tin diacetate, dibutyl tin dilauryl sulfide, dibutyl tin dimercaptoacetate, dioctyl tin dimercaptoacetate, potassium acetate, potassium isooctanoate, potassium oleate, zinc isooctanoate and bismuth isooctanoate.
The foam stabilizer is one or a mixture of several of B8900 (commercially available, win-making specialty Chemie Co., ltd.), B8946 (commercially available, win-making specialty Chemie Co., ltd.), B8707LF2 (commercially available, win-making specialty Chemie Co., ltd.), DC5000 (commercially available, american air chemical products Co., ltd.), DC3042 (commercially available, american air chemical products Co., ltd.).
The foaming agent is a physical foaming agent, a chemical foaming agent or a mixture of the physical foaming agent and the chemical foaming agent.
The physical foaming agent is one or a mixture of more of HCFC-141b, dichloromethane and liquid carbon dioxide, and the chemical foaming agent is ammonia water, so that the double functions of crosslinking and foaming are achieved, and the mechanical strength is improved.
The filler is one or a mixture of a plurality of kaolin, talcum powder, calcium carbonate, diatomite, wollastonite powder, mica powder, titanium pigment, silicon micropowder, barite powder, gypsum powder and carbon black, and the filler can be added to strengthen and improve the open pore property of the whole system on one hand and reduce the cost on the other hand.
The component A can be added with other auxiliary agents such as defoamer, pore-disturbing agent, pigment, color paste and the like according to performance requirements.
The preparation method of the low hysteresis loss polyurethane foam tire comprises the following steps:
and (3) preparation of the component A: firstly, putting polyether polyol X and polytetrahydrofuran ether polyol into a reaction kettle for stirring, then adding a crosslinking agent, a chain extender, a catalyst, a foam stabilizer, a foaming agent and a filler, stirring for 1-2 hours at room temperature, and then sealing and preserving;
and (3) preparation of a component B: putting polyether polyol Y into a reaction kettle at normal temperature, stirring and heating to 90-100 ℃, dehydrating and degassing for 2-3h under vacuum condition, cooling to 40 ℃, adding diphenylmethane diisocyanate, heating to 80-85 ℃ for reacting for 2-3h, adding polymethylene polyphenyl isocyanate, stirring for 30min, testing that the mass content of-NCO reaches 20-30%, cooling to 40-50 ℃, and sealing and preserving;
and placing the A, B component in a tank corresponding to a low-pressure casting machine, preserving heat at 25-35 ℃, mixing the A component and the B component in proportion, casting into a tire mold, opening the mold for 3min, and trimming and exhausting to obtain the low-hysteresis-loss polyurethane foam tire.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention adopts high functionality high molecular weight polyether polyol to improve the chemical crosslinking density in polyurethane foam, and the polyether used adopts alkyl borane, boron salt or borate to catalyze pure epoxypropane to carry out ring-opening polymerization, so that the polyether polyol with the mass content of primary hydroxyl groups of more than or equal to 70 percent can be obtained without end capping of epoxyethane, and the high polyether functionality and the primary hydroxyl group content endow a formula system with sufficient crosslinking curing speed and post curing speed, thereby solving the problems of crosslinking curing and slow curing speed of the polyurethane foam and effectively improving the humidity and heat aging resistance of products.
(2) The polyurethane foam tire prepared by the invention has high supporting strength, low compression set and good rebound resilience, and effectively solves the bottleneck problems that the foam tire cannot rebound completely or rebound slowly after being loaded.
Detailed Description
The invention is further illustrated by the following examples.
All materials used in the examples are commercially available, except as specified.
Inonol C310, new material inc. Northwest, shandong (functionality 3, number average molecular weight 1000 g/mol);
inonol F3600, new material, eastern norwegian co.ltd (functionality 3, number average molecular weight 6000g/mol, EO-capped);
inonol F628, shandong monowiry new materials limited (functionality 6, number average molecular weight 12000g/mol, EO-capped);
inonol R403, new material inc. Northwest, shandong (functionality 4, number average molecular weight 300 g/mol);
inonol F414, new material limited of northwest, shandong (functionality 4, number average molecular weight 1400 g/mol);
polytetrahydrofuran ether polyol:
PTMG1000, mitsubishi chemical in Japan (functionality 2, number average molecular weight 1000 g/mol);
PTMG2000, mitsubishi chemical in Japan (functionality 2, number average molecular weight 2000 g/mol);
PTMG3000, mitsubishi chemical in Japan (functionality 2, number average molecular weight 3000 g/mol);
diphenylmethane diisocyanate: MDI-100, wanhua chemical group Co., ltd;
polymethylene polyphenyl isocyanates: PM-200, wanhua chemical group Co., ltd;
foam stabilizer, B8946, win specialty chemistry limited;
foam stabilizers, DC3042, air chemical products Co., ltd.
Preparation of polyether polyol X1:
(1) Adding 182g of sorbitol and 5g of KOH into a pressure-resistant reaction kettle, heating to 100 ℃ for dehydration for 1h after nitrogen replacement for 3 times, dropwise adding 1820g of propylene oxide at 110 ℃, controlling the pressure in the reaction process to be less than 0.30MPa, carrying out internal pressure reaction for 2h, vacuumizing to remove unreacted residual monomers, cooling to 85 ℃, sequentially adding 12.5g of 70% phosphoric acid, 70g of water and 2g of magnesium silicate, dehydrating and carrying out suction filtration to obtain the low molecular weight polyether polyol (1), wherein the functionality is 6, the hydroxyl value is 170mgKOH/g, the number average molecular weight is 1980g/mol, and the water content is 0.017;
(2) 21.5g of sorbitol (which is dried in a vacuum drying oven in advance, the moisture content is less than or equal to 0.02 wt.%), 100g of low molecular weight polyether polyol (1), 0.117g of tris (pentafluorophenyl) borane and 0.1g of tetraethyl sodium borate are added into a pressure-resistant reaction kettle, after 3 times of nitrogen replacement, the temperature is raised to 65 ℃, 2150g of propylene oxide is added dropwise, the pressure in the reaction process is controlled to be less than 0.30MPa, the internal pressure is reacted for 2 hours, vacuum pumping is carried out to remove unreacted residual monomers, and the target polyether polyol X1 is obtained, the hydroxyl value is 27.8mgKOH/g, the functionality is 6, the number average molecular weight is 12108g/mol, and the primary hydroxyl content is 72%.
Preparation of polyether polyol X2:
30.4g of xylitol (which is subjected to drying treatment in a vacuum drying oven in advance, the moisture content is less than or equal to 0.02 wt.%), 0.072g of triethylborophenyl lithium are added into a pressure-resistant reaction kettle, the temperature is raised to 100 ℃ after 3 times of nitrogen replacement, 2370g of propylene oxide is dripped, the pressure in the reaction process is controlled to be less than 0.30MPa, the internal pressure is controlled to react for 2 hours, vacuum pumping is carried out to remove unreacted residual monomers, and the target polyether polyol X2 with the hydroxyl value of 26.7mgKOH/g, the functionality degree of 5, the number average molecular weight of 10505g/mol and the primary hydroxyl content of 75% is obtained. Preparation of polyether polyol X3:
(1) Adding 228g of sucrose, 5g of pentaerythritol and 5.3g of KOH into a pressure-resistant reaction kettle, heating to 100 ℃ for dehydration for 1h after nitrogen replacement for 3 times, dropwise adding 2095g of propylene oxide at 110 ℃, controlling the pressure in the reaction process to be less than 0.30MPa, carrying out internal pressure reaction for 2h, vacuumizing to remove unreacted residual monomers, cooling to 85 ℃, sequentially adding 13.1g of 70% phosphoric acid, 74g of water and 2.1g of magnesium silicate, and carrying out dehydration and suction filtration to obtain low-molecular-weight polyether polyol (3), wherein the functionality is 7.8, the hydroxyl value is 113mgKOH/g, the number average molecular weight is 2970g/mol, and the water content is 0.015%;
(2) 297g of low molecular weight polyether polyol (3), 0.3g of trimethoxyphenyl butyl boron, 0.1g of tetraethyl amine triphenyl butyl boron and 0.04g of tributyl borane are added into a pressure resistant reaction kettle, after 3 times of nitrogen replacement, the temperature is raised to 30 ℃, 1905g of propylene oxide is dropwise added, the pressure in the reaction process is controlled to be less than 0.30MPa, the internal pressure is controlled to react for 2 hours, vacuum pumping is carried out to remove unreacted residual monomers, and the target polyether polyol X3 is obtained, the hydroxyl value is 22.3mgKOH/g, the functionality is 7.8, the number average molecular weight is 19622g/mol, and the primary hydroxyl content is 74%.
Preparation of polyether polyol X4:
61g of dipentaerythritol (the water content is less than or equal to 0.02wt.% in a vacuum drying oven in advance) and 0.30g of triethylboron phenyl tetramethylammonium salt are added into a pressure-resistant reaction kettle, the temperature is raised to 85 ℃ after 3 times of nitrogen replacement, 2940g of propylene oxide is dropwise added, the pressure in the reaction process is controlled to be less than 0.30MPa, the internal pressure is controlled to react for 2 hours, vacuum pumping is carried out to remove unreacted residual monomers, and the target polyether polyol X4 with the hydroxyl value of 28.2mgKOH/g, the functionality degree of 6, the number average molecular weight of 11894g/mol and the primary hydroxyl content of 71% is obtained.
Preparation of polyether polyol X5:
300g of INOVOL C310 (moisture 0.012 wt.%) and 0.156g of tris (pentafluorophenyl) borane are added into a pressure-resistant reaction kettle, after 3 times of nitrogen replacement, the temperature is raised to 80 ℃, 1650g of propylene oxide is added dropwise, the pressure in the reaction process is controlled to be less than 0.30MPa, the internal pressure is controlled to react for 2 hours, vacuum pumping is carried out to remove unreacted residual monomers, and the target polyether polyol X5 is obtained, the hydroxyl value is 27.7mgKOH/g, the functionality is 3, the number average molecular weight is 6076g/mol, and the primary hydroxyl content is 74%.
Polyether polyol Y1 (functionality 6, number average molecular weight 6000g/mol, EO cap) preparation method:
adding 720g of sorbitol and 60.84g of KOH into a pressure-resistant reaction kettle, heating to 100 ℃ for dehydration for 1h after nitrogen replacement for 3 times, dropwise adding 19980g of propylene oxide at 110 ℃, controlling the pressure in the reaction process to be less than 0.30MPa, carrying out internal pressure reaction for 2h, vacuumizing to remove unreacted residual monomers, dropwise adding 3660g of ethylene oxide at 115 ℃, controlling the pressure in the reaction process to be less than 0.30MPa, carrying out internal pressure reaction for 1h, vacuumizing to remove unreacted residual monomers, cooling to 85 ℃, sequentially adding 152.4g of 70% phosphoric acid, 852g of water and 24g of magnesium silicate, dehydrating and carrying out suction filtration to obtain the low molecular weight polyether polyol Y1, the functionality is 6, the hydroxyl value is 55.8mgKOH/g, and the number average molecular weight is 6027g/mol.
Polyether polyol Y2 (functionality 6, number average molecular weight 9000g/mol, EO cap) preparation method:
480g of sorbitol and 60.48g of KOH are added into a pressure-resistant reaction kettle, nitrogen is replaced for 3 times, the temperature is raised to 100 ℃ for dehydration for 1h, 20124g of propylene oxide is dripped at 110 ℃, the pressure in the reaction process is controlled to be less than 0.30MPa, the internal pressure is controlled to react for 2h, vacuum pumping is performed to remove unreacted residual monomers, 3636g of ethylene oxide is dripped at 115 ℃, the pressure in the reaction process is controlled to be less than 0.30MPa, the internal pressure is controlled to react for 1h, vacuum pumping is performed to remove unreacted residual monomers, the temperature is reduced to 85 ℃, 151.2g of 70% phosphoric acid, 852g of water and 24g of magnesium silicate are sequentially added, and the low molecular weight polyether polyol Y2 with the functionality of 6, the hydroxyl value of 37.3mgKOH/g and the number average molecular weight of 9016g/mol is obtained after dehydration and suction filtration.
Example 1
The preparation method of the low hysteresis loss polyurethane foam tire comprises the following steps:
and (3) preparation of the component A: 85kg of polyether polyol X1 and 15kg of PTMG2000 are weighed into a reaction kettle respectively and stirred at a speed of 100R/min, and then 2kg of INOVOL R403, 14kg of diethylene glycol, 0.4kg of A-33,0.2kg of A-1,0.05kg of T-12,0.5kg of potassium acetate, 0.8kg of B8946,7kg of talcum powder, 0.5kg of ammonia water and 12kg of HCFC-141B are added. Stirring at room temperature for 1 hr, mixing, and sealing.
And (3) preparation of a component B: adding 21kg of polyether polyol Y1 (with a functionality of 6 and a number average molecular weight of 6000g/mol and EO end-capped) into a reaction kettle at normal temperature, stirring and heating to 95+/-5 ℃, dehydrating and degassing for 2 hours under the vacuum degree of less than-0.088 MPa, cooling to 40 ℃, adding 74kg of MDI-100, reacting for 2 hours at 82+/-2.5 ℃, adding 5kg of PM-200, stirring for 30 minutes, sampling and detecting, measuring the concentration of the NCO to 25.0 wt%, cooling to 45+/-5 ℃ after being qualified, and sealing and storing.
When the polyurethane foaming tyre is used, the temperature of A, B components is maintained at 30+/-5 ℃, the components A and B are poured into a dynamic tyre mould according to the mass ratio of 100:50, the mould temperature is 52+/-2 ℃, the mould is opened for 3min, and the polyurethane foaming tyre is prepared by natural curing for 1h after trimming and exhausting.
Example 2
The preparation method of the low hysteresis loss polyurethane foam tire comprises the following steps:
and (3) preparation of the component A: 85kg of polyether polyol X2 and 15kg of PTMG3000 are weighed respectively, put into a reaction kettle and stirred at a speed of 100r/min, and then 2kg of INOVOL F414, 6kg of 1, 4-butanediol, 4kg of ethylene glycol, 0.4kg of A-33,0.1kg of tetramethyl-propylenediamine, 0.1kg of tris (dimethylaminopropyl) hexahydrotriazine, 0.05kg of T-12,0.5kg of potassium isooctanoate, 0.8kg of B8946,7kg of kaolin and 16kg of dichloromethane are added. Stirring at room temperature for 1 hr, mixing, and sealing.
And (3) preparation of a component B: putting 21kg of polyether polyol Y2 (with a functionality of 6, a number average molecular weight of 9000g/mol and EO end-capped) into a reaction kettle at normal temperature, stirring and heating to 95+/-5 ℃, dehydrating and degassing for 2.5 hours under the condition that the vacuum degree is lower than-0.088 MPa, cooling to 40 ℃, adding 33kg of MDI-100, reacting for 2.5 hours at 82+/-2.5 ℃, adding 3kg of PM-200, stirring for 30 minutes, sampling and detecting, measuring that the-NCO concentration is 20.2wt.%, cooling to 45+/-5 ℃ after being qualified, and sealing and storing.
When the polyurethane foaming tyre is used, the temperature of A, B components is maintained at 30+/-5 ℃, the components A and B are poured into a dynamic tyre mould according to the mass ratio of 100:59.5, the mould temperature is 52+/-2 ℃, the mould is opened for 3min, and the polyurethane foaming tyre is prepared by naturally curing for 1h after trimming and exhausting.
Example 3
The preparation method of the low hysteresis loss polyurethane foam tire comprises the following steps:
and (3) preparation of the component A: 80kg of polyether polyol X3 and 20kg of PTMG1000 are weighed respectively, put into a reaction kettle and stirred at a speed of 100r/min, and then 1.5kg of glycerin, 2kg of methyl propylene glycol, 7kg of diethylene glycol, 0.6kg of A-33,0.03kg of T-9,0.5kg of potassium oleate, 0.8kg of B8946,7kg of calcium carbonate, 0.5kg of ammonia water and 10kg of liquid carbon dioxide are added. Stirring at room temperature for 1 hr, mixing, and sealing.
And (3) preparation of a component B: putting 21kg of INOVOL F628 into a reaction kettle at normal temperature, stirring and heating to 95+/-5 ℃, dehydrating and degassing for 3 hours under the vacuum degree lower than-0.088 MPa, cooling to 40 ℃, adding 160kg of MDI-100, reacting for 3 hours at 82+/-2.5 ℃, adding 4kg of PM-200, stirring for 30min, sampling and detecting, wherein the measured-NCO concentration is 29.6 wt%, cooling to 45+/-5 ℃ after passing, and sealing and preserving.
When the polyurethane foaming tyre is used, the temperature of A, B components is maintained at 30+/-5 ℃, the components A and B are poured into a dynamic tyre mould according to the mass ratio of 100:40.8, the mould temperature is 52+/-2 ℃, the mould is opened for 3min, and the polyurethane foaming tyre is prepared by naturally curing for 1h after trimming and exhausting.
Example 4
The preparation method of the low hysteresis loss polyurethane foam tire comprises the following steps:
and (3) preparation of the component A: 60kg of polyether polyol X4 and 40kg of PTMG2000 are weighed respectively, put into a reaction kettle and stirred at a speed of 100R/min, and then 3.5kg of INOVOL R403, 16.5kg of diethylene glycol, 0.45kg of A-33,0.05kg of T-12,0.5kg of B8946,5kg of talcum powder, 0.7kg of ammonia water, 7.0kg of HCFC-141B and 2.3kg of dichloromethane are added. Stirring at room temperature for 1 hr, mixing, and sealing.
And (3) preparation of a component B: adding 21kg of polyether polyol Y1 (with a functionality of 6, a number average molecular weight of 6000 and EO end capping) into a reaction kettle at normal temperature, stirring and heating to 95+/-5 ℃, dehydrating and degassing for 2.5 hours under the vacuum degree of less than-0.088 MPa, cooling to 40 ℃, adding 74kg of MDI-100, reacting for 2.5 hours at 82+/-2.5 ℃, adding 5kg of PM-200, stirring for 30 minutes, sampling and detecting, measuring the concentration of the-NCO to 25.0 wt%, cooling to 45+/-5 ℃ after being qualified, and sealing and storing.
When the polyurethane foaming tyre is used, the temperature of A, B components is maintained at 30+/-5 ℃, the components A and B are poured into a dynamic tyre mould according to the mass ratio of 100:59, the mould temperature is 52+/-2 ℃, the mould is opened for 3min, and the polyurethane foaming tyre is prepared by natural curing for 1h after trimming and exhausting.
Example 5
The preparation method of the low hysteresis loss polyurethane foam tire comprises the following steps:
and (3) preparation of the component A: 90kg of polyether polyol X1 and 10kg of PTMG1000 are weighed respectively, put into a reaction kettle and stirred at a speed of 100r/min, and then 5kg of 1, 4-butanediol, 3kg of ethylene glycol, 0.6kg of A-33,0.05kg of T-12,0.8kg of bismuth iso-octoate, 1.5kg of DC3042, 20kg of mica powder, 0.3kg of ammonia water, 10kg of HCFC-141b,4kg of liquid carbon dioxide and 5.5kg of methylene dichloride are added. Stirring at room temperature for 1 hr, mixing, and sealing.
And (3) preparation of a component B: adding 21kg of polyether polyol Y1 (with a functionality of 6, a number average molecular weight of 6000 and EO end capping) into a reaction kettle at normal temperature, stirring and heating to 95+/-5 ℃, dehydrating and degassing for 2.5 hours under the vacuum degree of less than-0.088 MPa, cooling to 40 ℃, adding 74kg of MDI-100, reacting for 2.5 hours at 82+/-2.5 ℃, adding 5kg of PM-200, stirring for 30 minutes, sampling and detecting, measuring the concentration of the-NCO to 25.0 wt%, cooling to 45+/-5 ℃ after being qualified, and sealing and storing.
When the polyurethane foaming tyre is used, the temperature of A, B components is maintained at 30+/-5 ℃, the components A and B are poured into a dynamic tyre mould according to the mass ratio of 100:41, the mould temperature is 52+/-2 ℃, the mould is opened for 3min, and the polyurethane foaming tyre is prepared by natural curing for 1h after trimming and exhausting.
Comparative example 1
This comparative example differs from example 1 only in that polyether polyol X5 was used instead of polyether polyol X1 to prepare a polyurethane foam tire; the preparation method is the same as in example 1.
Comparative example 2
This comparative example differs from example 1 only in that polyether polyol inovaol F628 was used instead of polyether polyol X1 to prepare a polyurethane foam tire; the preparation method is the same as in example 1.
Comparative example 3
This comparative example differs from example 1 only in that polyether polyol INOVOL F3600 was used in place of polyether polyol X1 to prepare a polyurethane foam tire; the preparation method is the same as in example 1.
The rebound speed testing method comprises the following steps: pressing a heavy object with the mass of 1 ton on the product prepared by the method for 24 hours, and recording the rebound time of the product;
compression set was tested according to GB/T10653-2001 determination of compression set of high Polymer porous elastic Material;
hysteresis loss is tested according to GB/T33609-2017 Soft foam polymeric Material hysteresis loss test method;
tensile strength and elongation at break were tested according to GB/T6344-2008 determination of tensile Strength and elongation at break of Soft foam Polymer Material;
resistance to thermal aging under humidity: the mixture was treated at a temperature of 85℃and a humidity of 85% for 500 hours, and the tensile strength and elongation at break loss were calculated.
TABLE 1 results of polyurethane foam tire Performance test of examples 1-5 and comparative examples 1-3
As can be seen from Table 1, the polyurethane foam tires prepared in examples 1 to 5 and comparative example 2 using higher functionality polyether polyol have lower compression set, hysteresis loss and rebound time than comparative examples 1 and 3, and because of the high functionality, more crosslinked network structure can be formed in the reaction, which is advantageous for improving the mechanical properties of the materials; examples 1-5 and comparative example 1 use pure propylene oxide to prepare high activity polyether polyol X, compared to comparative examples 2 and 3; the inomol C310 used in the polyether polyol X5 used in comparative example 1 is a glycerol-based polyether polyol, unlike other small molecular alcohols or low molecular weight polyether polyols used in examples, the resulting polyether polyol X5 has a low functionality, and thus the examples have better performance than comparative example 1.

Claims (9)

1. A low hysteresis loss polyurethane foaming tyre is characterized in that the tyre is prepared by reacting an A component and a B component according to the mass ratio of 100 (40-60); the component A comprises the following raw materials in parts by weight:
60-90 parts of polyether polyol X;
10-40 parts of polytetrahydrofuran ether polyol;
8-20 parts of cross-linking and chain extender;
0.5-1.5 parts of catalyst;
0.5-1.5 parts of foam stabilizer;
10-20 parts of foaming agent;
5-20 parts of filler;
the component B is polyether polyol Y modified isocyanate and consists of the following raw materials in parts by mass:
11-37 parts of polyether polyol Y;
57-87 parts of diphenylmethane diisocyanate;
2-6 parts of polymethylene polyphenyl isocyanate;
the polyether polyol X is a polyether polyol with the functionality of 5-8 and the number average molecular weight of 10000-20000g/mol, and the content of primary hydroxyl is more than or equal to 70%;
the polytetrahydrofuran ether polyol has the functionality of 2-3 and the number average molecular weight of 1000-3000 g/mol;
the polyether polyol Y is a polyether polyol with the functionality of 6 and the number average molecular weight of 6000-12000 g/mol;
the polyether polyol X is prepared by ring-opening polymerization of a small molecular alcohol, a low molecular weight polyether polyol or a composite initiator composed of the small molecular alcohol and the low molecular weight polyether polyol by adding propylene oxide into a catalyst for the polymerization of the polyether polyol X at the temperature of 30-100 ℃, and the catalyst for the polymerization of the polyether polyol X is alkyl borane, boron salt or borate;
the small molecular alcohol is one or a mixture of more of pentaerythritol, xylitol, mannitol, sorbitol, inositol, dipentaerythritol, sucrose, alpha-methyl glucoside, benzene hexaphenol and 2,3,6,7,10, 11-hexahydroxy triphenyl;
the low molecular weight polyether polyol is prepared by polymerizing the low molecular weight polyether polyol serving as an initiator with propylene oxide under the catalysis of KOH, and carrying out neutralization, adsorption and dehydration, wherein the number average molecular weight is 1000-3000g/mol, and the water content is less than or equal to 0.02wt.%.
2. The low hysteresis loss polyurethane foam tire according to claim 1, wherein the alkyl borane, boron salt or borate catalyst is one or a mixture of several of triethylborane, tributylborane, tris (pentafluorophenyl) borane, triphenylborane, triphenylbutylborane, trimethyloxybutylboro, triethylphenylbutylboron, tetraethylsodium borate, triethylphenyllithium borate and triethylphenyltetramethylammonium salt, and the amount thereof is 30-200ppm based on the total mass of the reaction system raw materials.
3. The low hysteresis loss polyurethane foam tire according to claim 1, wherein the crosslinking, chain extender is two or more of inodiol R403, inodiol R405, inodiol F414, glycerol, ethylene glycol, 1, 4-butanediol, diethylene glycol, triethylene glycol, 1, 6-hexanediol, cyclohexanediol, hydroquinone dihydroxyethyl ether, methylpropanediol, resorcinol dihydroxyethyl ether, 4-hydroxyethyl oxyethyl-1-hydroxyethyl benzene diether, 1, 7-heptanediol, 1, 8-octanediol, 1, 9-nonanediol, or 1, 10-decanediol.
4. The low hysteresis loss polyurethane foam tire according to claim 1, wherein the catalyst is one or a mixture of two of a tertiary amine-based catalyst and an organometallic catalyst.
5. The low hysteresis loss polyurethane foam tire according to claim 4, wherein the tertiary amine catalyst is one or a mixture of several of triethylenediamine solution a-33, bis (dimethylaminoethyl) ether solution a-1, tetramethylpropanediamine, tris (dimethylaminopropyl) hexahydrotriazine, dimethylacetamide, diethylacetamide, bis (dimethylamino) -2-propanol, and amine delay catalysts.
6. The low hysteresis loss polyurethane foam tire according to claim 4, wherein the organometallic catalyst is one or a mixture of several of dibutyltin dilaurate T-12, stannous octoate T-9, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dimercaptoacetate, dioctyltin dimercaptoacetate, potassium acetate, potassium isooctanoate, potassium oleate, zinc isooctanoate, bismuth isooctanoate.
7. The low hysteresis loss polyurethane foam tire according to claim 1, wherein the foaming agent is a physical foaming agent, a chemical foaming agent, or a mixture of a physical foaming agent and a chemical foaming agent.
8. The low hysteresis loss polyurethane foam tire according to claim 7, wherein the physical blowing agent is one or a mixture of more of HCFC-141b, methylene chloride and liquid carbon dioxide, and the chemical blowing agent is ammonia.
9. A method for preparing the low hysteresis loss polyurethane foam tire according to any one of claims 1 to 8, comprising the steps of:
and (3) preparation of the component A: firstly, putting polyether polyol X and polytetrahydrofuran ether polyol into a reaction kettle for stirring, then adding a crosslinking agent, a chain extender, a catalyst, a foam stabilizer, a foaming agent and a filler, stirring at room temperature, and then sealing and preserving;
and (3) preparation of a component B: putting polyether polyol Y into a reaction kettle at normal temperature, stirring and heating to 90-100 ℃, dehydrating and degassing for 2-3 hours under vacuum condition, cooling, adding diphenylmethane diisocyanate, heating to 80-85 ℃ for reacting for 2-3 hours, adding polymethylene polyphenyl isocyanate, stirring, testing that the mass content of-NCO reaches 20-30%, cooling to 40-50 ℃, and sealing and preserving;
and placing the A, B component in a tank corresponding to a low-pressure casting machine, preserving heat at 25-35 ℃, mixing the A component and the B component in proportion, casting into a tire mold, opening the mold, trimming, and exhausting to obtain the low-hysteresis-loss polyurethane foam tire.
CN202311152327.6A 2023-09-08 2023-09-08 Polyurethane foaming tyre with low hysteresis loss and preparation method thereof Active CN116874714B (en)

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