CN113583432A - High-wear-resistance low-internal-heat-generation TPU material and preparation method thereof - Google Patents
High-wear-resistance low-internal-heat-generation TPU material and preparation method thereof Download PDFInfo
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- CN113583432A CN113583432A CN202110954049.0A CN202110954049A CN113583432A CN 113583432 A CN113583432 A CN 113583432A CN 202110954049 A CN202110954049 A CN 202110954049A CN 113583432 A CN113583432 A CN 113583432A
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- tpu material
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- screw extruder
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- 239000000463 material Substances 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 38
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 38
- 229920002121 Hydroxyl-terminated polybutadiene Polymers 0.000 claims abstract description 36
- 239000002994 raw material Substances 0.000 claims abstract description 29
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 19
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 33
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 30
- WTPYFJNYAMXZJG-UHFFFAOYSA-N 2-[4-(2-hydroxyethoxy)phenoxy]ethanol Chemical compound OCCOC1=CC=C(OCCO)C=C1 WTPYFJNYAMXZJG-UHFFFAOYSA-N 0.000 claims description 23
- 239000002245 particle Substances 0.000 claims description 21
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 18
- -1 polyethylene Polymers 0.000 claims description 18
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical group C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- 238000005259 measurement Methods 0.000 claims description 10
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 9
- 238000011049 filling Methods 0.000 claims description 9
- 238000010907 mechanical stirring Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 238000000520 microinjection Methods 0.000 claims description 9
- 239000004970 Chain extender Substances 0.000 claims description 7
- 229940075507 glyceryl monostearate Drugs 0.000 claims description 7
- 239000000314 lubricant Substances 0.000 claims description 7
- 239000001788 mono and diglycerides of fatty acids Substances 0.000 claims description 7
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 7
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 claims description 6
- TXQVDVNAKHFQPP-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CO)(CO)CO TXQVDVNAKHFQPP-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 238000006136 alcoholysis reaction Methods 0.000 claims description 4
- DFWZIKINBHKJOB-UHFFFAOYSA-N benzene-1,3-diol;2-(2-hydroxyethoxy)ethanol Chemical compound OCCOCCO.OC1=CC=CC(O)=C1 DFWZIKINBHKJOB-UHFFFAOYSA-N 0.000 claims description 4
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims 3
- 229920000573 polyethylene Polymers 0.000 claims 3
- WERYXYBDKMZEQL-UHFFFAOYSA-N 1,4-butanediol Substances OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims 2
- 239000004433 Thermoplastic polyurethane Substances 0.000 abstract description 43
- 229920002803 thermoplastic polyurethane Polymers 0.000 abstract description 43
- 229920001971 elastomer Polymers 0.000 abstract description 8
- 230000020169 heat generation Effects 0.000 abstract description 5
- 239000000806 elastomer Substances 0.000 abstract description 4
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 26
- 229920002379 silicone rubber Polymers 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 239000004945 silicone rubber Substances 0.000 description 5
- NSPSPMKCKIPQBH-UHFFFAOYSA-K bismuth;7,7-dimethyloctanoate Chemical compound [Bi+3].CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O NSPSPMKCKIPQBH-UHFFFAOYSA-K 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 229920000921 polyethylene adipate Polymers 0.000 description 4
- 239000005060 rubber Substances 0.000 description 4
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- BWVAOONFBYYRHY-UHFFFAOYSA-N [4-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=C(CO)C=C1 BWVAOONFBYYRHY-UHFFFAOYSA-N 0.000 description 3
- 238000013016 damping Methods 0.000 description 3
- 238000012938 design process Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920003225 polyurethane elastomer Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- FYSJYVHOKOFOAP-UHFFFAOYSA-N hexanedioic acid;propane-1,3-diol Chemical compound OCCCO.OC(=O)CCCCC(O)=O FYSJYVHOKOFOAP-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 229920000616 Poly(1,4-butylene adipate) Polymers 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- ZJOLCKGSXLIVAA-UHFFFAOYSA-N ethene;octadecanamide Chemical compound C=C.CCCCCCCCCCCCCCCCCC(N)=O.CCCCCCCCCCCCCCCCCC(N)=O ZJOLCKGSXLIVAA-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- YQEMORVAKMFKLG-UHFFFAOYSA-N glycerine monostearate Natural products CCCCCCCCCCCCCCCCCC(=O)OC(CO)CO YQEMORVAKMFKLG-UHFFFAOYSA-N 0.000 description 1
- SVUQHVRAGMNPLW-UHFFFAOYSA-N glycerol monostearate Natural products CCCCCCCCCCCCCCCCC(=O)OCC(O)CO SVUQHVRAGMNPLW-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 230000035924 thermogenesis Effects 0.000 description 1
Classifications
-
- 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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/69—Polymers of conjugated dienes
- C08G18/698—Mixtures with compounds of group C08G18/40
-
- 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
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to a high-wear-resistance low-endogenous-heat TPU material and a preparation method thereof, belonging to the technical field of thermoplastic polyurethane elastomers. The high-wear-resistance low-internal-heat-generation TPU material comprises the following raw materials: polyester polyol, hydroxyl-terminated polybutadiene, diisocyanate and modified nano Al2O3(ii) a The number average molecular weight of the polyester polyol is 1500-3500; the number average molecular weight of the hydroxyl-terminated polybutadiene is 1500-. The high-wear-resistance low-internal-heat-generation TPU material disclosed by the invention has excellent wear resistance and lower internal heat generation performance; the invention also provides the advantages of simplicityThe preparation method of the line.
Description
Technical Field
The invention relates to a high-wear-resistance low-endogenous-heat TPU material and a preparation method thereof, belonging to the technical field of thermoplastic polyurethane elastomers.
Background
Thermoplastic polyurethane elastomer (TPU) is a novel, environmentally friendly polymeric material. The material has excellent physical and mechanical properties such as high modulus, high strength, high elongation, high elasticity, high wear resistance and the like, has elasticity and toughness of rubber and thermoplasticity and mechanical strength of plastics, and is widely applied to the fields of sealing injection molding parts, sheets, shoe materials, automobiles, cables, medical treatment, films and the like. The polyurethane elastomer has higher internal consumption and can be widely applied to the fields of shock absorption, noise reduction and the like as a high-performance damping material. But it has to be pointed out that the high endogenous heat of the material itself under dynamic conditions greatly limits its application under high speed dynamic conditions such as automobile tires, casters, rubber rollers, etc.
In view of the excellent comprehensive properties and easy processing of TPU materials, people begin to apply TPU materials widely in the fields of automobile tires, casters, rubber rollers, and the like. How to improve the dynamic mechanical property of polyurethane elastomer and obtain TPU material with less internal consumption and less internal heat generation becomes the key point of research of people.
Patent CN112662164A "a wear-resistant polyurethane material for tires and a preparation method thereof" discloses a wear-resistant polyurethane material for tires and a preparation method thereof, wherein the strength and wear resistance of the silicone rubber thermoplastic polyurethane composite material are enhanced by improving the components of the tires and carrying out composite modification on thermoplastic polyurethane by using silicone rubber to obtain the silicone rubber thermoplastic polyurethane composite material. In addition, the terpene resin is introduced into the silicone rubber, and the damping property of the silicone rubber is increased, so that the polymer can convert the vibration mechanical energy into heat energy, the vibration strength of the tire can be reduced, and the stability of the tire is improved. However, the TPU material and the silicon rubber material are blended and modified by the method, although the TPU material and the silicon rubber material have excellent wear resistance and rebound resilience, the method has the greatest defects that the compatibility of the silicon rubber and the thermoplastic polyurethane is poor, and the mechanical property is poor; the silicon rubber increases the damping property, so that the composite material generates heat too fast, and the wide application of the material is limited.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and providing a high-wear-resistance low-internal-heat-generation TPU material which has excellent wear resistance and lower internal heat generation performance; the invention also provides a simple and feasible preparation method.
The high-wear-resistance low-internal-heat-generation TPU material comprises the following raw materials: polyester polyol, hydroxyl-terminated polybutadiene, diisocyanate and modified nano Al2O3；
The number average molecular weight of the polyester polyol is 1500-3500;
the number average molecular weight of the hydroxyl-terminated polybutadiene is 1500-.
Preferably, the polyester polyol is one or more of polyethylene adipate glycol, polyethylene adipate glycol-1, 3-propylene glycol, polyethylene adipate glycol-1, 4-butylene glycol or polyethylene adipate 1, 4-butylene glycol.
Preferably, the addition amount of the hydroxyl-terminated polybutadiene is 5-20% of the total mass of the polyester polyol and the hydroxyl-terminated polybutadiene.
Preferably, the diisocyanate is a symmetric aromatic diisocyanate including 4,4' -diphenylmethane diisocyanate (MDI), phenylene-1, 4-diisocyanate (PPDI), or 1, 5-Naphthalene Diisocyanate (NDI).
Preferably, the modified nano Al2O3Is silane coupling agent KH550 modified Al2O3The size is 100-500 nm.
Preferably, the modified nano Al2O3The preparation method comprises the following steps:
(1) taking a certain amount of nano Al2O3Dispersing the particles in ethanol, and ultrasonically vibrating at 25-35 deg.C for 0.5-1h to obtain uniformly dispersed Al2O3Suspending liquid;
(2) dissolving a proper amount of silane coupling agent in an ethanol solvent for alcoholysis, adjusting the pH value of the solution, and performing ultrasonic vibration hydrolysis at 25-35 ℃ for 0.5-1 h;
(3) micron Al obtained in the step (1)2O3Adding into silane coupling agent solution, and magnetically treating in water bath at 40-50 deg.CStirring for 1-1.5h to obtain the modified micron Al2O3A material;
(4) modified micron Al2O3And carrying out suction filtration, washing and drying on the material for later use.
Preferably, the amount of the silane coupling agent used in the step (2) is micron Al2O310% of the addition amount; the pH value of the alcoholysis solution of the silane coupling agent is controlled to be 5-7.
Preferably, the raw materials also comprise a chain extender, a lubricant and an additional catalyst.
Preferably, the chain extender is an aromatic diol including one or more of terephthalyl alcohol (PXG), hydroquinone-bis (β -hydroxyethyl) ether (HQEE) or resorcinol-bis (β -Hydroxyethyl) Ether (HER).
Preferably, the lubricant is one or more of glyceryl monostearate, pentaerythritol stearate, E-wax or ethylene bis stearamide.
Preferably, the catalyst is organic bismuth or organic tin. Further preferred is the organotin catalyst stannous octoate (T-9).
Preferably, the high-wear-resistance low-internal-heat-generation TPU material comprises the following raw materials in percentage by mass:
the dosage of the added catalyst is polyester polyol, hydroxyl-terminated polybutadiene, diisocyanate, a chain extender, a lubricant and modified nano Al2O30.05-0.1% of the total mass.
The preparation method of the high-wear-resistance low-endogenous-heat TPU material comprises the following steps:
(1) polyester polyol, hydroxyl-terminated polybutadiene, a chain extender, a lubricant and modified micron Al2O3Adding the mixture into a reaction kettle A with a mechanical stirring and temperature control system for mixing, wherein the temperature of the reaction kettle A is 110-125 ℃; placing diisocyanate in a reaction kettle B for stirring, wherein the temperature of the reaction kettle B is 80-135 ℃;
(2) when the materials in the two reaction kettles are uniformly stirred, the raw materials in the A, B reaction kettle are injected into a feeding port of a double-screw extruder through a filling system with accurate measurement, a catalyst is injected into the feeding port of the double-screw extruder through a micro-injection pump, the mixture is reacted and plasticized in a cylinder of the double-screw extruder, and the mixture is cut into elliptical particles through an underwater granulator; the temperature of the double-screw extruder is 150-200 ℃, and the rotating speed is 180-240 r/min.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, the molecular structure is optimized by using the mixed polyol of polyester polyol and hydroxyl-terminated polybutadiene, the TPU material with low internal heat generation is prepared, the internal heat generation performance can be reduced by 39%, and the TPU material can be widely applied to the fields of sealing elements, pipes, cables, automobile accessories and the like;
(2) the invention is prepared by modifying nano Al2O3The particles are uniformly dispersed in the TPU material and used as a filling agent, so that the acting force among TPU molecules is enhanced, the wear resistance of the material is improved, the wear resistance can be improved by 31 percent, and the problem that the material is quickly worn in the using process is solved;
(3) the preparation method is simple and feasible, and is beneficial to industrial production.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the practice of the invention.
All the starting materials used in the examples are commercially available, except where otherwise indicated.
The modified nano Al2O3Preparation of particles:
taking 100g of nano Al2O3Dispersing the particles in ethanol, and ultrasonically vibrating at 30 deg.C for 0.5h to obtain uniformly dispersed Al2O3The suspension, labeled liquid A. Dissolving 10g of silane coupling agent in an ethanol solvent for alcoholysis, adjusting the pH value of the solution to 5.5 by using acetic acid, and performing ultrasonic vibration hydrolysis at 30 ℃ for 1h to obtain liquid B. Adding the liquid A into the liquid B, and magnetically stirring for 1h in a water bath kettle at 45 ℃ to obtain the modified micron Al2O3A material. Modified micron Al2O3The material is filtered and washed by ethanol, and dried for standby at 80 ℃.
Example 1
A high-wear-resistance low-internal-heat-generation TPU material is prepared from the following raw materials in percentage by mass and a catalyst:
polyethylene adipate 1, 3-propanediol glycol (M ═ 3000): 52.05 percent
Hydroxyl-terminated polybutadiene (M ═ 3000): 13.01 percent
(wherein the hydroxyl-terminated polybutadiene accounts for 20% of the total amount of the polyester polyol/hydroxyl-terminated polybutadiene.)
4,4' -diphenylmethane diisocyanate (MDI-100): 20.37 percent
Hydroquinone-bis (β -hydroxyethyl) ether (HQEE): 11.67 percent
Glyceryl monostearate: 0.2 percent of
E, wax: 0.2 percent of
Modified nano Al2O3：2.5％
Wherein the dosage of the catalyst stannous octoate (T-9) is 0.06 percent of the total mass of the raw materials.
The preparation method comprises the following steps:
5205g of polyethylene glycol adipate-1, 3-propylene glycol (M is 3000), 1301g of hydroxyl-terminated polybutadiene (M is 3000), 1167g of hydroquinone-bis (beta-hydroxyethyl) ether (HQEE), 20g E wax, 20g of glycerin monostearate and 250g of modified nano Al2O3Adding the mixture into a reaction kettle A with a mechanical stirring and temperature control system, setting the temperature to be 120 ℃, and stirring; 2037g of MDI-100 was placed in the B reactor, and the temperature was set at 80 ℃.
When the materials in the A/B reaction kettles are melted and uniformly stirred and the temperature is stable, the raw materials in A, B reaction kettles are injected into a feeding port of a double-screw extruder according to components through a filling system with accurate measurement, 6g of stannous octoate (T9) is accurately measured and injected into the feeding port of the double-screw extruder through a micro-injection pump, the mixture is uniformly reacted and plasticized in the cylinder of the double-screw extruder, and is cut into elliptical particles with uniform particle size through an underwater granulator, the temperature of the double-screw extruder is 180 +/-20 ℃, and the rotating speed of the double-screw extruder is 200 r/min.
Example 2
A high-wear-resistance low-internal-heat-generation TPU material is prepared from the following raw materials in percentage by mass and a catalyst:
poly-1, 4-butylene glycol adipate diol (M ═ 2000): 52.32 percent
Hydroxyl-terminated polybutadiene (M ═ 2000): 9.23 percent
(wherein the hydroxyl-terminated polybutadiene accounts for 15% of the total amount of the polyester polyol/hydroxyl-terminated polybutadiene.)
4,4' -diphenylmethane diisocyanate (MDI-100): 23.69 percent
Hydroquinone-bis (β -hydroxyethyl) ether (HQEE): 12.46 percent
Ethylene bis stearamide: 0.2 percent of
Pentaerythritol stearate: 0.1 percent of
Modified nano Al2O3：2％
Wherein the dosage of the catalyst stannous octoate (T-9) is 0.08 percent of the total mass of the raw materials.
The preparation method comprises the following steps:
5232g of poly (1, 4-butylene adipate) glycol (M ═ 2000), 923g of hydroxyl-terminated polybutadiene (M ═ 2000), 1246g of hydroquinone-bis (beta-hydroxyethyl) ether (HQEE), 20g of ethylene bis stearamide, 10g of pentaerythritol stearate and 200g of modified nano Al2O3Adding the mixture into a reaction kettle A with a mechanical stirring and temperature control system, setting the temperature to be 120 ℃, and stirring; 2369g of MDI-100 was placed in the B reactor at 75 ℃.
When the materials in the A/B reaction kettles are melted and uniformly stirred and the temperature is stable, the raw materials in A, B reaction kettles are injected into a feeding port of a double-screw extruder according to components through a filling system with accurate measurement, 8g of stannous octoate (T9) is accurately measured and injected into the feeding port of the double-screw extruder through a micro-injection pump, the mixture is uniformly reacted and plasticized in the cylinder of the double-screw extruder, and is cut into elliptical particles with uniform particle size through an underwater granulator, the temperature of the double-screw extruder is 180 +/-20 ℃, and the rotating speed of the double-screw extruder is 220 r/min.
Example 3
A high-wear-resistance low-internal-heat-generation TPU material is prepared from the following raw materials in percentage by mass and a catalyst:
polyethylene adipate glycol (M3300): 52.97 percent
Hydroxyl-terminated polybutadiene (M ═ 3300): 5.89 percent
(wherein, hydroxyl-terminated polybutadiene accounts for 10% of the total amount of the polyester polyol/hydroxyl-terminated polybutadiene.)
Phenylene-1, 4-diisocyanate (PPDI): 19.18 percent
Resorcinol-bis (β -Hydroxyethyl) Ether (HER): 20.06 percent
Ethylene bis stearamide: 0.1 percent of
Pentaerythritol stearate: 0.3 percent of
Modified nano Al2O3：1.5％
Wherein the dosage of the catalyst stannous octoate (T-9) is 0.08 percent of the total mass of the raw materials.
The preparation method comprises the following steps:
5297g of polyethylene glycol adipate glycol (M ═ 3300), 589g of hydroxyl-terminated polybutadiene (M ═ 3300), 2006g of resorcinol-bis (beta-Hydroxyethyl) Ether (HER), 10g of ethylene bis-stearic acid amide, 30g of pentaerythritol stearate, and 150g of modified nano Al2O3Adding the mixture into a reaction kettle A with a mechanical stirring and temperature control system, setting the temperature to be 110 ℃, and stirring; 1918g of PPDI was placed in the B reactor, setting the temperature at 115 ℃.
When the materials in the A/B reaction kettles are melted and uniformly stirred and the temperature is stable, the raw materials in A, B reaction kettles are injected into a feeding port of a double-screw extruder according to components through a filling system with accurate measurement, 8g of stannous octoate (T9) is accurately measured and injected into the feeding port of the double-screw extruder through a micro-injection pump, the mixture is uniformly reacted and plasticized in the cylinder of the double-screw extruder, and is cut into elliptical particles with uniform particle size through an underwater granulator, the temperature of the double-screw extruder is 180 +/-20 ℃, and the rotating speed of the double-screw extruder is 180 r/min.
Example 4
A high-wear-resistance low-internal-heat-generation TPU material is prepared from the following raw materials in percentage by mass and a catalyst:
polyethylene adipate 1, 4-butanediol glycol (M ═ 1500): 46.79 percent
Hydroxyl-terminated polybutadiene (M1500): 2.46 percent
(wherein, hydroxyl-terminated polybutadiene accounts for 5% of the total amount of the polyester polyol/hydroxyl-terminated polybutadiene)
1, 5-Naphthalene Diisocyanate (NDI): 32.52 percent
Terephthalyl alcohol (PXG): 16.73 percent
Ethylene bis stearamide: 0.2 percent of
E, wax: 0.3 percent of
Modified nano Al2O3：1％
Wherein the dosage of the catalyst bismuth neodecanoate (C-83) is 0.1 percent of the total mass of the raw materials.
The preparation method comprises the following steps:
4679g of polyethylene glycol adipate-1, 4-butanediol ester diol (M is 1500), 246g of hydroxyl-terminated polybutadiene (M is 1500), 1673g of terephthalyl alcohol (PXG), 20g of ethylene bis stearamide, 30g of E wax and 100g of modified nano Al2O3Adding the mixture into a reaction kettle A with a mechanical stirring and temperature control system, setting the temperature to be 125 ℃, and stirring; 3252g of NDI was placed in the B reactor, setting the temperature at 135 ℃.
When the materials in the A/B reaction kettles are melted and uniformly stirred and the temperature is stable, the raw materials in A, B reaction kettles are injected into a feeding port of a double-screw extruder according to components through a filling system with accurate measurement, 10g of bismuth neodecanoate (C83) is accurately measured and injected into the feeding port of the double-screw extruder through a micro-injection pump, the mixture is uniformly reacted and plasticized in the cylinder of the double-screw extruder and is cut into elliptical particles with uniform particle size through an underwater granulator, the temperature of the double-screw extruder is 180 +/-20 ℃, and the rotating speed of the double-screw extruder is 240 r/min.
Comparative example 1
The unused modified nano Al2O3The TPU material used as the comparative example 1 has the same product design and production process as the example 1, and specifically comprises the following components in percentage by massThe raw materials are as follows:
polyethylene adipate 1, 3-propanediol glycol (M ═ 3000): 53.38 percent
Hydroxyl-terminated polybutadiene (M ═ 3000): 13.35 percent
(wherein the hydroxyl-terminated polybutadiene accounts for 20% of the total amount of the polyester polyol/hydroxyl-terminated polybutadiene.)
4,4' -diphenylmethane diisocyanate (MDI-100): 20.90 percent
Hydroquinone-bis (β -hydroxyethyl) ether (HQEE): 11.97 percent
Glyceryl monostearate: 0.2 percent of
E, wax: 0.2 percent of
Wherein the dosage of the catalyst stannous octoate (T-9) is 0.06 percent of the total mass of the raw materials.
The preparation method comprises the following steps:
adding 5338g of poly (ethylene adipate-1, 3-propylene glycol) glycol (M is 3000), 1335g of hydroxyl-terminated polybutadiene (M is 3000), 1197g of hydroquinone-bis (beta-hydroxyethyl) ether (HQEE), 20g E wax and 20g of glyceryl monostearate into a reaction kettle A with a mechanical stirring and temperature control system, setting the temperature to 120 ℃, and stirring; 2090g of MDI-100 was placed in the B reactor at 80 ℃.
When the materials in the A/B reaction kettles are melted and uniformly stirred and the temperature is stable, the raw materials in A, B reaction kettles are injected into a feeding port of a double-screw extruder according to components through a filling system with accurate measurement, 6g of stannous octoate (T9) is accurately measured and injected into the feeding port of the double-screw extruder through a micro-injection pump, the mixture is uniformly reacted and plasticized in the cylinder of the double-screw extruder, and is cut into elliptical particles with uniform particle size through an underwater granulator, the temperature of the double-screw extruder is 180 +/-20 ℃, and the rotating speed of the double-screw extruder is 200 r/min.
Comparative example 2
The TPU material without hydroxyl-terminated polybutadiene is used as a comparative example 2, the product design and production process are the same as those of the example 1, and the TPU material is specifically prepared from the following raw materials in percentage by mass:
polyethylene adipate 1, 3-propanediol glycol (M ═ 3000): 65.06 percent
4,4' -diphenylmethane diisocyanate (MDI-100): 20.37 percent
Hydroquinone-bis (β -hydroxyethyl) ether (HQEE): 11.67 percent
Glyceryl monostearate: 0.2 percent of
E, wax: 0.2 percent of
Modified nano Al2O3：2.5％
Wherein the dosage of the catalyst stannous octoate (T-9) is 0.06 percent of the total mass of the raw materials.
The preparation method comprises the following steps:
6506g of poly (ethylene adipate-1, 3-propylene glycol) diol (M is 3000), 1167g of hydroquinone-bis (beta-hydroxyethyl) ether (HQEE), 20g E wax, 20g of glycerin monostearate and 250g of modified nano Al2O3Adding the mixture into a reaction kettle A with a mechanical stirring and temperature control system, setting the temperature to be 120 ℃, and stirring; 2037g of MDI-100 was placed in the B reactor, and the temperature was set at 80 ℃.
When the materials in the A/B reaction kettles are melted and uniformly stirred and the temperature is stable, the raw materials in A, B reaction kettles are injected into a feeding port of a double-screw extruder according to components through a filling system with accurate measurement, 6g of stannous octoate (T9) is accurately measured and injected into the feeding port of the double-screw extruder through a micro-injection pump, the mixture is uniformly reacted and plasticized in the cylinder of the double-screw extruder, and is cut into elliptical particles with uniform particle size through an underwater granulator, the temperature of the double-screw extruder is 180 +/-20 ℃, and the rotating speed of the double-screw extruder is 200 r/min.
Comparative example 3
The unused hydroxyl-terminated polybutadiene and the modified nano Al are mixed2O3The TPU material is used as a comparative example, the product design and production process are the same as those of the example 1, and the TPU material is specifically prepared from the following raw materials in percentage by mass:
polyethylene adipate 1, 3-propanediol glycol (M ═ 3000): 66.73 percent
4,4' -diphenylmethane diisocyanate (MDI-100): 20.90 percent
Hydroquinone-bis (β -hydroxyethyl) ether (HQEE): 11.97 percent
Glyceryl monostearate: 0.2 percent of
E, wax: 0.2 percent of
Wherein the dosage of the catalyst stannous octoate (T-9) is 0.06 percent of the total mass of the raw materials.
The preparation method comprises the following steps:
6673g of polyethylene glycol adipate-1, 3-propanediol glycol (M ═ 3000), 1197g of hydroquinone-bis (β -hydroxyethyl) ether (HQEE), 20g E wax and 20g of glycerol monostearate were added to a reaction kettle a with a mechanical stirring and temperature control system, the temperature was set at 120 ℃ and stirring was carried out; 2090g of MDI-100 was placed in the B reactor at 80 ℃.
When the materials in the A/B reaction kettles are melted and uniformly stirred and the temperature is stable, the raw materials in A, B reaction kettles are injected into a feeding port of a double-screw extruder according to components through a filling system with accurate measurement, 6g of stannous octoate (T9) is accurately measured and injected into the feeding port of the double-screw extruder through a micro-injection pump, the mixture is uniformly reacted and plasticized in the cylinder of the double-screw extruder, and is cut into elliptical particles with uniform particle size through an underwater granulator, the temperature of the double-screw extruder is 180 +/-20 ℃, and the rotating speed of the double-screw extruder is 200 r/min.
And (3) detecting the performance of the TPU material:
the TPU materials prepared in examples 1 to 4 and comparative examples 1 to 3 were tested for their properties:
the Shore hardness of the thermoplastic polyurethane elastomer is measured according to GB/T531-2009 standard;
tensile strength test is measured according to GB/T528-2009 standard;
performing GB/T529-2008 standard test on DIN abrasion of TPU materials;
GB/T1687.3-2016 Standard was carried out to test the dynamic heat buildup of TPU material (RH-2000N type dynamic compression thermogenesis tester measurement, stroke 4.45mm, compressive stress 1 MPa).
The results are shown in Table 1.
TABLE 1
According to the detection result, the high-wear-resistance low-endogenous heat polyurethane elastomer synthesized by the method essentially reduces the endogenous heat of the TPU material, and the endogenous heat can be reduced by 39%; meanwhile, the wear resistance of the material is improved by 31 percent, the problems that the TPU material is easy to heat up and deform and is easy to wear and drop in the dynamic use process (compression, rotation and the like) are solved, and the TPU material can be widely applied to the fields of automobile tires, trundles, rubber rollers and the like.
The foregoing is merely an example of the present invention and common general knowledge of known specific structures and features of the embodiments is not described herein in any greater detail. It should be noted that, for those skilled in the art, without departing from the structure of the present invention, several changes and modifications can be made, which should also be regarded as the protection scope of the present invention, and these will not affect the effect of the implementation of the present invention and the practicability of the patent. The scope of the claims of the present application shall be determined by the contents of the claims, and the description of the embodiments and the like in the specification shall be used to explain the contents of the claims.
Claims (10)
1. A high-wear-resistance low-endogenous-heat TPU material is characterized in that:
the method comprises the following raw materials: polyester polyol, hydroxyl-terminated polybutadiene, diisocyanate and modified nano Al2O3；
The number average molecular weight of the polyester polyol is 1500-3500;
the number average molecular weight of the hydroxyl-terminated polybutadiene is 1500-.
2. A high wear resistance low internal heat TPU material as set forth in claim 1 wherein: the polyester polyol is one or more of polyethylene glycol adipate glycol, polyethylene glycol-1, 3-propylene glycol adipate glycol, polyethylene glycol-1, 4-butanediol adipate glycol or polyethylene glycol-1, 4-butanediol adipate glycol.
3. A high wear resistance low internal heat TPU material as set forth in claim 1 wherein: the addition amount of the hydroxyl-terminated polybutadiene is 5-20% of the total mass of the polyester polyol and the hydroxyl-terminated polybutadiene.
4. A high wear resistance low internal heat TPU material as set forth in claim 1 wherein: the diisocyanate is 4,4' -diphenylmethane diisocyanate, phenylene-1, 4-diisocyanate or 1, 5-naphthalene diisocyanate.
5. A high wear resistance low internal heat TPU material as set forth in claim 1 wherein: modified nano Al2O3Is silane coupling agent KH550 modified Al2O3The size is 100-500 nm.
6. A high wear resistance low internal heat TPU material as set forth in claim 1 wherein: modified nano Al2O3The preparation method comprises the following steps:
(1) taking nano Al2O3Dispersing the particles in ethanol, and ultrasonically vibrating at 25-35 deg.C for 0.5-1h to obtain uniformly dispersed Al2O3Suspending liquid;
(2) dissolving a silane coupling agent in an ethanol solvent for alcoholysis, adjusting the pH value of the solution, and performing ultrasonic vibration hydrolysis at 25-35 ℃ for 0.5-1 h;
(3) micron Al obtained in the step (1)2O3Adding into silane coupling agent solution, magnetically stirring in water bath at 40-50 deg.C for 1-1.5 hr to obtain modified micrometer Al2O3A material;
(4) modified micron Al2O3And carrying out suction filtration, washing and drying on the material for later use.
7. A high wear resistance low internal heat TPU material as set forth in claim 1 wherein: the raw materials also comprise a chain extender, a lubricant and an additional catalyst.
8. A high wear resistance low internal heat TPU material as set forth in claim 7 wherein: the chain extender is one or more of hydroquinone, hydroquinone-bis (beta-hydroxyethyl) ether or resorcinol-bis (beta-hydroxyethyl) ether; the lubricant is one or more of glyceryl monostearate, pentaerythritol stearate, E wax or ethylene bis stearamide; the catalyst is organic bismuth or organic tin.
9. A method for preparing the TPU material with high wear resistance and low endogenous heat according to claim 7, which comprises the following steps: the method comprises the following steps:
(1) polyester polyol, hydroxyl-terminated polybutadiene, a chain extender, a lubricant and modified micron Al2O3Adding the mixture into a reaction kettle A with a mechanical stirring and temperature control system for mixing, and placing diisocyanate into a reaction kettle B for stirring;
(2) when the materials in the two reaction kettles are uniformly stirred, the raw materials in the A, B reaction kettle are injected into a feeding port of a double-screw extruder through a filling system with accurate measurement, a catalyst is injected into the feeding port of the double-screw extruder through a micro-injection pump, the mixture is reacted and plasticized in a cylinder of the double-screw extruder, and the mixture is cut into elliptical particles through an underwater granulator.
10. The method for preparing a high wear resistance low endotherm TPU material of claim 9, wherein: in the step (1), the temperature of the reaction kettle A is 110-125 ℃, and the temperature of the reaction kettle B is 80-135 ℃; the temperature of the double-screw extruder in the step (2) is 150-200 ℃, and the rotating speed is 180-240 r/min.
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