CN104140666A - High-abrasion-resistance transparent thermoplastic polyurethane elastomer for ball film and manufacturing method thereof - Google Patents
High-abrasion-resistance transparent thermoplastic polyurethane elastomer for ball film and manufacturing method thereof Download PDFInfo
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- CN104140666A CN104140666A CN201410371122.1A CN201410371122A CN104140666A CN 104140666 A CN104140666 A CN 104140666A CN 201410371122 A CN201410371122 A CN 201410371122A CN 104140666 A CN104140666 A CN 104140666A
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Abstract
The invention provides high-abrasion-resistance transparent thermoplastic polyurethane elastomer for a ball film and a manufacturing method of the high-abrasion-resistance transparent thermoplastic polyurethane elastomer. The thermoplastic polyurethane elastomer is made of nano-modification TPU composite materials, and the nano-modification TPU composite materials are formed by mixing, by weight, 70-90 parts of polyurethane-nano-powder composite components, 3-10 parts of chain extenders, 0.5-2 parts of antioxidants, 1.2-4 parts of hydrolytic stabilizers, 1-3 parts of slipping agents, 1-3 parts of antiblocking agents, 3-20 parts of fillers and 0.8-3 parts of fire retardant. The nano-modification TPU composite materials manufactured by modifying and innovating all raw material components and the configuration proportion of the TPU composite materials have the unique advantages of being high in hardness and abrasion resistance, strong in elasticity and toughness, high in transparency, high in hydrolysis resistance, good in environmental protection, capable of achieving high-frequency welding and the like, the wide application of the TPU materials is promoted, and the wide market prospect is achieved.
Description
Technical field
The present invention relates to TPU material technology field, relate to more specifically a kind of for the elastomeric nano modification TPU of ball film high abrasion transparent thermoplastic polyurethane matrix material and preparation method thereof.
Background technology
TPU (Thermoplastic polyurethanes) material is a kind of Polyurethane Thermoplastic Elastomer material, have that durometer level is wide, the advantage such as wear-resistance and oil-resistance, transparent, good springiness, therefore be used widely in fields such as daily necessities, sports goods, toy, finishing material, and have and progressively replace PVC to meet the trend of more and more field environmental requirements.Therefore TPU material is a kind of novel material with wide market outlook, there is following technical problem in existing TPU material: wear resistance, elasticity and toughness can't meet the application demand of some particular technology areas, as the preparation field of football film, existing TPU material ubiquity in football film preparation hardness not, wear no resistance and the defect such as elasticity and toughness deficiency, limited the widespread use of TPU in similar techniques fields such as football films.
Summary of the invention
The present invention is based on above-mentioned prior art problem, a kind of nano modification TPU matrix material for ball film and preparation method thereof is proposed, by the each component of raw material and allocation ratio thereof are carried out to modification innovation, and in conjunction with the long-term test adjustment of our company, a kind of hardness wear resistance of proposition of innovation is high, strong transparency is high simultaneously, hydrolytic resistance is high, the feature of environmental protection good for elasticity and toughness, brand-new nano modification TPU matrix material that can hight frequency welding and preparation method thereof.
It is as follows that the present invention solves the problems of the technologies described above taked technical scheme:
A kind of nano modification TPU matrix material, by urethane-nano-powder composite components of 70-90 weight part, the chainextender of 3-10 part weight part, the antioxidant of 0.5-2 weight part, the hydrolysis stabilizer of 1.2-4 weight part, the slipping agent of 1-3 weight part, antiblocking agent, the weighting agent of 3-20 weight part and mixing the making of fire retardant of 0.8-3 weight part of 1-3 weight part, wherein said urethane-nano-powder composite components is by polyether glycol, isocyanic ester, composite nano powder, silane coupling agent, chainextender and foam stabilizer reaction make, during described urethane-nano-powder composite components self forms, the parts by weight of contained each composition are: polyether glycol 30-75 weight part, isocyanic ester 10-40 weight part, composite nano powder 10-25 weight part, silane coupling agent 1.5-9 weight part, chainextender 5-25 weight part, foam stabilizer 0.5-3 weight part, the particle diameter of wherein said composite nano powder is between 20-50nm, and described composite nano powder by particle diameter in 20-50nm and mass percentage content the nano SiC at 70-80%, particle diameter is the nano-TiO at 5-8% in 30-40nm and mass percentage content
2, particle diameter in 30-60nm and mass percentage content at the nano-ZnO of 3-5%, particle diameter in 30-60nm and mass percentage content the nanometer Cr at 1-3%
2o
3, particle diameter in 30-40nm and mass percentage content the nanometer AL at 8-10%
2o
3with particle diameter 30-50nm and the mass percentage content nanometer SiO at 3-6%
2composition.
Further according to nano modification TPU matrix material of the present invention, wherein said chainextender is selected from ethylene glycol, 1,2-propylene glycol, 1, ammediol, 1,4-butyleneglycol, Diethylene Glycol, dipropylene glycol, neopentyl glycol, 1,6-hexylene glycol, cyclohexanedimethanol, 3,3 '-bis-is chloro-4, one or more mixtures in 4-diaminodiphenylmethane.
Further, according to nano modification TPU matrix material of the present invention, wherein said antioxidant is oxidation inhibitor-264, dihydroxyphenyl propane, triphenyl phosphite, oxidation inhibitor-1010, antioxidant 1076 or tris phosphite, described hydrolysis stabilizer is charing diimine, described slipping agent is the one in erucicamide, stearylamide, Zinic stearas or amine hydroxybenzene, described antiblocking agent is the one in paraffin, erucicamide, stearylamide or nano silicon, described weighting agent is the one in calcium carbonate, fine silica powder or kaolin, the polypropylene of the melting index that described fire retardant is 45%-60% by mass percentage content in 5-10g/10min, mass percentage content is that the melting index of 10%-20% is at the polyethylene of 1.0-1.8g/10min, mass percentage content is the powdered talc that is selected from of 20%-30%, kaolinite, sericite, what at least one mineral filler in silicon-dioxide and diatomite and mass percentage content were 10%-25% is selected from decabrominated dipheny base ether, the organic fire-resisting halogenide mixing of ten dichloro ten dihydro dimethano-benzene azoles cyclooctene or its mixture makes.
Further, according to nano modification TPU matrix material of the present invention, wherein said foam stabilizer is modified silicone surfactants; Described polyether glycol be a kind of in a kind of and propylene oxide in propylene glycol, glycerine, TriMethylolPropane(TMP), dihydroxyphenyl propane, triisocyanate, tolylene diamine, epoxy hexane, butylene oxide ring make by polyaddition reaction there is the polyether glycol that 2 functionality and molecular-weight average are 1000-3000; Described isocyanic ester is selected from tolylene diisocyanate (TDI), 4,4-diphenylmethanediisocyanate (MDI), PPDI (PPDI), dimethyl diphenyl vulcabond (TODI), 1,5-is the mixture of one or both in vulcabond (NDI), PPDI (PPDI), hexamethylene vulcabond (HDI), dicyclohexyl methane diisocyanate (HMDI) how.
Further, according to nano modification TPU matrix material of the present invention, wherein said silane coupling agent reacts and makes for 8 hours according to mol ratio 1:1, at 60-80 DEG C by any two kinds in triethyl vinyl silanes, γ-aminopropyl triethoxysilane, γ-glycidyl ether oxygen propyl trimethoxy silicane, triple phenoxyl vinyl silanes, phenylamino methyltrimethoxy silane, aminoethyl aminopropyl trimethoxysilane and methacryloxypropyl trimethoxy silane.
Further according to nano modification TPU matrix material of the present invention, the concentrated hydrochloric acid neutralizing agent hybrid reaction that the sodium hydroxide hydrolysis agent that γ-aminopropyl dimethoxy-methyl silane that wherein said silane coupling agent is 18% by mass percentage content, the methyl acrylate that mass percentage content is 12%, Virahol organic solvent that mass percentage content is 35%, the concentration that mass percentage content is 25% are 20% and mass percentage content are 10% makes.
Further according to nano modification TPU matrix material of the present invention, wherein said silane coupling agent is by the terephthalic acid calcium of 20-30 weight part, the para-phthalic sodium of 10-15 weight part, the terephthalic acid aluminium of 10-20 weight part, 10-15 weight part two-(the silica-based propyl group of γ-triethoxy) tetrasulfide, the gamma-mercaptopropyltriethoxysilane of 8-12 weight part, the γ-aminopropyl triethoxysilane of 12-20 weight part, the γ-(2 of 5-10 weight part, 3-epoxy the third oxygen) propyl trimethoxy silicane, the white carbon black hybrid reaction of the stearic acid of 2-6 weight part and 5-12 weight part makes.
Further according to nano modification TPU matrix material of the present invention, the shore hardness of wherein said nano modification TPU matrix material be 90-95A, abrasion intensity meet under 9kPa pressure, grind 650 turn after without wear phenomenon, resistance to xanthochromia grade more than level Four, fusing point in 170-175 DEG C, melting index in 55-60g/10min, tensile strength in 40-60Mpa, tear strength >=90kgf/cm, viscosity in 8200-8240ps/200 DEG C, elongation >=550%.
A preparation method for nano modification TPU matrix material, comprises the following steps:
Step 1, prepare composite nano powder, by nano SiC, nano-TiO
2, nano-ZnO, nanometer Cr
2o
3, nanometer AL
2o
3with nanometer SiO
2according to fully mixing after above-mentioned mass percentage content configuration, and the particle diameter of mixture is ground to 20-50nm, obtains composite nano powder.
Step 2, select one of following manner to prepare silane coupling agent, mode one: to react according to mol ratio 1:1, at 60-80 DEG C and within 8 hours, make silane coupling agent by any two kinds in triethyl vinyl silanes, γ-aminopropyl triethoxysilane, γ-glycidyl ether oxygen propyl trimethoxy silicane, triple phenoxyl vinyl silanes, phenylamino methyltrimethoxy silane, aminoethyl aminopropyl trimethoxysilane and methacryloxypropyl trimethoxy silane; Mode two: the concentrated hydrochloric acid neutralizing agent hybrid reaction that the sodium hydroxide hydrolysis agent that the γ-aminopropyl dimethoxy-methyl silane that is 18% by mass percentage content, methyl acrylate that mass percentage content is 12%, Virahol organic solvent that mass percentage content is 35%, the concentration that mass percentage content is 25% are 20% and mass percentage content are 10% makes silane coupling agent; Mode three: by the terephthalic acid aluminium of the para-phthalic sodium of the terephthalic acid calcium of 20-30 weight part, 10-15 weight part, 10-20 weight part, 10-15 weight part two-(the silica-based propyl group of γ-triethoxy) tetrasulfide, the gamma-mercaptopropyltriethoxysilane of 8-12 weight part, the γ-aminopropyl triethoxysilane of 12-20 weight part, γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane, the stearic acid of 2-6 weight part and the white carbon black hybrid reaction of 5-12 weight part of 5-10 weight part make silane coupling agent;
Step 3, get composite nano powder 10-25 weight part prepared by step 1, get silane coupling agent 1.5-9 weight part prepared by step 2, fully mix and be incorporated in stirring reaction 6h at 85-95 DEG C, then at 105-120 DEG C, be dried after 12h, put into again ball mill ball mill pulverizing 0.5 hour, obtain the composite nano powder of modification;
Step 4, polyether glycol vacuum hydro-extraction at 100-120 DEG C of getting 30-75 weight part, be cooled to 30-50 DEG C, under rapid stirring, add the isocyanic ester of 10-40 weight part, insulation reaction 2h at 70-90 DEG C, the isocyanate terminated performed polymer that synthetic massfraction is 5%;
Step 5, get the isocyanate terminated performed polymer that modification composite nano powder that chainextender 5-25 weight part, foam stabilizer 0.5-3 weight part make with described step 3 and step 4 make and evenly mix, and be added in twin screw extruder, be 150-250rpm at screw speed, temperature is melt pelletization at 170-195 DEG C, obtains urethane-nano-powder composite components;
Step 6, get urethane-nano-powder composite components 70-90 weight part that step 5 makes, get chainextender 3-10 weight part, get oxidation inhibitor 0.5-2 weight part, get hydrolysis stabilizer 1.2-4 weight part, get slipping agent 1-3 weight part, get antiblocking agent 1-3 weight part, get weighting agent 3-20 weight part, get fire retardant 0.8-3 weight part and mix 10-20min in stirrer high speed, the rotating speed of stirrer is 80-200r/min, carry out the combined shaping reaction of material, temperature is controlled at 60-100 DEG C, finally under 80-120 DEG C of condition, dry 2-2.5h obtains described nano modification TPU matrix material.
Further according to the preparation method of nano modification TPU matrix material of the present invention, wherein described in the mode two of step 2, the concrete preparation method of silane coupling agent is: by above-mentioned mass content, γ-aminopropyl dimethoxy-methyl silane and Virahol organic solvent are put in reactor, and between 30～40 DEG C, in whipping process, drip the methyl acrylate of above-mentioned mass content, and when methyl acrylate add after cooling placement predetermined amount of time, then reactant is warming up to 55～65 DEG C, under vacuum condition, underpressure distillation is about 30 minutes, residue in reactor is ester type intermediate, again the sodium hydroxide hydrolysis agent of above-mentioned mass content is mixed with described ester type intermediate, stirring heating is carried out back hydrolysis reaction, controlling agitator speed is 200～300 revs/min, back hydrolysis obtains sodium salt intermediate water solution after the reaction scheduled time, the most backward described sodium salt intermediate water solution adds the concentrated hydrochloric acid neutralizing agent of above-mentioned mass content, under the condition of heated and stirred, carry out neutralization reaction, neutralization reaction obtains neutralization reactant after the scheduled time, neutralization reactant is cooled to 65～75 DEG C afterwards, open vacuum valve to reaction kettle for vacuumizing, vacuum is pulled out the low-boiling-point substance in reactor, afterwards reactor is cooled to room temperature, material suction filtration in reactor is taken out, obtain described silane coupling agent, wherein described in the mode three of step 2, the concrete preparation method of silane coupling agent is: by above-mentioned weight part by terephthalic acid calcium, para-phthalic sodium and terephthalic acid aluminium and stearic acid jointly add in stirring tank under the rotating speed of turn at 1800-2000/min and stir 5-10min, then stop activation 15-30min, add again white carbon black to mix, again stir 5-10min with turn/min of 1800-2000 speed, at the uniform velocity add again described pair-(the silica-based propyl group of γ-triethoxy) tetrasulfide, gamma-mercaptopropyltriethoxysilane, γ-aminopropyl triethoxysilane and γ-(2, 3-epoxy the third oxygen) propyl trimethoxy silicane, continue to stir 10-20min with turn/min of 1800-2000 speed, obtain described silane coupling agent.
At least can reach following technique effect by technical scheme of the present invention:
1), the present invention by innovating urethane-nano-powder composite components in nano modification TPU matrix material, greatly improve the performances such as hardness, wear resistance, elasticity and the toughness of nano modification TPU composites, promoted TPU material in football film preparation etc., elasticity toughness to be had the widespread use of the technical field of unique need;
2), nano modification TPU matrix material of the present invention is introduced the components such as antioxidant, fire retardant, hydrolysis stabilizer, slipping agent, antiblocking agent and weighting agent with the component concentration of original creation simultaneously, make that made nano modification TPU composites has that wear resistance is high, transparency is high, hydrolytic resistance is high, good springiness, cold-resistant, durable, material environmental protection, to human body without any stealth injure, can print, can hight frequency welding etc. unique technology advantage, promote being widely used of TPU material, there are wide market outlook.
Embodiment
Below technical scheme of the present invention is described in detail, so that those skilled in the art can more clearly understand the present invention, but does not therefore limit the scope of the invention.
Hardness of the present invention is large, wear resistance good, elasticity and the strong nano modification TPU matrix material of toughness by urethane-nano-powder composite components, chainextender, antioxidant, hydrolysis stabilizer, slipping agent, antiblocking agent, weighting agent and fire retardant melting mixing after curtain coating form, the content of wherein counting by weight each component is:
| Urethane-nano-powder composite components | 70-90 part |
| Chainextender | 3-10 part |
| Antioxidant | 0.5-2 part |
| Hydrolysis stabilizer | 1.2-4 part |
| Slipping agent | 1-3 part |
| Antiblocking agent | 1-3 part |
| Weighting agent | 3-20 part |
| Fire retardant | 0.8-3 part |
The described chainextender of using in wherein said nano modification TPU matrix material preparation is BDO, 1, one or more in 6-hexylene glycol, ethylene glycol or 1,2-PD.
Wherein said antioxidant is oxidation inhibitor-264, dihydroxyphenyl propane, triphenyl phosphite, oxidation inhibitor-1010, antioxidant 1076 or tris phosphite.
Wherein said hydrolysis stabilizer is charing diimine.
Wherein said slipping agent is the one in erucicamide, stearylamide, Zinic stearas or amine hydroxybenzene.
Wherein said antiblocking agent is paraffin, erucicamide, stearylamide or nano silicon.
Wherein said weighting agent is the one in calcium carbonate, fine silica powder or kaolin.
Wherein said fire retardant is the polypropylene in 5-10g/10min by the melting index of (by mass percentage) 45%-60%, the melting index of 10%-20% is at the polyethylene of 1.0-1.8g/10min, 20%-30% is selected from powdered talc, kaolinite, sericite, in silicon-dioxide and diatomite, the mineral filler of at least one and 10%-25%'s is selected from decabrominated dipheny base ether, the organic fire-resisting halogenide mixing of ten dichloro ten dihydro dimethano-benzene azoles cyclooctene or its mixture makes.
Wherein said urethane-nano-powder composite components is made by polyether glycol, isocyanic ester, composite nano powder, silane coupling agent, chainextender and foam stabilizer reaction, the content that each component is counted by weight in described urethane-nano-powder composite components self composition is (note: the selection of these parts by weight is the weight configuration relations between himself the included each component providing for the ease of the preparation of urethane-nano-powder composite components, be not the actual weight umber in whole nano modification TPU matrix material, other parts are roughly the same):
| Polyether glycol | 30-75 part |
| Isocyanic ester | 10-40 part |
| Composite nano powder | 10-25 part |
| Silane coupling agent | 1.5-9 part |
| Chainextender | 5-25 part |
| Foam stabilizer | 0.5-3 part |
Wherein the chainextender in above-mentioned urethane-nano-powder composite components preparation is selected from ethylene glycol, 1,2-propylene glycol, 1, ammediol, 1,4-butyleneglycol, Diethylene Glycol, dipropylene glycol, neopentyl glycol, 1,6-hexylene glycol, cyclohexanedimethanol, 3,3 '-bis-is chloro-4, one or more mixtures in 4-diaminodiphenylmethane, the chainextender that preferably chain extension coefficient is 0.9.
Wherein the foam stabilizer in above-mentioned urethane-nano-powder composite components preparation is modified silicone surfactants.
Wherein the polyether glycol in the preparation of above-mentioned urethane-nano-powder composite components be one in a kind of and propylene oxide in propylene glycol, glycerine, TriMethylolPropane(TMP), dihydroxyphenyl propane, triisocyanate, tolylene diamine, epoxy hexane, butylene oxide ring by polyaddition reaction gained, the polyether glycol that to be preferably 2 functionality, molecular-weight average be 1000-3000.
Wherein the isocyanic ester in above-mentioned urethane-nano-powder composite components preparation is tolylene diisocyanate (TDI), 4,4-diphenylmethanediisocyanate (MDI), PPDI (PPDI), dimethyl diphenyl vulcabond (TODI), 1,5-is the mixture of one or both in vulcabond (NDI), PPDI (PPDI), hexamethylene vulcabond (HDI), dicyclohexyl methane diisocyanate (HMDI) etc. how.
Nano inoganic particle is with its small particle size, bigger serface, in polymer materials and between matrix, there is stronger bonding force adding to, not only can improve rigidity, hardness and the wear resisting property of polymer materials, can also play toughening effect simultaneously, what therefore the present invention innovated adds nano inoganic particle in urethane, composite nano powder in concrete above-mentioned urethane-nano-powder composite components preparation is that median size is between 20-50nm taking nano SiC as main composite nano powder.Wherein in whole composite nano powder, the weight percent of each component is: nano SiC accounts for 70-80%, particle diameter 20-50nm; Nano-TiO
2account for 5-8%, particle diameter 30-40; Nano-ZnO accounts for 3-5%, particle diameter 30-60nm; Nanometer Cr
2o
3account for 1-3%, particle diameter 30-60nm; Nanometer Al
2o
3account for 8-10%, particle diameter 30-40nm; Nanometer SiO
2account for 3-6%, particle diameter 30-50nm.By mixing ZnO and Cr
2o
3can improve the electrostatic shielding performance of composite nano powder in polymkeric substance, by mixing nano-TiO
2can improve material uv absorption property, by mixing nanometer Al
2o
3can improve linked reaction, increase consistency.
Because above-mentioned composite nano powder belongs to ultra-fine micropowder material, surface can be larger, adding to, Cluster Phenomenon in polymer materials is more serious, for ensureing that these composite nano powders can be distributed in polymer matrix material very uniformly, need especially it to be carried out to surface modification treatment, coupling agent can improve the affinity between nano-powder material and polymer materials, the present invention finds that by long-term experiment adopting silane coupling agent to carry out organic modification for above-mentioned composite nano powder can be good at improving the dispersion affinity of nano-powder material in polymkeric substance.In order to improve the modification performance to composite nano powder of the present invention, the present invention carries out long-term research to the silane coupling agent that is applicable to this composite nano powder, find that by research the silane coupling agent of using in above-mentioned urethane-nano-powder composite components preparation generally can be chosen as: by triethyl vinyl silanes, γ-aminopropyl triethoxysilane, γ-glycidyl ether oxygen propyl trimethoxy silicane, triple phenoxyl vinyl silanes, phenylamino methyltrimethoxy silane, in aminoethyl aminopropyl trimethoxysilane and methacryloxypropyl trimethoxy silane any two kinds according to mol ratio 1:1, at 60-80 DEG C, react 8h and obtain silane coupling agent.The silane coupling agent further preferably providing for the silane coupling agent silane coupling agent that also following the first optimal way provides or second optimal way of composite nano powder modification of the present invention.The first optimal way: the material component of described silane coupling agent is: the sodium hydroxide hydrolysis agent that γ-aminopropyl dimethoxy-methyl silane that mass percent is 18%, the methyl acrylate that mass percent is 12%, Virahol organic solvent that mass percent is 35%, the concentration that mass percent is 25% are 20%, the concentrated hydrochloric acid neutralizing agent that mass percent is 10%.The preparation process of described silane coupling agent is: γ-aminopropyl dimethoxy-methyl silane and the Virahol organic solvent of above-mentioned mass parts are put in reactor, and in whipping process, dripped methyl acrylate between 30～40 DEG C of temperature; Cooling preventing 6 hours after methyl acrylate adds, then reactant is warming up to 55～65 DEG C, open vacuum, under 0.098 atmospheric vacuum condition, carry out underpressure distillation, organic solvent and superfluous methyl acrylate are separated from reactant, underpressure distillation 30 minutes, the residue in reactor is ester type intermediate; Sodium hydroxide hydrolysis agent and described ester type intermediate in formula are put in the reactor that is provided with condensation reflux unit, stirring heating is carried out back hydrolysis reaction, agitator speed is 200～300 revs/min, reactor is warming up to 98 DEG C, back hydrolysis 60 minutes used times of reaction, the aqueous solution of acquisition sodium salt intermediate; The aqueous solution to the described sodium salt intermediate in reactor adds the concentrated hydrochloric acid neutralizing agent in formula, under the condition of heated and stirred, carry out neutralization reaction, 10 minutes neutralization reaction used times, obtain neutralization reactant, neutralization reactant is cooled to 65～75 DEG C afterwards, open vacuum valve to reaction kettle for vacuumizing, vacuum tightness is 0.098 normal atmosphere, vacuum is pulled out the low-boiling-point substance in still, vacuum is pulled out 30 minutes used times, reactor cools to room temperature afterwards, and the material suction filtration in reactor is taken out, and obtains silane coupling agent.The second optimal way: the material component (quality) of described silane coupling agent is: terephthalic acid calcium 20-30 part, para-phthalic sodium 10-15 part, terephthalic acid aluminium 10-20 part, two-(the silica-based propyl group of γ-triethoxy) tetrasulfide 10-15 part, gamma-mercaptopropyltriethoxysilane 8-12 part, γ-aminopropyl triethoxysilane 12-20 part, γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane 5-10 part, stearic acid 2-6 part, white carbon black 5-12 part.The preparation method of silane coupling agent described in the second optimal way, by the terephthalic acid calcium of above-mentioned mass parts, para-phthalic sodium and terephthalic acid aluminium and stearic acid jointly add in stirring tank under the rotating speed of turn at 1800-2000/min and stir 5-10min, then stop activation 15-30min, add again white carbon black to mix, stir 5-10min with turn/min of 1800-2000 speed, at the uniform velocity add again above-mentioned pair-(the silica-based propyl group of γ-triethoxy) tetrasulfide, gamma-mercaptopropyltriethoxysilane, γ-aminopropyl triethoxysilane and γ-(2, 3-epoxy the third oxygen) propyl trimethoxy silicane, continue to stir 10-20min with turn/min of 1800-2000 speed, obtain described silane coupling agent.
The preparation process that further provides nano modification TPU matrix material of the present invention below, specifically comprises the following steps:
Step 1, according to above-mentioned component content configuration composite nano powder, and be ground to 20-50nm particle diameter, make according to the method described above the silane coupling agent for modification composite nano powder simultaneously;
Step 2, according to above-mentioned metering ratio, silane coupling agent synthetic step 1 and composite nano powder are mixed, and at 85-95 DEG C stirring reaction 6h, then at 105-120 DEG C after dry 12h, put into again ball mill ball mill pulverizing at least 0.5 hour, obtain the composite nano powder of modification;
Step 3, according to above-mentioned metering ratio, by polyether glycol vacuum hydro-extraction at 100-120 DEG C, be cooled to 30-50 DEG C, under rapid stirring, add described isocyanic ester, insulation reaction 2h at 70-90 DEG C, the isocyanate terminated performed polymer that synthetic massfraction is 5%;
Step 4, by the isocyanate terminated performed polymer obtaining in the modification composite nano powder obtaining in step 2 and step 3 connect agent with the expansion of above-mentioned metering, foam stabilizer evenly mixes, add in twin screw extruder, be 150-250rpm at screw speed, temperature is melt pelletization at 170-195 DEG C, obtains urethane-nano-powder composite components;
Step 5, according to above-mentioned metering ratio, urethane-nano-powder composite components that step 4 is made mixes 10-20min with chainextender, oxidation inhibitor, hydrolysis stabilizer, slipping agent, antiblocking agent, weighting agent and the fire retardant of above-mentioned metering in stirrer high speed, the rotating speed of stirrer is 80-200r/min, carry out the combined shaping reaction of material, temperature is controlled at 60-100 DEG C, and finally under 80-120 DEG C of condition, dry 2-2.5h obtains nano modification TPU matrix material of the present invention.
Test by experiment, its Shore A hardness of nano modification TPU matrix material making of the present invention is 90-95A, abrasion intensity is under 9Kpa pressure, mill 650 turns rear without wear phenomenon, more than resistance to xanthochromia level Four, fusing point is 170-175 DEG C, melting index is 55-60g/10min, tensile strength 40-60Mpa, tear strength >=90kgf/cm, viscosity is 8200-8240ps/200 DEG C, elongation >=550%, and then the nano modification TPU matrix material obtaining by scheme of the present invention to have wear resistant high, hydrolytic resistance is high, good springiness, cold-resistant, durable, material environmental protection, human body is injured without any stealth, can print, can hight frequency welding etc. technical superiority, the various undesirable elements of TPU film in sports equipment application are fundamentally solved, expand the Application Areas of nano modification TPU matrix material.
Embodiment 1
Nano modification TPU matrix material preparation process as the present invention's the first preferred implementation is as follows:
(1) configuration composite nano powder, wherein the nano SiC of particle diameter 20-50nm accounts for the nano-TiO of 70 % by weight, particle diameter 30-40
2the nano-ZnO that accounts for 8 % by weight, particle diameter 30-60nm accounts for the nanometer Cr of 3 % by weight, particle diameter 30-60nm
2o
3account for the nanometer Al of 3 % by weight, particle diameter 30-40nm
2o
3account for the nanometer SiO of 10 % by weight, particle diameter 30-50nm
2account for 6 % by weight, above-mentioned each nano-component is fully mixed and its median size is ground to 20-50nm, make composite nano powder.
(2) prepare silane coupling agent, by in triethyl vinyl silanes, γ-aminopropyl triethoxysilane, γ-glycidyl ether oxygen propyl trimethoxy silicane, triple phenoxyl vinyl silanes, phenylamino methyltrimethoxy silane, aminoethyl aminopropyl trimethoxysilane and methacryloxypropyl trimethoxy silane any two kinds according to mol ratio 1:1, between 60-80 DEG C, react 8h and make silane coupling agent.
(3) get 10 parts of the prepared composite nano powders of step (1), get 1.5 parts of the prepared silane coupling agents of step (2), fully mix and be incorporated in 85 DEG C of stirring reaction 6h, then at 105 DEG C, be dried after 12h, put into again ball mill ball mill pulverizing 0.5 hour, obtain the composite nano powder of modification.
(4) get polyether glycol vacuum hydro-extraction at 100 DEG C of 30 weight parts, be cooled to 30 DEG C, under rapid stirring, add the isocyanic ester of 10 weight parts, insulation reaction 2h at 70 DEG C, synthetic massfraction is 5% isocyanate terminated performed polymer, and wherein polyether glycol is propylene glycol, glycerine, TriMethylolPropane(TMP), dihydroxyphenyl propane, triisocyanate, one in tolylene diamine and propylene oxide, epoxy hexane, one in butylene oxide ring is by polyaddition reaction gained, and is 2 functionality, molecular-weight average is the polyether glycol of 1000-3000, and described isocyanic ester is tolylene diisocyanate (TDI), 4,4-diphenylmethanediisocyanate (MDI), PPDI (PPDI), dimethyl diphenyl vulcabond (TODI), how vulcabond (NDI) of 1,5-, PPDI (PPDI), hexamethylene vulcabond (HDI), the mixture of one or both in dicyclohexyl methane diisocyanate (HMDI) etc.
(5) get and expand even agent 5 weight parts, the isocyanate terminated performed polymer that the modification composite nano powder that foam stabilizer 0.5 weight part makes with above-mentioned steps (3) and step (4) make evenly mixes, and be added in twin screw extruder, be 150rpm at screw speed, temperature is melt pelletization at 170 DEG C, obtain urethane-nano-powder composite components, it is 0.9 and by ethylene glycol that wherein said chainextender is selected from chain extension coefficient, 1, 2-propylene glycol, 1, ammediol, 1, 4-butyleneglycol, Diethylene Glycol, dipropylene glycol, neopentyl glycol, 1, 6-hexylene glycol, cyclohexanedimethanol, 3, 3 '-bis-chloro-4, the chainextender of one or more compositions of mixtures in 4-diaminodiphenylmethane, described foam stabilizer is selected from modified silicone surfactants.
(6) get urethane-nano-powder composite components 70 weight parts that step (5) makes, get chainextender 3 weight parts, get oxidation inhibitor 0.5 weight part, get hydrolysis stabilizer 1.2 weight parts, get slipping agent 1 weight part, get antiblocking agent 1 weight part, get weighting agent 3 weight parts, get fire retardant 0.8 weight part and mix 10min in stirrer high speed, the rotating speed of stirrer is 80r/min, carry out the combined shaping reaction of material, temperature is controlled at 60 DEG C, finally under 80 DEG C of conditions, dry 2h obtains nano modification TPU matrix material of the present invention, chainextender is wherein BDO, 1,6-hexylene glycol, one or more in ethylene glycol or 1,2-PD, antioxidant is wherein oxidation inhibitor-264, dihydroxyphenyl propane, triphenyl phosphite, oxidation inhibitor-1010, antioxidant 1076 or tris phosphite, wherein said hydrolysis stabilizer is charing diimine, wherein said slipping agent is erucicamide, stearylamide, one in Zinic stearas or amine hydroxybenzene, wherein said antiblocking agent is paraffin, erucicamide, stearylamide or nano silicon, wherein said weighting agent is calcium carbonate, one in fine silica powder or kaolin, wherein said fire retardant is the polypropylene in 5-10g/10min by 50% melting index, 15% melting index is at the polyethylene of 1.0-1.8g/10min, 25% the decabrominated dipheny base ether mixing that is selected from powdered talc and kaolinic mineral filler and 10% makes.
Embodiment 2
Nano modification TPU matrix material preparation process as the present invention's the second preferred implementation is as follows:
(1) configuration composite nano powder, wherein the nano SiC of particle diameter 20-50nm accounts for the nano-TiO of 80 % by weight, particle diameter 30-40
2the nano-ZnO that accounts for 5 % by weight, particle diameter 30-60nm accounts for the nanometer Cr of 3 % by weight, particle diameter 30-60nm
2o
3account for the nanometer Al of 1 % by weight, particle diameter 30-40nm
2o
3account for the nanometer SiO of 8 % by weight, particle diameter 30-50nm
2account for 3 % by weight, above-mentioned each nano-component is fully mixed and its median size is ground to 20-50nm, make composite nano powder.
(2) prepare silane coupling agent, first according to the raw materials component of following mass ratio preparation silane coupling agent: γ-aminopropyl dimethoxy-methyl silane that mass percent is 18%, mass percent is 12% methyl acrylate, mass percent is 35% Virahol organic solvent, mass percent is the sodium hydroxide hydrolysis agent that 25% concentration is 20%, mass percent is 10% concentrated hydrochloric acid neutralizing agent, concrete preparation process is: γ-aminopropyl dimethoxy-methyl silane and the Virahol organic solvent of above-mentioned mass parts are put in reactor, and between 30～40 DEG C of temperature, in whipping process, drip methyl acrylate, cooling placement 6 hours after methyl acrylate adds, then reactant is warming up to 55～65 DEG C, open vacuum, under 0.098 atmospheric vacuum condition, carry out underpressure distillation, organic solvent and superfluous methyl acrylate are separated from reactant, underpressure distillation 30 minutes, the residue in reactor is ester type intermediate, sodium hydroxide hydrolysis agent and described ester type intermediate in formula are put in the reactor that is provided with condensation reflux unit, stirring heating is carried out back hydrolysis reaction, agitator speed is 200～300 revs/min, reactor is warming up to 98 DEG C, back hydrolysis 60 minutes used times of reaction, the aqueous solution of acquisition sodium salt intermediate, the aqueous solution to the described sodium salt intermediate in reactor adds the concentrated hydrochloric acid neutralizing agent in formula, under the condition of heated and stirred, carry out neutralization reaction, 10 minutes neutralization reaction used times, obtain neutralization reactant, neutralization reactant is cooled to 65～75 DEG C afterwards, open vacuum valve to reaction kettle for vacuumizing, vacuum tightness is 0.098 normal atmosphere, vacuum is pulled out the low-boiling-point substance in still, vacuum is pulled out 30 minutes used times, reactor cools to room temperature afterwards, and the material suction filtration in reactor is taken out, and obtains silane coupling agent.
(3) get 25 parts of the prepared composite nano powders of step (1), get 9 parts of the prepared silane coupling agents of step (2), fully mix and be incorporated in stirring reaction 6h at 95 DEG C, then at 120 DEG C, be dried after 12h, put into again ball mill ball mill pulverizing 0.5 hour, obtain the composite nano powder of modification.
(4) get polyether glycol vacuum hydro-extraction at 120 DEG C of 75 weight parts, be cooled to 50 DEG C, under rapid stirring, add the isocyanic ester of 40 weight parts, insulation reaction 2h at 90 DEG C, synthetic massfraction is 5% isocyanate terminated performed polymer, and the preparation of polyether glycol and isocyanic ester self is similar to Example 1.
(5) getting the isocyanate terminated performed polymer that modification composite nano powder that chainextender 25 weight parts, foam stabilizer 3 weight parts make with above-mentioned steps (3) and step (4) make evenly mixes, and be added in twin screw extruder, be 250rpm at screw speed, temperature is melt pelletization at 195 DEG C, obtain urethane-nano-powder composite components, the preparation of wherein said chainextender and foam stabilizer is with embodiment 1.
(6) get urethane-nano-powder composite components 90 weight parts that step (5) makes, get chainextender 10 weight parts, get oxidation inhibitor 2 weight parts, get hydrolysis stabilizer 4 weight parts, get slipping agent 3 weight parts, get antiblocking agent 3 weight parts, get weighting agent 20 weight parts, get fire retardant 3 weight parts and mix 20min in stirrer high speed, the rotating speed of stirrer is 200r/min, carry out the combined shaping reaction of material, temperature is controlled at 100 DEG C, finally under 120 DEG C of conditions, dry 2.5h obtains nano modification TPU matrix material of the present invention, wherein chainextender, antioxidant, hydrolysis stabilizer, slipping agent, antiblocking agent, weighting agent, the selection of fire retardant is with reference to embodiment 1.
Embodiment 3
Nano modification TPU matrix material preparation process as the present invention's the 3rd preferred implementation is as follows:
(1) configuration composite nano powder, wherein the nano SiC of particle diameter 20-50nm accounts for the nano-TiO of 75 % by weight, particle diameter 30-40
2the nano-ZnO that accounts for 6 % by weight, particle diameter 30-60nm accounts for the nanometer Cr of 4 % by weight, particle diameter 30-60nm
2o
3account for the nanometer Al of 2 % by weight, particle diameter 30-40nm
2o
3account for the nanometer SiO of 9 % by weight, particle diameter 30-50nm
2account for 4 % by weight, above-mentioned each nano-component is fully mixed and its median size is ground to 20-50nm, make composite nano powder.
(2) prepare silane coupling agent, the raw material composition (mass fraction in self forming) of described silane coupling agent is: 25 parts of terephthalic acid calcium, 12 parts of para-phthalic sodiums, 15 parts, terephthalic acid aluminium, two-13 parts of (the silica-based propyl group of γ-triethoxy) tetrasulfides, 10 parts of gamma-mercaptopropyltriethoxysilanes, 16 parts of γ-aminopropyl triethoxysilanes, γ-(2, 3-epoxy the third oxygen) 8 parts of propyl trimethoxy silicanes, 8 parts of 5 parts of stearic acid and white carbon blacks, concrete preparation method is by the terephthalic acid calcium of above-mentioned mass parts, para-phthalic sodium and terephthalic acid aluminium and stearic acid jointly add in stirring tank under the rotating speed of turn 2000/min and stir 5min, then stop activation 15min, add again white carbon black to mix, stir 10min with 2000 turn/min speed, at the uniform velocity add again above-mentioned pair-(the silica-based propyl group of γ-triethoxy) tetrasulfide, gamma-mercaptopropyltriethoxysilane, γ-aminopropyl triethoxysilane and γ-(2, 3-epoxy the third oxygen) propyl trimethoxy silicane, continue to stir 10min with 2000 turn/min speed, obtain described silane coupling agent.
(3) get 16 parts of the prepared composite nano powders of step (1), get 5 parts of the prepared silane coupling agents of step (2), fully mix and be incorporated in stirring reaction 6h at 90 DEG C, then at 110 DEG C, be dried after 12h, put into again ball mill ball mill pulverizing 0.5 hour, obtain the composite nano powder of modification.
(4) get polyether glycol vacuum hydro-extraction at 110 DEG C of 60 weight parts, be cooled to 40 DEG C, under rapid stirring, add the isocyanic ester of 30 weight parts, insulation reaction 2h at 80 DEG C, synthetic massfraction is 5% isocyanate terminated performed polymer, and the preparation of polyether glycol and isocyanic ester self is described above.
(5) getting the isocyanate terminated performed polymer that modification composite nano powder that chainextender 15 weight parts, foam stabilizer 2 weight parts make with above-mentioned steps (3) and step (4) make evenly mixes, and be added in twin screw extruder, be 200rpm at screw speed, temperature is melt pelletization at 180 DEG C, obtains urethane-nano-powder composite components.
(6) get urethane-nano-powder composite components 80 weight parts that step (5) makes, get chainextender 7 weight parts, get oxidation inhibitor 1 weight part, get hydrolysis stabilizer 3 weight parts, get slipping agent 2 weight parts, get antiblocking agent 2 weight parts, get weighting agent 12 weight parts, get fire retardant 2 weight parts and mix 15min in stirrer high speed, the rotating speed of stirrer is 150r/min, carry out the combined shaping reaction of material, temperature is controlled at 80 DEG C, finally under 100 DEG C of conditions, dry 2h obtains nano modification TPU matrix material of the present invention, wherein chainextender, antioxidant, hydrolysis stabilizer, slipping agent, antiblocking agent, weighting agent, the selection of fire retardant is with reference to embodiment 1.
Test by experiment, the shore hardness of the prepared nano modification TPU matrix material of the present invention of above-described embodiment 1-3 is in 90-95A, abrasion intensity is under 9Kpa pressure, mill 650 turns rear without wear phenomenon, more than resistance to xanthochromia level Four, fusing point is 170-175 DEG C, melting index is in 55-60g/10min, tensile strength is greater than 40Mpa, tear strength is greater than 90kgf/cm, viscosity is 8200-8240ps/200 DEG C, elongation is greater than 550%, thereby there is more superior performance by the prepared nano modification TPU of the present invention matrix material, can be applicable to more wide Application Areas.
Below be only that the preferred embodiment of the present invention is described; technical scheme of the present invention is not limited to this; the any known distortion that those skilled in the art do on the basis of major technique design of the present invention all belongs to the claimed technology category of the present invention, and the concrete protection domain of the present invention is as the criterion with the record of claims.
Claims (10)
1. a nano modification TPU matrix material, it is characterized in that, by urethane-nano-powder composite components of 70-90 weight part, the chainextender of 3-10 part weight part, the antioxidant of 0.5-2 weight part, the hydrolysis stabilizer of 1.2-4 weight part, the slipping agent of 1-3 weight part, antiblocking agent, the weighting agent of 3-20 weight part and mixing the making of fire retardant of 0.8-3 weight part of 1-3 weight part, wherein said urethane-nano-powder composite components is by polyether glycol, isocyanic ester, composite nano powder, silane coupling agent, chainextender and foam stabilizer reaction make, during described urethane-nano-powder composite components self forms, the parts by weight of contained each composition are: polyether glycol 30-75 weight part, isocyanic ester 10-40 weight part, composite nano powder 10-25 weight part, silane coupling agent 1.5-9 weight part, chainextender 5-25 weight part, foam stabilizer 0.5-3 weight part, the particle diameter of wherein said composite nano powder is between 20-50nm, and described composite nano powder by particle diameter in 20-50nm and mass percentage content the nano SiC at 70-80%, particle diameter is the nano-TiO at 5-8% in 30-40nm and mass percentage content
2, particle diameter in 30-60nm and mass percentage content at the nano-ZnO of 3-5%, particle diameter in 30-60nm and mass percentage content the nanometer Cr at 1-3%
2o
3, particle diameter in 30-40nm and mass percentage content the nanometer AL at 8-10%
2o
3with particle diameter 30-50nm and the mass percentage content nanometer SiO at 3-6%
2composition.
2. nano modification TPU matrix material according to claim 1, it is characterized in that, wherein said chainextender is selected from ethylene glycol, 1,2-propylene glycol, 1, ammediol, BDO, Diethylene Glycol, dipropylene glycol, neopentyl glycol, 1,6-hexylene glycol, cyclohexanedimethanol, 3,3 '-bis-is chloro-4, one or more mixtures in 4-diaminodiphenylmethane.
3. nano modification TPU matrix material according to claim 1 and 2, is characterized in that, described antioxidant is oxidation inhibitor-264, dihydroxyphenyl propane, triphenyl phosphite, oxidation inhibitor-1010, antioxidant 1076 or tris phosphite, described hydrolysis stabilizer is charing diimine, described slipping agent is the one in erucicamide, stearylamide, Zinic stearas or amine hydroxybenzene, described antiblocking agent is the one in paraffin, erucicamide, stearylamide or nano silicon, described weighting agent is the one in calcium carbonate, fine silica powder or kaolin, the polypropylene of the melting index that described fire retardant is 45%-60% by mass percentage content in 5-10g/10min, mass percentage content is that the melting index of 10%-20% is at the polyethylene of 1.0-1.8 g/10min, mass percentage content is the powdered talc that is selected from of 20%-30%, kaolinite, sericite, what at least one mineral filler in silicon-dioxide and diatomite and mass percentage content were 10%-25% is selected from decabrominated dipheny base ether, the organic fire-resisting halogenide mixing of ten dichloro ten dihydro dimethano-benzene azoles cyclooctene or its mixture makes.
4. according to the nano modification TPU matrix material described in claim 1-3 any one, it is characterized in that, described foam stabilizer is modified silicone surfactants; Described polyether glycol be a kind of in a kind of and propylene oxide in propylene glycol, glycerine, TriMethylolPropane(TMP), dihydroxyphenyl propane, triisocyanate, tolylene diamine, epoxy hexane, butylene oxide ring make by polyaddition reaction there is the polyether glycol that 2 functionality and molecular-weight average are 1000-3000; Described isocyanic ester is selected from tolylene diisocyanate (TDI), 4,4-diphenylmethanediisocyanate (MDI), PPDI (PPDI), dimethyl diphenyl vulcabond (TODI), 1,5-is the mixture of one or both in vulcabond (NDI), PPDI (PPDI), hexamethylene vulcabond (HDI), dicyclohexyl methane diisocyanate (HMDI) how.
5. according to the nano modification TPU matrix material described in claim 1-4 any one, it is characterized in that, described silane coupling agent reacts and makes for 8 hours according to mol ratio 1:1, at 60-80 DEG C by any two kinds in triethyl vinyl silanes, γ-aminopropyl triethoxysilane, γ-glycidyl ether oxygen propyl trimethoxy silicane, triple phenoxyl vinyl silanes, phenylamino methyltrimethoxy silane, aminoethyl aminopropyl trimethoxysilane and methacryloxypropyl trimethoxy silane.
6. according to the nano modification TPU matrix material described in claim 1-4 any one, it is characterized in that, the concentrated hydrochloric acid neutralizing agent hybrid reaction that the sodium hydroxide hydrolysis agent that γ-aminopropyl dimethoxy-methyl silane that described silane coupling agent is 18% by mass percentage content, the methyl acrylate that mass percentage content is 12%, Virahol organic solvent that mass percentage content is 35%, the concentration that mass percentage content is 25% are 20% and mass percentage content are 10% makes.
7. according to the nano modification TPU matrix material described in claim 1-4 any one, it is characterized in that, described silane coupling agent is by the terephthalic acid calcium of 20-30 weight part, the para-phthalic sodium of 10-15 weight part, the terephthalic acid aluminium of 10-20 weight part, 10-15 weight part two-(the silica-based propyl group of γ-triethoxy) tetrasulfide, the gamma-mercaptopropyltriethoxysilane of 8-12 weight part, the γ-aminopropyl triethoxysilane of 12-20 weight part, the γ-(2 of 5-10 weight part, 3-epoxy the third oxygen) propyl trimethoxy silicane, the white carbon black hybrid reaction of the stearic acid of 2-6 weight part and 5-12 weight part makes.
8. according to the nano modification TPU matrix material described in claim 1-7 any one, it is characterized in that, the Shao Er hardness of described nano modification TPU matrix material be 90-95A, abrasion intensity meet under 9kPa pressure, grind 650 turn after without wear phenomenon, resistance to xanthochromia grade more than level Four, fusing point in 170-175 DEG C, melting index in 55-60g/10min, tensile strength in 40-60Mpa, tear strength >=90kgf/cm, viscosity in 8200-8240ps/200 DEG C, elongation >=550%.
9. a preparation method for nano modification TPU matrix material described in claim 1-8 any one, is characterized in that, comprises the following steps:
Step 1, prepare composite nano powder, by nano SiC, nano-TiO
2, nano-ZnO, nanometer Cr
2o
3, nanometer AL
2o
3with nanometer SiO
2according to fully mixing after above-mentioned mass percentage content configuration, and the particle diameter of mixture is ground to 20-50nm, obtains composite nano powder;
Step 2, select one of following manner to prepare silane coupling agent, mode one: to react according to mol ratio 1:1, at 60-80 DEG C and within 8 hours, make silane coupling agent by any two kinds in triethyl vinyl silanes, γ-aminopropyl triethoxysilane, γ-glycidyl ether oxygen propyl trimethoxy silicane, triple phenoxyl vinyl silanes, phenylamino methyltrimethoxy silane, aminoethyl aminopropyl trimethoxysilane and methacryloxypropyl trimethoxy silane; Mode two: the concentrated hydrochloric acid neutralizing agent hybrid reaction that the sodium hydroxide hydrolysis agent that the γ-aminopropyl dimethoxy-methyl silane that is 18% by mass percentage content, methyl acrylate that mass percentage content is 12%, Virahol organic solvent that mass percentage content is 35%, the concentration that mass percentage content is 25% are 20% and mass percentage content are 10% makes silane coupling agent; Mode three: by the terephthalic acid aluminium of the para-phthalic sodium of the terephthalic acid calcium of 20-30 weight part, 10-15 weight part, 10-20 weight part, 10-15 weight part two-(the silica-based propyl group of γ-triethoxy) tetrasulfide, the gamma-mercaptopropyltriethoxysilane of 8-12 weight part, the γ-aminopropyl triethoxysilane of 12-20 weight part, γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane, the stearic acid of 2-6 weight part and the white carbon black hybrid reaction of 5-12 weight part of 5-10 weight part make silane coupling agent;
Step 3, get composite nano powder 10-25 weight part prepared by step 1, get silane coupling agent 1.5-9 weight part prepared by step 2, fully mix and be incorporated in stirring reaction 6h at 85-95 DEG C, then at 105-120 DEG C, be dried after 12h, put into again ball mill ball mill pulverizing 0.5 hour, obtain the composite nano powder of modification;
Step 4, polyether glycol vacuum hydro-extraction at 100-120 DEG C of getting 30-75 weight part, be cooled to 30-50 DEG C, under rapid stirring, add the isocyanic ester of 10-40 weight part, insulation reaction 2h at 70-90 DEG C, the isocyanate terminated performed polymer that synthetic massfraction is 5%;
Step 5, the modification composite nano powder that chainextender 5-25 weight part, foam stabilizer 0.5-3 weight part, step 3 are made are evenly mixed in the isocyanate terminated pre-polymerization body fluid that step 4 makes, then be added in twin screw extruder, be 150-250rpm at screw speed, temperature is melt pelletization at 170-195 DEG C, obtains urethane-nano-powder composite components;
Step 6, get urethane-nano-powder composite components 70-90 weight part that step 5 makes, get chainextender 3-10 weight part, get oxidation inhibitor 0.5-2 weight part, get hydrolysis stabilizer 1.2-4 weight part, get slipping agent 1-3 weight part, get antiblocking agent 1-3 weight part, get weighting agent 3-20 weight part, get fire retardant 0.8-3 weight part and mix 10-20min in stirrer high speed, the rotating speed of stirrer is 80-200r/min, carry out the combined shaping reaction of material, temperature is controlled at 60-100 DEG C, finally under 80-120 DEG C of condition, dry 2-2.5h obtains described nano modification TPU matrix material.
10. the preparation method of nano modification TPU matrix material according to claim 9, it is characterized in that, wherein described in the mode two of step 2, the concrete preparation method of silane coupling agent is: by above-mentioned mass content, γ-aminopropyl dimethoxy-methyl silane and Virahol organic solvent are put in reactor, and between 30～40 DEG C, in whipping process, drip the methyl acrylate of above-mentioned mass content, and when methyl acrylate add after cooling placement predetermined amount of time, then reactant is warming up to 55～65 DEG C, under vacuum condition, underpressure distillation is about 30 minutes, residue in reactor is ester type intermediate, again the sodium hydroxide hydrolysis agent of above-mentioned mass content is mixed with described ester type intermediate, stirring heating is carried out back hydrolysis reaction, controlling agitator speed is 200～300 revs/min, back hydrolysis obtains sodium salt intermediate water solution after the reaction scheduled time, the most backward described sodium salt intermediate water solution adds the concentrated hydrochloric acid neutralizing agent of above-mentioned mass content, under the condition of heated and stirred, carry out neutralization reaction, neutralization reaction obtains neutralization reactant after the scheduled time, neutralization reactant is cooled to 65～75 DEG C afterwards, open vacuum valve to reaction kettle for vacuumizing, vacuum is pulled out the low-boiling-point substance in reactor, afterwards reactor is cooled to room temperature, material suction filtration in reactor is taken out, obtain described silane coupling agent, wherein described in the mode three of step 2, the concrete preparation method of silane coupling agent is: by above-mentioned weight part by terephthalic acid calcium, para-phthalic sodium and terephthalic acid aluminium and stearic acid jointly add in stirring tank under the rotating speed of turn at 1800-2000/min and stir 5-10min, then stop activation 15-30min, add again white carbon black to mix, again stir 5-10min with turn/min of 1800-2000 speed, at the uniform velocity add again described pair-(the silica-based propyl group of γ-triethoxy) tetrasulfide, gamma-mercaptopropyltriethoxysilane, γ-aminopropyl triethoxysilane and γ-(2, 3-epoxy the third oxygen) propyl trimethoxy silicane, continue to stir 10-20min with turn/min of 1800-2000 speed, obtain described silane coupling agent.
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| CN111171271B (en) * | 2020-02-25 | 2022-08-19 | 广州市环友高分子新材料有限公司 | Preparation method of heat-resistant polyurethane elastomer |
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| CN113736246B (en) * | 2021-09-09 | 2022-03-29 | 上海鹤城高分子科技有限公司 | Casting polyurethane for fitness equipment and preparation method thereof |
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