CN111533868B - Polyurethane for low-speed solid tire - Google Patents
Polyurethane for low-speed solid tire Download PDFInfo
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- CN111533868B CN111533868B CN202010465476.8A CN202010465476A CN111533868B CN 111533868 B CN111533868 B CN 111533868B CN 202010465476 A CN202010465476 A CN 202010465476A CN 111533868 B CN111533868 B CN 111533868B
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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
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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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
- B60C7/00—Non-inflatable or solid tyres
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3215—Polyhydroxy compounds containing aromatic groups or benzoquinone groups
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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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3225—Polyamines
- C08G18/3237—Polyamines aromatic
- C08G18/3243—Polyamines aromatic containing two or more aromatic rings
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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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4202—Two or more polyesters of different physical or chemical nature
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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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4244—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups
- C08G18/4247—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids
- C08G18/4252—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids derived from polyols containing polyether groups and polycarboxylic acids
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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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6648—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6651—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
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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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6648—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6655—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
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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
- B60C7/00—Non-inflatable or solid tyres
- B60C2007/005—Non-inflatable or solid tyres made by casting, e.g. of polyurethane
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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
- C08G2110/00—Foam properties
- C08G2110/0083—Foam properties prepared using water as the sole blowing agent
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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
- C08G2380/00—Tyres
Abstract
The polyurethane for the low-speed solid tire is obtained by reacting an isocyanate-reactive component A and an isocyanate-containing prepolymer component B, wherein the molar ratio of isocyanate-reactive groups in the component A to-NCO groups in the component B is (0.95-1.05): 1; the component A contains: polyether ester polyols, binary primary alcohols; a polyalcohol amine; the component B comprises: polyisocyanates, polyetherester polyols, aromatic diols and/or aromatic diamines; the polyurethane product obtained by the synergistic effect of the component A and the component B has excellent properties such as wear resistance, tensile strength, tear strength, tensile strength, rebound resilience, compression deformation and the like, and when the product is used as a low-speed solid tire, the tire has good bearing and deformation resistance, good elasticity and obvious buffering effect, and in addition, the product can be used in outdoor environment for a long time and can keep excellent physical and mechanical properties.
Description
Technical Field
The invention belongs to the technical field of polyurethane, relates to polyurethane, and relates to a low-speed solid tire finished product obtained from the polyurethane.
Background
Tires, which are main accessories of vehicles, are largely classified into pneumatic tires and solid tires. The pneumatic tire has good buffering effect, but is easy to wear and leak, so the pneumatic tire is generally applied to vehicles with higher requirements on comfort level and running speed; the solid tire has a relatively poor buffering effect due to relatively high density of the tire body, but the load-bearing performance of the solid tire is generally higher than that of a pneumatic tire, and the solid tire is mainly used for vehicles which run at low speed, have requirements on load and are used outdoors for a long time. Traditional solid tire materials are mainly made of rubber, such as patents CN110511445A, CN108752657A, etc.
In recent years, along with the improvement of the requirements of the market on the comfort, the buffer effect and the like of the solid tire, the requirement of the polyurethane solid tire with certain elasticity is increased, and the wear-resistant polyurethane solid tire disclosed in the patent CN106800637A is formed by casting a prepolymer system by using a polyol, wherein the polyol which is one of main raw materials is polyether polyol with the molecular weight of 6000-8000, but the method has the advantages of long vulcanization time after subsequent vulcanization, low production efficiency and poor tensile strength; the polyurethane solid tire reported in patent CN104497252A adopts two polyether polyols with different molecular weights and 3 functionalities, and although the method for manufacturing the solid tire is simple and easy to implement and high in production efficiency, the tire manufactured by adopting the polyether polyol and the modified black material is generally low in breaking elongation and poor in flexibility; the patent CN105330811A discloses a polyurethane solid tire material, which comprises a component A and a component B, wherein the component A is polyester polyol, a chain extender, a foaming agent, a catalyst A and a foam stabilizer, and the component B is isocyanate, polyester polyol and polyether polyol. At present, the solid tire prepared from the polyurethane material has the performance of good buffering, high strength, hydrolysis resistance, wear resistance and the like. Therefore, on the premise of ensuring that the polyurethane solid tire has certain buffering capacity and improves comfort, the physical mechanical strength, the hydrolyzability and the wear resistance of the tire are effectively improved, and the polyurethane solid tire has important significance for wide application on vehicles.
Disclosure of Invention
The technical problem is as follows: in order to overcome the defects of the prior art, the invention provides the polyurethane for the low-speed solid tire, and the polyurethane provided by the invention has the properties of good buffering effect, good bearing and deformation resistance, high wear resistance, high hydrolysis resistance, high strength and the like.
The technical scheme is as follows: the polyurethane for the low-speed solid tire is obtained by reacting an isocyanate-reactive component A and an isocyanate-containing prepolymer component B, wherein the molar ratio of isocyanate-reactive groups in the component A to-NCO groups in the component B is (0.95-1.05): 1;
the component A which has reactivity to isocyanate comprises the following components in parts by weight:
a1: 70-100 parts by weight of polyether ester polyol with the number average molecular weight of 2000-3000 and the average hydroxyl functionality of more than 2 and less than 3;
a3: 5-15 parts by weight of a binary primary alcohol having 2-6 carbon atoms;
a4: 0.3 to 1.2 parts by weight of polyalcohol amine;
the isocyanate-containing prepolymer B component comprises the following components in parts by weight: the prepolymerization reaction obtains:
b1: 56-72 parts by weight of polyisocyanate;
a1: 26-40 parts by weight of polyether ester polyol with the number average molecular weight of 2000-3000 and the average hydroxyl functionality of more than 2 and less than 3;
b2: 2-4 parts by weight of aromatic diol and/or aromatic diamine;
the-NCO group of the B component of the isocyanate prepolymer is calculated based on the total mass of the B component, and the mass content is 17-21 wt%.
Wherein the content of the first and second substances,
the component A with reactivity to isocyanate also comprises polyester polyol A2 with the number average molecular weight of 1500-3000 and the average hydroxyl functionality of 2, a catalyst, a foaming agent, a foam stabilizer, a plasticizer and one or more aging resistant agents.
The polyether ester polyol A1 is obtained by taking polyether diol with the number average molecular weight of 250-650 as an initiator and carrying out condensation reaction with dibasic acid, micromolecular diol and micromolecular polyol.
The polyether ester polyol A1 has an average hydroxyl functionality of 2.1-2.6.
The carbon atom number of the binary primary alcohol A3 is 2-6.
The polyalcohol amine A4 at least contains 2 hydroxyl groups, and the molecular chain contains 4-10 carbon atoms.
The polyether diol is one or more selected from polyethylene oxide diol, polypropylene oxide diol, polyethylene oxide propylene oxide diol and polytetramethylene ether glycol.
The dibasic acid is selected from one or more than one aliphatic dibasic acid with a molecular main chain containing 5-10 carbon atoms as a straight chain.
The micromolecular dihydric alcohol is respectively selected from one or more than one linear chain aliphatic dihydric alcohol with a molecular main chain containing 2-8 carbon atoms.
The micromolecular polyol is selected from one or more than one straight chain or branched chain aliphatic polyol of which the molecular main chain contains 3-10 carbon atoms and the number of hydroxyl groups is at least 3.
The polyisocyanate B1 at least contains one aromatic polyisocyanate or at least one aliphatic polyisocyanate;
the aromatic polyisocyanate is selected from one or more of diphenylmethane diisocyanate MDI, tetramethyl m-xylylene diisocyanate TMXDI, xylylene diisocyanate XDI, isomers and/or derivatives thereof and/or modified polymers,
the aliphatic polyisocyanate is selected from one or more of dicyclohexylmethane diisocyanate HMDI, 1, 4-cyclohexane diisocyanate CHDI and isomers and/or derivatives and/or modified polymers thereof.
The aromatic dihydric alcohol B2 is selected from one or more of 3-hydroxyethyl oxyethyl-1-hydroxyethyl benzene diether, bisphenol A dihydroxyethyl ether, bisphenol A diisopropyl ether, hydroquinone dihydroxyethyl ether and resorcinol dihydroxyethyl ether.
The aromatic diamine B2 is one or more selected from 4,4' -di-sec-butyl amino diphenylmethane, N ' -di-sec-butyl p-phenylenediamine, 2- (ethylene dithio) diphenylamine, 4' -methylene bis-o-chloroaniline and 3, 5-diethyl toluenediamine.
The solid tire of the present invention can be obtained by mixing the component A and the component B and then casting them in a mold having a certain shape.
Has the advantages that: according to the technical scheme, the polyurethane product obtained through the synergistic effect of the component A and the component B has excellent performances such as wear resistance, tensile strength, tearing strength, tensile strength, rebound resilience, compression deformation and the like, and when the product is used as a low-speed solid tire, the tire has good bearing deformation resistance, good elasticity and obvious buffering effect, and in addition, the product can be used in an outdoor environment for a long time and can keep excellent physical and mechanical properties.
Detailed Description
According to the embodiment, the polyether ester polyol A1 is obtained by taking polyether diol with the number average molecular weight of 250-650 as an initiator to react with dibasic acid, micromolecular diol and micromolecular polyol, and the polyether ester polyol A can be polymerized by a method known by a person skilled in the art, wherein the number average molecular weight is 2000-3000, and the average hydroxyl functionality is more than 2 and less than 3;
in some preferred embodiments of the present invention, the polyetherester polyol A1 has an average hydroxyl functionality of 2.1 to 2.6;
according to the embodiment, the polyester polyol A2 is obtained by condensation reaction of dibasic acid and at least one small molecular diol by a method known by a person skilled in the art, the number average molecular weight is 1500-3000, and the average hydroxyl functionality is 2;
in some preferred embodiments, the component A contains both polyether ester polyol A1 and polyester polyol A2;
in some embodiments of the present invention, the polyether glycol comprises at least polytetramethylene ether glycol;
the dibasic acid at least contains one of 1, 5-glutaric acid and 1, 6-adipic acid;
the micromolecular dihydric alcohol at least contains one of 1, 2-ethanediol, 1, 4-butanediol and 1, 6-hexanediol;
the molecular structure of the small molecular polyol at least contains 3 hydroxyl groups, the number of the hydroxyl groups is 3-6, the preferred embodiment is that the hydroxyl groups include but are not limited to one or more of glycerol, trimethylolpropane, trimethylolethane and trihydroxyhexane;
according to the embodiment, the binary primary alcohol A3 can be selected from one or more of 1, 2-ethanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol and 1, 6-hexanediol;
according to an embodiment, the polyalcohol amine a4 may be selected from one or more of diethanolamine, triethanolamine, methyldiethanolamine, triisopropanolamine;
the polyisocyanate B1 at least contains one aromatic polyisocyanate or at least one aliphatic polyisocyanate, the aromatic polyisocyanate is selected from one or more of diphenylmethane diisocyanate (MDI), tetramethyl m-xylylene diisocyanate (TMXDI), Xylylene Diisocyanate (XDI) and isomers and/or derivatives and/or modified polymers thereof, the aliphatic polyisocyanate is selected from one or more of dicyclohexyl methane diisocyanate (HMDI), 1, 4-cyclohexane diisocyanate (CHDI) and isomers and/or derivatives and/or modified polymers thereof;
MDI which may be used as an example may be one or more of isomers and/or derivatives of MDI and/or modified polymers such as 2,2' -MDI, 2,4' -MDI, 4' -MDI, carbodiimide modified MDI (liquefied MDI);
the aromatic diol B2 is selected from one or more of 3-hydroxyethyl oxyethyl-1-hydroxyethyl benzene diether, bisphenol A dihydroxyethyl ether, bisphenol A diisopropyl ether, hydroquinone dihydroxyethyl ether and resorcinol dihydroxyethyl ether;
the aromatic diamine B2 is selected from one or more of 4,4' -di-sec-butyl amino diphenylmethane, N ' -di-sec-butyl p-phenylenediamine, 2- (ethylene dithio) diphenylamine, 4' -methylene bis-o-chloroaniline and 3, 5-diethyl toluenediamine;
according to an example, the preparation process of the polyurethane of the present invention may comprise the steps of:
(1) preparation of component A
Adding an additive into polyether ester polyol A1, binary primary alcohol A3, polyalcohol amine A4 and/or polyester polyol A2 at the temperature of 45-50 ℃ in a molten state, uniformly mixing, and sealing for storage;
the type and the addition amount of the additive in the component A have no special requirements, and the additive is added according to the performance characteristics to be obtained on the premise of not generating deterioration influence on the polyurethane and the solid tire obtained by the polyurethane;
for example, adding a catalyst to accelerate the reaction speed of the component A and the component B, adding a foaming agent and a foam stabilizer to foam polyurethane to a certain extent to ensure the elastic characteristic of the polyurethane, adding a plasticizer to increase the plastic characteristic, adding an aging resistant agent to improve the light stability and the thermal stability of the material and the like;
in some embodiments of the present invention, the isocyanate-reactive A component contains a catalyst selected from the group consisting of triethylenediamine, dimethylcyclohexylamine, N-methyldicyclohexylamine, pentamethyldipropylenetriamine, bis (dimethylaminoethyl) ether, N-methylimidazole, 1, 8-diazacycloundecene, dibutyltin dilaurate;
the foaming agent is water;
the foam stabilizer is selected from commercially available foam stabilizers, such as DC-3043 (commercially available, American Airtight chemical industry), DC-193 (commercially available, American Airtight chemical industry), L-1580 (commercially available, American Meiji corporation), L-1507 (commercially available, American Meiji corporation), and L-1540 (commercially available, American Meiji corporation);
the plasticizer is selected from dioctyl adipate, tributyl aconitate, propylene carbonate, glycerol triacetate, diethyl succinate and butanediol cyclohexanedicarboxylate;
the aging resistant agent is selected from a light stabilizer Chisorb 770, a light stabilizer Chisorb 5411, a light stabilizer Tinuvin 765, a purple light stabilizer Tinuvin101, an antioxidant 245, an antioxidant 1135, an antioxidant 1010 and an antioxidant 1726;
(2) preparation of component B
Adding polyisocyanate B1, polyether ester polyol A1, aromatic diol and/or aromatic diamine B2 into a reaction kettle, reacting above the melting temperature of the prepolymer, controlling the temperature at 70-80 ℃, reacting for 2-3 hours until the-NCO content is kept within the range of 17-21 wt%, and sealing for storage.
According to the embodiment, the method for preparing the low-speed solid tire by using the polyurethane can be used for keeping the A component and the B component in a molten state respectively, fully and uniformly mixing the A component and the B component, injecting the mixture into a rotating and centrifugal tire mold, and casting and molding to obtain the polyurethane tire.
Examples
The materials mainly used are as follows:
polyether ester polyol 1:1, 4-butanediol-1, 6-adipic acid polytetramethylene ether Polyol (PTMEK) having a number average molecular weight of 2000 and an average hydroxyl functionality of 2.12;
polyether ester polyol 2: 1, 4-butanediol 1, 6-adipic acid polytetramethylene ether polyol, number average molecular weight 3000, average hydroxyl functionality 2.30;
polyether ester polyol 3: 1, 6-hexanedioic acid polytetramethylene ether 1, 6-hexanediol glycerol ester polyol, the number average molecular weight is 2000, and the average hydroxyl functionality is 2.58;
polyether ester polyol 4: 1, 4-butanediol 1, 6-hexanedioic acid polytetramethylene ether 1, 4-butanediol trimethylolethane polyol having a number average molecular weight of 3000 and an average hydroxyl functionality of 3.6;
polyester polyol 1:1, 4-butanediol poly (1, 6-ethanedioic acid glycol) 1, 6-butanediol polyol, having a number average molecular weight of 3000 and an average hydroxyl functionality of 2;
polyester polyol 2: a poly (1, 6-adipate glycol ester polyol) having a number average molecular weight of 2000 and an average hydroxyl functionality of 2;
1, binary primary alcohol: 1, 4-butanediol;
binary primary alcohol 2: ethylene glycol;
polyalcohol amine 1: diethanolamine;
polyisocyanate 1: 4,4' -MDI;
polyisocyanate 2: TMXDI;
polyisocyanate 3: liquefying MDI;
aromatic diol 1: 3-hydroxyethyloxyethyl-1-hydroxyethylbenzenediether;
aromatic diamine 2: 4,4' -bis-sec-butylaminodiphenylmethane;
wherein, the additives comprise the following components:
catalyst: triethylene diamine;
foaming agent: water;
foam stabilizer: DC-3043;
plasticizer: dioctyl adipate;
light stabilizer 1: tinuvin 101;
light stabilizer 2: chisorb 770;
light stabilizer 3: tinuvin 765;
antioxidant: an antioxidant 1135;
in order to better illustrate the technical effects of the present invention, the preparation methods of the specific examples of the present invention and the comparative examples are the same, and the specific methods are as follows:
(1) preparation of component A
Melting polyether ester polyol A1, binary primary alcohol A3, polyalcohol amine A4 and/or polyester polyol A2 at 45 ℃, adding an additive, uniformly mixing, sealing and storing for later use;
(2) preparation of component B
Adding aromatic polyisocyanate B1, polyether ester polyol A1, aromatic dihydric alcohol and/or aromatic diamine B2 into a reaction kettle, controlling the temperature at 80 ℃, reacting for 2-3 hours until the-NCO content is kept within the range of 17-21 wt%, and sealing and storing.
The additive types and additive amounts of the examples and comparative examples of the invention are kept constant, and 6.05 parts by weight in total comprise the following components:
catalyst: 2 parts by weight, foaming agent: 0.25 part by weight, foam stabilizer: 0.4 part by weight, plasticizer: 3 parts by weight of a light stabilizer 1: 0.1 part by weight, light stabilizer 2: 0.1 part by weight, light stabilizer 3: 0.1 part by weight, antioxidant: 0.1 part by weight;
example 1
The component A with reactivity to isocyanate is as follows:
100 parts by weight of a polyetherester polyol 1;
5 parts by weight of binary primary alcohol 2;
1.2 parts by weight of polyalcohol amine 1;
6.05 parts by weight of additives;
the component B of the prepolymer containing isocyanate is obtained by the prepolymerization reaction of the following materials:
46.9 parts by weight of polyisocyanate 1;
10 parts by weight of polyisocyanate 2;
3 parts by weight of polyisocyanate 3;
36.4 parts by weight of polyetherester polyol 1;
3.7 parts by weight of aromatic diamine 2;
the mass content of-NCO groups in the obtained isocyanate-containing prepolymer B component was 17 wt%, based on the total mass of the B component;
example 2
The component A with reactivity to isocyanate is as follows:
70 parts by weight of polyether ester polyol 1;
30 parts by weight of polyester polyol 1;
15 parts by weight of binary primary alcohol 2;
0.3 part by weight of polyalcohol amine 1;
6.05 parts by weight of additives;
the component B of the prepolymer containing isocyanate is obtained by the prepolymerization reaction of the following materials:
52.3 parts by weight of polyisocyanate 1;
10 parts by weight of polyisocyanate 2;
3 parts by weight of polyisocyanate 3;
30.7 parts by weight of polyetherester polyol 2;
4 parts by weight of aromatic diamine 2;
the mass content of-NCO groups in the obtained isocyanate-containing prepolymer component B is 20 wt%, calculated based on the total mass of the component B;
example 3
The component A with reactivity to isocyanate is as follows:
85 parts by weight of polyetherester polyol 3;
15 parts by weight of polyester polyol 2;
12 parts by weight of binary primary alcohol 1;
0.5 part by weight of polyalcohol amine 1;
6.05 parts by weight of additives;
the component B of the prepolymer containing isocyanate is obtained by the prepolymerization reaction of the following materials:
56.1 parts by weight of polyisocyanate 1;
10 parts by weight of polyisocyanate 2;
3 parts by weight of polyisocyanate 3;
28.2 parts by weight of polyetherester polyol 3;
2.7 parts by weight of aromatic diol 1;
the mass content of-NCO groups in the obtained isocyanate-containing prepolymer component B was 21 wt%, based on the total mass of the component B;
example 4
The component A with reactivity to isocyanate is as follows:
78 parts by weight of polyetherester polyol 2;
22 parts by weight of polyester polyol 2;
6 parts by weight of binary primary alcohol 2;
1 part by weight of polyalcohol amine 1;
6.05 parts by weight of additives;
the component B of the prepolymer containing isocyanate is obtained by the prepolymerization reaction of the following materials:
54.8 parts by weight of polyisocyanate 1;
4 parts by weight of polyisocyanate 3;
37.3 parts by weight of polyetherester polyol 2;
3.9 parts by weight of aromatic diamine 2;
the mass content of-NCO groups in the obtained isocyanate-containing prepolymer B component was 17 wt%, based on the total mass of the B component;
comparative example 1
The component A with reactivity to isocyanate is as follows:
100 parts by weight of polyester polyol 2;
5 parts by weight of binary primary alcohol 2;
1.2 parts by weight of polyalcohol amine 1;
6.05 parts by weight of additives;
the component B of the prepolymer containing isocyanate is obtained by the prepolymerization reaction of the following materials:
46.6 parts by weight of polyisocyanate 1;
10 parts by weight of polyisocyanate 2;
3 parts by weight of polyisocyanate 3;
36.7 parts by weight of polyester polyol 2;
3.7 parts by weight of aromatic diamine 2;
the mass content of-NCO groups in the obtained isocyanate-containing prepolymer B component was 17 wt%, based on the total mass of the B component;
comparative example 2
The component A with reactivity to isocyanate is as follows:
70 parts by weight of polyether ester polyol 1;
30 parts by weight of polyester polyol 1;
15 parts by weight of binary primary alcohol 2;
0.3 part by weight of polyalcohol amine 1;
6.05 parts by weight of additives;
the component B of the prepolymer containing isocyanate is obtained by the prepolymerization reaction of the following materials:
49.7 parts by weight of polyisocyanate 1;
10 parts by weight of polyisocyanate 2;
3 parts by weight of polyisocyanate 3;
37.3 parts by weight of polyetherester polyol 2;
the mass content of-NCO groups in the obtained isocyanate-containing prepolymer component B is 20 wt%, calculated based on the total mass of the component B;
comparative example 3
The component A with reactivity to isocyanate is as follows:
100 parts by weight of polyester polyol 2;
12 parts by weight of binary primary alcohol 1;
0.5 part by weight of polyalcohol amine 1;
6.05 parts by weight of additives;
the component B of the prepolymer containing isocyanate is obtained by the prepolymerization reaction of the following materials:
53 parts by weight of polyisocyanate 1;
10 parts by weight of polyisocyanate 2;
3 parts by weight of polyisocyanate 3;
34 parts by weight of polyester polyol 2;
the mass content of-NCO groups in the obtained isocyanate-containing prepolymer component B was 21 wt%, based on the total mass of the component B;
comparative example 4
The component A with reactivity to isocyanate is as follows:
100 parts by weight of a polyetherester polyol 4;
6 parts by weight of binary primary alcohol 2;
1 part by weight of polyalcohol amine 1;
6.05 parts by weight of additives;
the component B of the prepolymer containing isocyanate is obtained by the prepolymerization reaction of the following materials:
56.8 parts by weight of polyisocyanate 1;
4 parts by weight of polyisocyanate 3;
35.3 parts by weight of polyetherester polyol 4;
3.9 parts by weight of aromatic diamine 2;
the mass content of-NCO groups in the obtained isocyanate-containing prepolymer B component was 17 wt%, based on the total mass of the B component;
keeping the temperature of the component A of the examples and the comparative examples at 50 ℃, keeping the temperature of the component B at 45 ℃, fully and uniformly mixing the A, B component according to the molar ratio of the isocyanate reactive group in the component A to the-NCO group in the component B of 1:1, injecting the A, B component mixture into a mold, wherein the mold size meets the following performance test requirements, wherein for better comparison of performance differences, the mass of the A, B component mixture injected into the mold is kept constant in the test, so that the molding density after foaming is kept at 0.5g/cm3. After forming and demolding, polyurethane test pieces were obtained and tested for their properties, as shown in table 1:
TABLE 1
TABLE 1 (continuation)
According to the data of the embodiment and the comparative example, the polyurethane product obtained by the technical scheme of the invention has obviously excellent performances such as wear resistance, tensile strength, tearing strength, tensile strength and the like, and under the condition of improving hydrolysis resistance without adding hydrolysis resistance agent, the water resistance can still be kept above 85% after being placed for 14 days in a high-temperature high-humidity environment, and the compression deformation is less than 25%. The product is suitable for long-term outdoor use and is a tire material with high requirement on bearing deformation resistance, and in addition, the vertical resilience of the product is close to 50 percent, so that the product has good elasticity, small change of hardness along with temperature and good buffering effect when being used as a low-speed tire.
Claims (9)
1. The polyurethane for the low-speed solid tire is characterized by being obtained by reacting an isocyanate-reactive component A with a component B containing isocyanate prepolymer, wherein the molar ratio of isocyanate-reactive groups in the component A to-NCO groups in the component B is (0.95-1.05): 1;
the component A which has reactivity to isocyanate comprises the following components in parts by weight:
a1: 70-100 parts by weight of polyether ester polyol with the number average molecular weight of 2000-3000 and the average hydroxyl functionality of more than 2 and less than 3;
a3: 5-15 parts by weight of a binary primary alcohol having 2-6 carbon atoms;
a4: 0.3 to 1.2 parts by weight of polyalcohol amine;
the isocyanate-containing prepolymer B component comprises the following components in parts by weight: the prepolymerization reaction obtains:
b1: 56-72 parts by weight of polyisocyanate;
a1: 26-40 parts by weight of polyether ester polyol with the number average molecular weight of 2000-3000 and the average hydroxyl functionality of more than 2 and less than 3;
b2: 2-4 parts by weight of aromatic diol and/or aromatic diamine;
the-NCO group of the component B of the isocyanate prepolymer is calculated based on the total mass of the component B, and the mass content is 17-21 wt%;
the polyether ester polyol A1 is obtained by taking polyether diol with the number average molecular weight of 250-650 as an initiator and carrying out condensation reaction with dibasic acid, micromolecular diol and micromolecular polyol;
the dibasic acid is selected from one or more than one linear chain aliphatic dibasic acid with a molecular main chain containing 5-10 carbon atoms;
the micromolecular dihydric alcohol is selected from one or more than one linear chain aliphatic dihydric alcohol with a molecular main chain containing 2-8 carbon atoms;
the micromolecular polyol is selected from the polyol which has a molecular main chain containing 3-10 carbon atoms and at least 3 hydroxyl groups
One or more of linear or branched aliphatic polyols.
2. The polyurethane for a low-speed solid tire according to claim 1, wherein the isocyanate-reactive component A further comprises one or more of polyester polyol A2 having a number average molecular weight of 1500-3000 and an average hydroxyl functionality of 2, a catalyst, a foaming agent, a foam stabilizer, a plasticizer and an aging resistor.
3. The polyurethane for a low speed solid tire according to claim 1, wherein the polyether ester polyol A1 has an average hydroxyl functionality of 2.1 to 2.6.
4. The polyurethane for a low speed solid tire according to claim 1, wherein the number of carbon atoms of said binary primary alcohol A3 is 2 to 6.
5. The polyurethane for low-speed solid tires according to claim 1, characterized in that the polyalcohol amine A4 contains at least 2 hydroxyl groups and 4 to 10 carbon atoms in the molecular chain.
6. The polyurethane for a low speed solid tire according to claim 1, wherein the polyether glycol is one or more selected from the group consisting of polyethylene oxide glycol, polypropylene oxide glycol, polyethylene oxide propylene oxide glycol, and polytetramethylene ether glycol.
7. The polyurethane for a low speed solid tire according to claim 1, wherein said polyisocyanate B1 contains at least one aromatic polyisocyanate or at least one aliphatic polyisocyanate;
the aromatic polyisocyanate is selected from one or more of diphenylmethane diisocyanate MDI, tetramethyl m-xylylene diisocyanate TMXDI, xylylene diisocyanate XDI, isomers and/or derivatives thereof and/or modified polymers,
the aliphatic polyisocyanate is selected from one or more of dicyclohexylmethane diisocyanate HMDI, 1, 4-cyclohexane diisocyanate CHDI and isomers and/or derivatives and/or modified polymers thereof.
8. The polyurethane for low-speed solid tires according to claim 1, characterized in that the aromatic diol B2 is selected from one or more of 3-hydroxyethyloxyethyl-1-hydroxyethylbenzene diether, bisphenol A dihydroxyethyl ether, bisphenol A diisopropanol ether, hydroquinone dihydroxyethyl ether, and resorcinol dihydroxyethyl ether.
9. The polyurethane for a low speed solid tire as claimed in claim 1, wherein said aromatic diamine B2 is selected from one or more of 4,4' -bis-sec-butylaminodiphenylmethane, N ' -di-sec-butylp-phenylenediamine, 2- (ethylenedithio) diphenylamine, 4' -methylenebis-o-chloroaniline, and 3, 5-diethyltoluenediamine.
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| CN116102711B (en) * | 2023-04-05 | 2023-06-20 | 广州艾科新材料股份有限公司 | Polyurethane solid tire material with low rolling resistance and high resilience and preparation method thereof |
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|---|---|---|---|---|
| US4095637A (en) * | 1975-06-09 | 1978-06-20 | The Goodyear Tire & Rubber Company | Solid polyurethane tire/wheel assembly |
| US5145883A (en) * | 1989-05-12 | 1992-09-08 | Asahi Glass Company Ltd. | Methods for producing polyether ester polyols and polyurethanes |
| JP2008150583A (en) * | 2006-11-20 | 2008-07-03 | Cci Corp | Composition for solid tire and solid tire |
| CN105330811A (en) * | 2015-11-27 | 2016-02-17 | 嘉兴禾欣化学工业有限公司 | Polyurethane solid tire material and preparation method thereof |
| CN105939870A (en) * | 2013-12-20 | 2016-09-14 | 亨茨曼国际有限公司 | Polyurethane filled tires |
| CN106800637A (en) * | 2017-02-08 | 2017-06-06 | 滁州市玉林聚氨酯有限公司 | A kind of abrasion resistant polyurethane solid tyre |
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2020
- 2020-05-28 CN CN202010465476.8A patent/CN111533868B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4095637A (en) * | 1975-06-09 | 1978-06-20 | The Goodyear Tire & Rubber Company | Solid polyurethane tire/wheel assembly |
| US5145883A (en) * | 1989-05-12 | 1992-09-08 | Asahi Glass Company Ltd. | Methods for producing polyether ester polyols and polyurethanes |
| JP2008150583A (en) * | 2006-11-20 | 2008-07-03 | Cci Corp | Composition for solid tire and solid tire |
| CN105939870A (en) * | 2013-12-20 | 2016-09-14 | 亨茨曼国际有限公司 | Polyurethane filled tires |
| CN105330811A (en) * | 2015-11-27 | 2016-02-17 | 嘉兴禾欣化学工业有限公司 | Polyurethane solid tire material and preparation method thereof |
| CN106800637A (en) * | 2017-02-08 | 2017-06-06 | 滁州市玉林聚氨酯有限公司 | A kind of abrasion resistant polyurethane solid tyre |
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