CN105330811A - Polyurethane solid tire material and preparation method thereof - Google Patents
Polyurethane solid tire material and preparation method thereof Download PDFInfo
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- CN105330811A CN105330811A CN201510852762.9A CN201510852762A CN105330811A CN 105330811 A CN105330811 A CN 105330811A CN 201510852762 A CN201510852762 A CN 201510852762A CN 105330811 A CN105330811 A CN 105330811A
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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
-
- 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
- C08G18/28—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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- 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
- C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
- C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
- C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
- C08G18/4213—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from terephthalic acid and dialcohols
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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
- C08G18/425—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 the polyols containing one or two ether 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
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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
-
- 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
- B60C2001/0091—Compositions of non-inflatable or solid tyres
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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
- C08G2110/0041—Foam properties having specified density
- C08G2110/005—< 50kg/m3
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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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
- C08J2203/142—Halogenated saturated hydrocarbons, e.g. H3C-CF3
-
- 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
- C08J2375/06—Polyurethanes from polyesters
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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
Abstract
The invention relates to a polyurethane solid tire material. The polyurethane solid tire material comprises a component A and a component B, wherein the component A is a mixture prepared by mixing polyester polyol, a chain extender, a foaming agent, a catalyst A and a foam stabilizer according to a mass ratio of 100:(5 to 30):(0.3 to 3.0):(0.3 to 3.0):(0.3 to 2.5), the component B is prepared by prepolymerizing isocyanate, polyester polyol and polyether polyol under the existence of a side reaction inhibitor according to a mass ratio of 100:(20 to 50):(0 to 30), and the polyester polyol in the component A and the component B is prepared by prepolymerizing binary acid and polyhydric alcohols under the action of a catalyst B. The component A and the component B are fully mixed, and are then injected into a mold for reaction to form, and demolding and aging are performed, so as to prepare a tire product. The prepared tire product has the advantages of low density, stable size, high tread hardness, good abrasion resistance and good bonding capability with other accessories of the tire.
Description
Technical field
The invention belongs to polyurethane material field, be specifically related to a kind of polyurethane solid tyre material and preparation method thereof.
Background technology
Urethane is a kind of material of excellent performance, and in all elastomericss, the wear resisting property of urethanes is best, therefore has the title of " wear-resisting glue ", and compared with natural rubber, its abrasion resistance can improve 2 ~ 10 times more than.Meanwhile, it also has higher physical strength and tearing toughness, in addition its damping, buffering performance of excellence of possessing, made it the possess ability of " defeating a force with a tenderness " preferably, is comparatively suitable for making various tire product and uses.The range of application of pu tire is comparatively wide, and result of use is also very characteristic, and the solid tyre made with urethane is very wear-resisting durable, and lightweight, neither there is the problem being punctured the inner tube of a tyre by hard stone, iron nail, also need not give inflation of tire.It is applied to plain trolley, perambulator, toy car, wheelchair etc. on building site, and effect is all fine.Chinese patent CN200610033348 " a kind of polyurethane solid tyre and manufacture method thereof " describes oligomer polyol-diphenylmethanediisocyanate/tolylene diisocyanate system and oligomer polyol-3,3 '-dimethyl-4, the pu tire of 4 '-biphenyl diisocyanate system, but containing organic solvent in its formula, easy contaminate environment.
Summary of the invention
The object of the invention is to propose a kind of polyurethane solid tyre material and preparation method thereof, have finished product density by the solid tyre that this polyurethane material is made low, tyre surface hardness is high, and wear resisting property is good, reaches the application requiring of goods.
This polyurethane solid tyre material comprises component A and B component, described component A be polyester polyol, chainextender, whipping agent, catalyst A and foam stabilizer with mass ratio 100: (5 ~ 30): (0.3 ~ 3.0): (0.3 ~ 3.0): the mixture that the ratio of (0.3 ~ 2.5) mixes; Described B component be by isocyanic ester, polyester polyol, polyether glycol under side reaction hold back agent exists with mass ratio 100: (20 ~ 50): the ratio of (0 ~ 30) is carried out prepolymerization reaction and obtained.
The preparation method of this polyurethane solid tyre material comprises the following steps:
(1) by diprotic acid and polyvalent alcohol under catalyst B effect, carry out polyesterification reaction in 140 DEG C ~ 250 DEG C under nitrogen protection, react to acid number and reduce to below 1mgKOH/g, stopped reaction when hydroxyl value is 30 ~ 200mgKOH/g, obtained polyester polyol;
(2) preparation of component A: polyester polyol and chainextender, whipping agent, catalyst A, the foam stabilizer of gained being prepared by step (1) add reactor, are warmed up to 50 ~ 80 DEG C and mix, then be cooled to 35 ~ 40 DEG C of dischargings, obtains component A;
(3) preparation of B component: polyester polyol and polyether glycol, the isocyanic ester of gained being prepared by step (1) react 2 ~ 3h under side reaction terminator exists under 70 ~ 80 DEG C of conditions, obtains B component.
After the component A of this polyurethane solid tyre material is fully mixed with B component, inject mould and react shaping, the demoulding, slaking, can obtain tire product, obtained tire product density is low, and the compact density of pu tire can regulate in 0.2 ~ 0.50g/cm3; Do not shrink after shaping, non-warping, dimensional stabilizing; The tyre surface hardness of pu tire is higher, is 70 ~ 100 shore A; Wear resisting property is good, is 2 ~ 10 times of General Purpose Rubber tire; The ratio of mixture latitude of component A and B component mixture is good, compound good fluidity, and the article removal time is short, surface quality good, and wear resisting property is high, good with other annex binding abilities of tire.And without organic solvent in formula, not easily cause environmental problem.
Embodiment
This polyurethane solid tyre material comprises component A and B component, and described component A is: polyester polyol, chainextender, whipping agent, catalyst A and foam stabilizer are with mass ratio 100: (5 ~ 30): (0.3 ~ 3.0): (0.3 ~ 3.0): the mixture that the ratio of (0.3 ~ 2.5) mixes; Described B component be by isocyanic ester, polyester polyol, polyether glycol under side reaction hold back agent exists with mass ratio 100: (20 ~ 50): the ratio of (0 ~ 30) is carried out prepolymerization reaction and obtained.Wherein component A be prepared as physical mixing processes, the effect of intensification is only and contributes to each component and mix, and because there being part polyvalent alcohol, viscosity is larger at normal temperatures, after heating up, viscosity reduces, be easy to mixing, final product is liquid 40 ~ 50 DEG C time, and viscosity is about 200 ~ 600CPs.
In this polyurethane solid tyre material, the polyester polyol in described component A or B component can carry out polyesterification reaction by diprotic acid and polyvalent alcohol and obtain under the effect of catalyst B.Described diprotic acid and the mass ratio of polyvalent alcohol can be 1: (0.5 ~ 2); Wherein, described diprotic acid can be hexanodioic acid (AA) and terephthalic acid (PTA) with mass ratio 1: the mixture of (0 ~ 1); Described polyvalent alcohol can be ethylene glycol (EG), glycol ether (DEG), 1,4-butyleneglycol (1, two or more 4-BG) with after the mixing of arbitrary ratio, then with TriMethylolPropane(TMP) (TMP) with mass ratio 1: the mixture that (0 ~ 0.05) is mixed to get mutually; Described catalyst B can be titanium isopropylate, also can use zinc acetate.
In this polyurethane solid tyre material, chainextender in described component A can be 1, one or more in 4-butyleneglycol (Isosorbide-5-Nitrae-BG), ethylene glycol (EG), glycol ether (DEG) are with the mixture of arbitrary proportion; Described whipping agent can be one or both in water, Chlorofluorocarbons (CFCs) with the mixture of arbitrary proportion; Described catalyst A can be one or more mixtures in dibutyl tin laurate, triethylene diamine, tetramethyl-diethylenetriamine; Described foam stabilizer can be one or more in DC-193, DC-3042 or DC-3043 with the mixture of arbitrary proportion.
In this polyurethane solid tyre material, isocyanic ester in described B component can be 4, and one or more in 4 '-diphenylmethanediisocyanate (MDI), Carbodiimide-Modified MDI, polyphenyl polymethylene polyisocyanates (PAPI) are with the mixture of arbitrary proportion; Described polyether glycol can be one or more in polyoxypropylene polyol, polyoxyethylene copolyether polyvalent alcohol and polytetrahydrofuran polyol; Described side reaction hold back agent can be that mineral acid is if phosphoric acid, organic acid are as Glacial acetic acid or Benzoyl chloride.
The preparation method of this polyurethane solid tyre material comprises the following steps:
(1) by diprotic acid and polyvalent alcohol under catalyst B effect, carry out polyesterification reaction in 140 DEG C ~ 250 DEG C under nitrogen protection, react to acid number and reduce to below 1mgKOH/g, stopped reaction when hydroxyl value is 30 ~ 200mgKOH/g, obtained polyester polyol; The functionality of polyester polyol controls 2 ~ 2.7.
(2) preparation of component A: polyester polyol and chainextender, whipping agent, catalyst A, the foam stabilizer of gained being prepared by step (1) add reactor, are warmed up to 50 ~ 80 DEG C and mix, then be cooled to 35 ~ 40 DEG C of dischargings, obtains component A; Final product is liquid 40 ~ 50 DEG C time, and viscosity is about 200 ~ 600CPs.
(3) preparation of B component: polyester polyol and polyether glycol, the isocyanic ester of gained being prepared by step (1) react 2 ~ 3h under side reaction terminator exists under 70 ~ 80 DEG C of conditions, obtains B component.Final product is liquid 40 ~ 50 DEG C time, and viscosity is about 100 ~ 300CPs.
Below in conjunction with example, the invention will be further described, but protection scope of the present invention is not limited to this.Embodiment 1 ~ 6 is the preparation of polyester polyol, and wherein embodiment 3, embodiment 4, embodiment 5, embodiment 6 respectively repeat 2 times, to obtain the polyester polyol sample embodiment later of q.s; Embodiment 7 ~ 12 is the preparation of polyurethane solid tyre material.In raw material used in each embodiment, polyether glycol selects the polyether glycol product purchased from Tianjin the 3rd petroleum chemical plant, and the trade mark is ZS-T280, and molecular weight is 4000; Organosilicon foam stabilizer selects purchased from American aerification chemical product Products, and the trade mark is DC-3043; All the other materials are industrial goods purchased from market or self-control.
Embodiment 1:
Prepare polyester polyol 1: mixed by 518gAA, 222gPTA, 203gEG, 203gDEG, 33.5gTMP and 5g catalyzer tetrabutyl titanate; be heated to 240 DEG C under nitrogen protection and carry out polyesterification reaction; reaction 20Hr; stopped reaction when acid number is 0.3mgKOH/g, hydroxyl value is 70mgKOH/g, obtained polyester polyol 960g.
Embodiment 2:
Prepare polyester polyol 2: mixed by 470gAA, 117gPTA, 111gEG, 258gDEG, 22gTMP and 5g catalyzer tetrabutyl titanate; be heated to 230 DEG C under nitrogen protection and carry out polyesterification reaction; reaction 18Hr; stopped reaction when acid number 0.3mgKOH/g, hydroxyl value are 56mgKOH/g, obtained 960g polyester polyol.
Embodiment 3:
Prepare polyester polyol 3: mixed by 707gAA, 142gEG, 330gDEG and 5g catalyzer tetrabutyl titanate; be heated to 220 DEG C under nitrogen protection and carry out polyesterification reaction; reaction 16Hr, stopped reaction when acid number 0.4mgKOH/g, hydroxyl value are 56mgKOH/g, obtained polyester polyol 961g.
Embodiment 4:
Prepare polyester polyol 4: mixed by 696gAA, 145gEG, 335gDEG and 5g catalyzer tetrabutyl titanate; be heated to 220 DEG C under nitrogen protection and carry out polyesterification reaction; reaction 16Hr, stopped reaction when acid number 0.3mgKOH/g, hydroxyl value are 74mgKOH/g, obtained polyester polyol 961g.
Embodiment 5:
Prepare polyester polyol 5: mixed by 741gAA, 135gEG, 316gBG and 5g catalyzer tetrabutyl titanate; be heated to 220 DEG C under nitrogen protection and carry out polyesterification reaction; reaction 16Hr, stopped reaction when acid number 0.3mgKOH/g, hydroxyl value are 56mgKOH/g, obtained polyester polyol 961g.
Embodiment 6:
Prepare polyester polyol 6: mixed by 570gAA, 143gPTA, 140gEG, 325gBG and 5g catalyzer tetrabutyl titanate; be heated to 230 DEG C under nitrogen protection and carry out polyesterification reaction; reaction 16Hr; stopped reaction when acid number 0.3mgKOH/g, hydroxyl value are 56mgKOH/g, obtained polyester polyol 960g.
Embodiment 7:
1, component A raw material:
Polyester polyol 250g,
Polyester polyol 450g,
Polyester polyol 6900g,
Chainextender (EG) 150g,
Organosilicon foam stabilizer 10g,
Whipping agent (HCFC-141B) 70g,
Catalyzer (triethylene diamine) 15g.
2, B component raw material:
4,4-diphenylmethanediisocyanate 620g,
Carbodiimide-Modified MDI40g,
Polyester polyol 6260g,
Polyether glycol ZS-T28080g,
Phosphoric acid 0.06g.
3, preparation process:
The raw material of component A is dropped in reactor, is warming up to 60 DEG C and mixes 3 hours, then discharging after being cooled to 40 DEG C, sealing is preserved;
The raw material of B component is placed in reactor, is warming up to 75 DEG C under nitrogen protection, react 2.5 hours, be cooled to 45 DEG C, sampling analysis free-NCO content is 20.5%, and sealing is preserved.
Embodiment 8:
1, component A raw material:
Polyester polyol 150g,
Polyester polyol 5500g,
Polyester polyol 6450g,
Chainextender (EG) 100g,
Chainextender (Isosorbide-5-Nitrae BG) 50g,
Organosilicon foam stabilizer 8g,
Water 4.5g,
Catalyzer (triethylene diamine) 16g.
2, B component raw material:
4,4-diphenylmethanediisocyanate 640g,
Carbodiimide-Modified MDI50g,
Polyester polyol 240g,
Polyester polyol 4240g,
Polyether glycol ZS-T28030g,
Phosphoric acid 0.06g.
3, preparation process:
The raw material of component A is dropped in reactor, is warming up to 60 DEG C and mixes 2 hours, then discharging after being cooled to 40 DEG C, sealing is preserved;
The raw material of B component is placed in reactor, is warming up to 75 DEG C under nitrogen protection, react 2.5 hours, be cooled to 45 DEG C, sampling analysis free-NCO content is 21.5%, and sealing is preserved.
Embodiment 9:
1, component A raw material:
Polyester polyol 1100g,
Polyester polyol 3400g,
Polyester polyol 4400g,
Chainextender (EG) 150g,
Organosilicon foam stabilizer 8g,
Water 4g,
Whipping agent (HCFC-141B) 30g,
Catalyzer (triethylene diamine) 20g.
2, B component raw material:
4,4-diphenylmethanediisocyanate 640g,
Carbodiimide-Modified MDI30g,
Polyphenyl polymethylene polyisocyanates 20g,
Polyester polyol 140g,
Polyester polyol 5225g,
Polyether glycol ZS-T28045g,
Phosphoric acid 0.06g.
3, preparation process:
The raw material of component A is dropped in reactor, is warming up to 60 DEG C and mixes 3 hours, then discharging after being cooled to 40 DEG C, sealing is preserved;
The raw material of B component is placed in reactor, is warming up to 75 DEG C under nitrogen protection, react 2.5 hours, be cooled to 45 DEG C, sampling analysis free-NCO content is 21.5%, and sealing is preserved.
Embodiment 10:
1, component A raw material:
Polyester polyol 250g,
Polyester polyol 3450g,
Polyester polyol 5500g,
Chainextender (EG) 150g,
Organosilicon foam stabilizer 10g,
Water 6g,
Catalyzer (triethylene diamine) 18g.
2, B component raw material:
4,4-diphenylmethanediisocyanate 650g,
Carbodiimide-Modified MDI60g,
Polyester polyol 150g,
Polyester polyol 3140g,
Polyester polyol 5100g,
Phosphoric acid 0.07g.
3, preparation process:
The raw material of component A is dropped in reactor, is warming up to 60 DEG C and mixes 2 hours, then discharging after being cooled to 40 DEG C, sealing is preserved;
The raw material of B component is placed in reactor, is warming up to 75 DEG C under nitrogen protection, react 3 hours, be cooled to 40 DEG C, sampling analysis free-NCO content is 22.3%, and sealing is preserved.
Embodiment 11:
1, component A raw material:
Polyester polyol 1100g,
Polyester polyol 4600g,
Polyester polyol 6300g,
Chainextender (EG) 180g,
Organosilicon foam stabilizer 8g,
Water 4g,
Whipping agent (HCFC-141B) 40g,
Catalyzer (triethylene diamine) 20g.
2, B component raw material:
4,4-diphenylmethanediisocyanate 620g,
Carbodiimide-Modified MDI100g,
Polyester polyol 2100g,
Polyester polyol 5130g,
Polyether glycol ZS-T28050g,
Phosphoric acid 0.07g.
3, preparation process:
The raw material of component A is dropped in reactor, is warming up to 60 DEG C and mixes 3 hours, then discharging after being cooled to 40 DEG C, sealing is preserved;
The raw material of B component is placed in reactor, is warming up to 75 DEG C under nitrogen protection, react 2.5 hours, be cooled to 45 DEG C, sampling analysis free-NCO content is 22.5%, and sealing is preserved.
Embodiment 12:
1, component A raw material:
Polyester polyol 1100g,
Polyester polyol 3500g,
Polyester polyol 5400g,
Chainextender (EG) 200g,
Organosilicon foam stabilizer 8g,
Water 6.5g,
Catalyzer (triethylene diamine) 18g.
2, B component raw material:
4,4-diphenylmethanediisocyanate 630g,
Carbodiimide-Modified MDI80g,
Polyphenyl polymethylene polyisocyanates 40g,
Polyester polyol 1120g,
Polyester polyol 590g,
Polyether glycol ZS-T28040g,
Phosphoric acid 0.065g.
3, preparation process:
The raw material of component A is dropped in reactor, is warming up to 60 DEG C and mixes 2.5 hours, then discharging after being cooled to 40 DEG C, sealing is preserved;
The raw material of B component is placed in reactor, is warming up to 75 DEG C under nitrogen protection, react 2.5 hours, be cooled to 45 DEG C, sampling analysis free-NCO content is 23.5%, and sealing is preserved.
Polyurethane solid tyre material obtained by embodiment 7 ~ 12 is made tire sample respectively, and method is:
The temperature controlling component A and B component is 40 ~ 50 DEG C, the consumption of adjustment component A and B component, the reactive hydrogen mole number of component A is made to be 100: 100 with the ratio of the mole number of-NCO of B component, two components are fully mixed, injects mould, under the effect of the catalyst A in component A, react shaping, 3 ~ 6min is about needed to react complete, the demoulding, slaking, obtains goods.Result is as following table:
Claims (5)
1. a polyurethane solid tyre material, comprise component A and B component, it is characterized in that described component A be polyester polyol, chainextender, whipping agent, catalyst A and foam stabilizer with mass ratio 100: (5 ~ 30): (0.3 ~ 3.0): (0.3 ~ 3.0): the mixture that the ratio of (0.3 ~ 2.5) mixes; Described B component be by isocyanic ester, polyester polyol, polyether glycol under side reaction hold back agent exists with mass ratio 100: (20 ~ 50): the ratio of (0 ~ 30) is carried out prepolymerization reaction and obtained.
2. polyurethane solid tyre material as claimed in claim 1, the polyester polyol that it is characterized in that in described component A or B component carries out polyesterification reaction by diprotic acid and polyvalent alcohol and obtains under the effect of catalyst B; The mass ratio of described diprotic acid and polyvalent alcohol is 1: (0.5 ~ 2); Wherein, described diprotic acid be hexanodioic acid and terephthalic acid with mass ratio 1: the mixture of (0 ~ 1); Described polyvalent alcohol be two or more in ethylene glycol, glycol ether, BDO with after the mixing of arbitrary ratio, then with TriMethylolPropane(TMP) with mass ratio 1: the mixture that (0 ~ 0.05) is mixed to get mutually; Described catalyst B is titanium isopropylate.
3. polyurethane solid tyre material as claimed in claim 2, the chainextender that it is characterized in that in described component A be one or more in BDO, ethylene glycol, glycol ether with the mixture of arbitrary proportion; Described whipping agent be one or both in water, Chlorofluorocarbons (CFCs) with the mixture of arbitrary proportion; Described catalyst A is one or more mixtures in dibutyl tin laurate, triethylene diamine, tetramethyl-diethylenetriamine; Described foam stabilizer be one or more in DC-193, DC-3042 or DC-3043 with the mixture of arbitrary proportion.
4. polyurethane solid tyre material as claimed in claim 3, it is characterized in that the isocyanic ester in described B component is 4, one or more in 4 '-diphenylmethanediisocyanate, Carbodiimide-Modified MDI, polyphenyl polymethylene polyisocyanates are with the mixture of arbitrary proportion; Described polyether glycol is one or more in polyoxypropylene polyol, polyoxyethylene copolyether polyvalent alcohol and polytetrahydrofuran polyol; Described side reaction hold back agent is mineral acid, organic acid or Benzoyl chloride.
5. the preparation method of the polyurethane solid tyre material described in claim 2,3 or 4, is characterized in that step is:
(1) by diprotic acid and polyvalent alcohol under the effect of catalyst B, carry out polyesterification reaction in 140 DEG C ~ 250 DEG C under nitrogen protection, react to acid number and reduce to below 1mgKOH/g, stopped reaction when hydroxyl value is 30 ~ 200mgKOH/g, obtained polyester polyol;
(2) preparation of component A: polyester polyol and chainextender, whipping agent, catalyst A, the foam stabilizer of gained being prepared by step (1) add reactor, are warmed up to 50 ~ 80 DEG C and mix, then be cooled to 35 ~ 40 DEG C of dischargings, obtains component A;
(3) preparation of B component: polyester polyol and polyether glycol, the isocyanic ester of gained being prepared by step (1) react 2 ~ 3h under side reaction terminator exists under 70 ~ 80 DEG C of conditions, obtains B component.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1807130A (en) * | 2006-01-27 | 2006-07-26 | 华南理工大学 | Polyurethane solid tyre and manufacturing method thereof |
| CN101486788A (en) * | 2008-12-30 | 2009-07-22 | 浙江华峰新材料股份有限公司 | Low density high hardness polyurethane micropore elastomer and preparation thereof |
| CN104193940A (en) * | 2014-08-27 | 2014-12-10 | 中科院广州化学有限公司南雄材料生产基地 | Organic silicon/montmorillonite composite modified polyester-type polyurethane elastomer as well as preparation method and application thereof |
| CN104497252A (en) * | 2014-12-11 | 2015-04-08 | 淄博德信联邦化学工业有限公司 | Polyurethane for making solid tires and preparation method thereof |
-
2015
- 2015-11-27 CN CN201510852762.9A patent/CN105330811A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1807130A (en) * | 2006-01-27 | 2006-07-26 | 华南理工大学 | Polyurethane solid tyre and manufacturing method thereof |
| CN101486788A (en) * | 2008-12-30 | 2009-07-22 | 浙江华峰新材料股份有限公司 | Low density high hardness polyurethane micropore elastomer and preparation thereof |
| CN104193940A (en) * | 2014-08-27 | 2014-12-10 | 中科院广州化学有限公司南雄材料生产基地 | Organic silicon/montmorillonite composite modified polyester-type polyurethane elastomer as well as preparation method and application thereof |
| CN104497252A (en) * | 2014-12-11 | 2015-04-08 | 淄博德信联邦化学工业有限公司 | Polyurethane for making solid tires and preparation method thereof |
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| CN109021191A (en) * | 2018-06-08 | 2018-12-18 | 明光速耐德实心轮胎有限公司 | A kind of antistatic solid tyre |
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| CN109608606B (en) * | 2018-11-01 | 2021-01-12 | 浙江禾欣科技有限公司 | Preparation method of polyurethane solid tire for mining vehicle |
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