At the bottom of a kind of polyether type polyurethane shoes and preparation method thereof
One, affiliated technical field:
The present invention relates at the bottom of a kind of polyurethane shoe and preparation method thereof, at the bottom of especially a kind of polyether type polyurethane shoes and preparation method thereof, belong to the manufacture method technical field of modified polyurethane sole.
Two, technical background:
Microporous polyurethane elastomer is owing to have utmost point excellent abrasive, resistance to tearing, shock-resistance, fabulous rebound resilience and comfortableness, being applied in the daily life more and more widely.Microporous polyurethane elastomer is as material for sole of shoe, realize industrialization the sixties in 20th century in Europe, enter North America market the seventies, be rapidly developed in the whole world eighties, at present, polyurethane material accounts for 8.0% in the whole world shoe industry, and at economically developed West Europe, north America region, ratio is up to 22%.
Stoste can be divided into polyester type and polyether-type two big classes by the type of used polyvalent alcohol at the bottom of the polyurethane shoe.Many performances at the bottom of the polyester type shoes such as tensile strength, tear strength, elongation at break, wear resistance, folding resistance are better than the polyether-type sole, therefore in whole polyurethane sole materials occupancy volume up to more than 85%, but its low-temperature performance is relatively poor, and hydrolysis and biological degradation take place easily; And the polyether-type sole has just in time overcome the weakness of PAUR sole, have stronger low-temperature performance, anti-hydrolytic performance and anti-mildew sex change energy, along with popularizing of people's outdoor activity, at the bottom of being arranged, the polyether type polyurethane shoes of good hydrolysis stability becomes the focus that people pay close attention to, especially at awful weather, in, cold district big as rainfall amount and the moist Working environment, the polyether-type sole has the irreplaceable effect of polyester type.But because its mechanical property intensity is relatively poor, except above special dimension, the polyether-type sole is difficult to be applied, occupancy volume less than 15% in polyurethane sole materials, in addition just at the early-stage in some country.
Why low than PAUR mechanical property polyether(poly)urethane is, and on the one hand by textural difference decision own, itself contains hydrogen atom polyester, very easily and form hydrogen bond between the isocyanic ester, increases internal cohesive energy; Relevant with the synthesis technique and the quality of polyethers on the other hand, common polyethers is to make initiator with potassium hydroxide, poly-hydroxy initiator propoxylation is prepared, exist the monomer propylene oxide isomerization to generate the side reaction of ally alcohol in this reaction, thereby cause holding the generation of unsaturated double-bond, influence molecular chain and increase, cause degradation.Though processing method is updated now, adopt bimetallic catalyst, ethylene oxide-capped, synthetic low-unsaturation-degree, high activity polyether, the generation of unsaturated link(age) is unavoidable, each tame product quality also exists than big-difference.
CN1453299A discloses a kind of polyether-type preparation of soles method, though product performance are better, must use the novel low-unsaturation-degree of double metal cyanide-catalyzed synthetic, polyether polyol with high activity, and is relatively harsher to the trade mark and the specification of quality of raw material.
CN1635026A discloses a kind of PU sole polyurethane material, rubber-plastic series nano modified synergistic agent and manufacture method thereof, but its complicated process of preparation is not suitable for the production of conventional polyurethanes sole casting molding machine.
US5856372 is disclosed also to be to utilize the low-unsaturation-degree high activity polyether to improve the physical and mechanical properties at the end in the low density.
US6329441 discloses wear resistance, flexibility and the surface imperfection of utilizing low-unsaturation-degree high activity polyether and POP to improve low density (0.150.50g/cm3) sole and the method for dimensional stability.
US6331577 discloses and has improved full water foamed low density (0.50g/cm3) low density sole, the rebound resilience of bearing circle and the method for dimensional stability, and its key problem in technology is that NCO content is relatively low in the performed polymer, less than 13%; The weight ratio of polyol component and performed polymer is less than 1 during foaming.
Three, summary of the invention:
The object of the present invention is to provide a kind of dependency that can reduce,, improve at the bottom of the polyether type polyurethane shoes of the physical and mechanical properties at the bottom of the common polyether type polyurethane shoes and preparation method thereof by filler modified to the polyethers raw material.
Technic relization scheme of the present invention is as follows:
At the bottom of a kind of polyether type polyurethane shoes, its special character is that its feed composition is
(1) polyvalent alcohol blending ingredients: be mixed in proportion by common polyether glycol, chainextender, water, tensio-active agent, according to weight ratio be: polyether glycol: chainextender: water: tensio-active agent=100: 5-15: 0.4-1.2: 0.2-1.0;
(2) filler modified A component: mixed by (1) polyvalent alcohol blending ingredients and filling modifier and catalyst by proportion, according to weight ratio be: filling modifier: catalyzer: polyvalent alcohol blending ingredients=5-15: 0.8-1.5: 100;
(3) performed polymer component: make the performed polymer component by vulcabond, polyether glycol and small molecular alcohol reaction, guarantee that isocyanate index is in the scope of 95-105, after this amount is determined, the weight ratio of performed polymer and polyvalent alcohol blending ingredients and definite naturally with the weight ratio of filler, what investigate in the actual production simultaneously also is isocyanate index.
Described polyether glycol is for being the polyether glycol of catalyzer with potassium hydroxide or being the polyether glycol of catalyzer or their mixture with bimetal (DMC or MMC).
Described polyether glycol comprises common polyether glycol with the PO chain extension, with end capped bottom saturation polyether glycol of PO chain extension EO or their mixture.
Described polyether glycol molecular weight is 3000-6000, and functionality is 2-3, can be the polyether glycol of initiator for one or more the mixture in propylene glycol, TriMethylolPropane(TMP), glycerol, the trolamine.
Described chainextender is ethylene glycol, Diethylene Glycol, 1,2-propylene glycol, 1, ammediol, dipropylene glycol, 1, one or more mixture in 4-butyleneglycol, the pentanediol.
Described tensio-active agent is silicone surfactant (Dabco DC3043 and Dabco DC193).
Described catalyzer is an amines catalyst, and amines catalyst comprises N, N dimethylcyclohexylamine, triethylene diamino, triethylamine, N, one or more mixture in N dimethylethanolamine, trolamine and the triethylene diamino salt.
Described filling modifier can be one or more the mixture in lime carbonate, silicon-dioxide, silicon-aluminium compound, the rubber powder; Preferred lime carbonate and silicon-dioxide, more preferably lime carbonate, particle size range is 50nm-300nm.
Described performed polymer is made by vulcabond, polyether glycol and small molecular alcohol reaction, wherein according to weight ratio, and vulcabond: polyether glycol: small molecular alcohol=250-500: 50-200: 10-50; The performed polymer product is little yellow transparent liquid, and liquid viscosity is 200-800mPa.s under the standard conditions, and NCO content is 17%-24%.
Above-mentioned vulcabond is 2,2-diphenylmethanediisocyanate, 2,4-diphenylmethanediisocyanate, 4,4-diphenylmethanediisocyanate, 2,4 toluene diisocyanate, 2, the mixture of one or more in the 6-tolylene diisocyanate.Preferred 4,4-diphenylmethanediisocyanate or it and 2,2-diphenylmethanediisocyanate, 2, the mixture of 4-diphenylmethanediisocyanate.
Preparation method at the bottom of a kind of polyether type polyurethane shoes of the present invention is as follows
(1) preparation of polyvalent alcohol blending ingredients
Metered common polyether glycol, chainextender, water, tensio-active agent are mixed in proportion, squeeze into the mixing batch can, be warmed up to 40-60 ℃, and under this temperature, mixed 0.5-1 hour, remove bubble, make the polyvalent alcohol blending ingredients;
(2) preparation of performed polymer
Performed polymer is made by vulcabond, polyether glycol and small molecular alcohol reaction; The reaction formula of vulcabond and polyether glycol (or small molecular alcohol) is as follows:
(3) sole preparation
Filling modifier and catalyst by proportion are added in the polyvalent alcohol blending ingredients, stir the A, the B batch can that add the sole casting molding machine after 5-30 minute with the performed polymer component respectively, be warmed up to 40-50 ℃, regulate two set of dispense than near central point by regulating the metering revolution speed, guarantee that isocyanate index is in the scope of 95-105; On the sole grinding tool coating release agent, dry up, cast, matched moulds, insulation 5-7 minute, the demoulding then makes the sole goods.
At the bottom of a kind of polyether type polyurethane shoes of the present invention and preparation method thereof, can reduce the dependency of product performance to the polyethers raw material, by filler modified, filler grain plays the effect of physical crosslinking point, overcome the weakness of polyether(poly)urethane material mechanical performance difference in the prior art to a great extent, make the material for sole of shoe tensile strength, tear strength obviously improves, thereby reach the purpose that improves polyether type polyurethane shoes substrate reason mechanical property, make at the bottom of the polyether type polyurethane shoes when keeping good hydrolysis stability, possess again the good physical mechanical property that is had at the bottom of the polyester type shoes is arranged, satisfy the shoe sole production actual demand, thereby make to have the applications well promotion prospect at the bottom of the polyether type polyurethane shoes of the present invention, will improve its market occupancy volume greatly.
Four, specific embodiments:
Below provide the specific embodiment of the present invention, be used for that the invention will be further described.
Embodiment
Preparation method at the bottom of a kind of polyether type polyurethane shoes, with common polyether glycol is raw material, by adding filling modifier in the mixed system that forms at polyether glycol, chainextender, water, tensio-active agent and catalyzer, make filler modified A component, filler modified A component and prepolymer reaction make goods at the bottom of the filler modified polyurethane shoe.
The preparation method of filler modified A component is as follows:
Metered polyether glycol, chainextender, water, tensio-active agent and catalyzer are squeezed into the mixing batch can, be warmed up to 40-50 ℃, under this temperature, mixed 0.5 hour, remove bubble, make the polyvalent alcohol blending ingredients.Add calcium carbonate modifier then in proportion, insulated and stirred 0.5 hour.The A, the B batch can that add the sole casting molding machine then with the performed polymer component respectively are warmed up to by regulating the metering revolution speed and regulate two set of dispense than near central point, guarantee that isocyanate index is in the scope of 95-105; On the sole grinding tool coating release agent, dry up, cast, matched moulds, insulation 5-7 minute, the demoulding then makes the sole goods.
Embodiment 1:
Molecular weight is the common polyether glycol of 6000 three-functionality-degrees, molecular weight is the common polyether glycol of 4,000 two functionality, the ethylene glycol chainextender, water, tensio-active agent (Dabco DC 3043), the wherein wt ratio is 50: 50: 6: 0.7: 0.3, squeeze into the stirring of mixing batch can successively and be the polyol blends component in 15 minutes, with particle diameter is in the pearl filler and catalyst by proportion adding polyol component of 50-100nm, the wherein wt ratio is: pearl filler: catalyzer (from controlling catalyst, butyleneglycol 25% solution of triethylene diamine): polyvalent alcohol blending ingredients=5: 1.0: 100; 55 ℃ mixed 1 hour, added the A batch can of sole casting molding machine; With NCO content is the B batch can that 23% performed polymer component adds the sole casting molding machine, regulates the material temperature to 45 ℃, regulates two set of dispense than near central point by regulating the metering revolution speed, guarantees that isocyanate index is in the scope of 95-105; On the sole grinding tool coating release agent, dry up, cast, matched moulds, insulation 7 minutes, the demoulding then makes end goods in the sports shoes.
Embodiment 2:
With molecular weight is the common polyether glycol of 4000 three-functionality-degrees, the polyether polyol with high activity, 1 that molecular weight is 6,000 two functionality, the agent of 4-chain expansion of succinic acid, water, tensio-active agent (Dabco DC 3043) are squeezed into mixing batch can, weight ratio 50: 50: 8.0: 0.5: 0.3.With particle diameter is that 100-200nm lime carbonate and catalyst by proportion add in the polyol component weight ratio: lime carbonate: catalyzer (from controlling catalyst, butyleneglycol 25% solution of triethylene diamine); Polyvalent alcohol blending ingredients=10: 1.2: 100; 60 ℃ mixed 1 hour, the A batch can that adds the sole casting molding machine, with NCO content is the B batch can that 20% performed polymer component adds the sole casting molding machine, regulate the material temperature to 45 ℃, regulate two set of dispense than near central point by regulating the metering revolution speed, guarantee that isocyanate index is in the scope of 95-105; On the sole grinding tool coating release agent, dry up, cast, matched moulds, insulation 6 minutes, the demoulding then, product is the low density outer bottom.
Embodiment 3:
With molecular weight is that polyether polyol with high activity, the molecular weight of 6000 three-functionality-degrees is 4000 two functionality polyether polyol with high activity, dipropylene glycol, 1,4-butyleneglycol, water, tensio-active agent (DabcoDC 3043) are squeezed into the mixing batch can, and part by weight is 50: 50: 3.0: 6.0: 0.4: 0.3.With particle diameter is in the pearl filler and catalyst by proportion adding polyol component of 200-300nm, the wherein wt ratio is: pearl filler: catalyzer (from controlling catalyst, butyleneglycol 25% solution of triethylene diamine): polyvalent alcohol blending ingredients=15: 1.2: 100; Insulated and stirred was mixed 1 hour, the A batch can that adds the sole casting molding machine, with NCO content is the B batch can that 18% performed polymer component adds the sole casting molding machine, regulate the material temperature to 45 ℃, regulate two set of dispense than near central point by regulating the metering revolution speed, guarantee with isocyanate index in the scope of 95-105; On the sole grinding tool coating release agent, dry up, cast, matched moulds, insulation 6 minutes, the demoulding then makes the sole goods, product is an outer bottom.
Table 1. test piece performance
Embodiment 4:
Be with the difference of embodiment 1: with molecular weight is that polyether polyol with high activity, the molecular weight of 3000 three-functionality-degrees is 6000 two functionality polyether polyol with high activity, dipropylene glycol, 1,4-butyleneglycol, water, tensio-active agent (Dabco DC 3043) are squeezed into the mixing batch can, and part by weight is 50: 50: 3.0: 5.0: 0.4: 0.2.With particle diameter is that the wherein wt ratio is: pearl filler: catalyzer: polyvalent alcohol blending ingredients=5: 0.8: 100 in the pearl filler and catalyst by proportion adding polyol component of 200-300nm.
Embodiment 5:
Be with the difference of embodiment 1: with molecular weight is that polyether polyol with high activity, the molecular weight of 5000 three-functionality-degrees is 3000 two functionality polyether polyol with high activity, 1,4-butyleneglycol, water, tensio-active agent (Dabco DC 3043) are squeezed into the mixing batch can, and part by weight is 50: 50: 15.0: 1.2: 1.0.With particle diameter is that the wherein wt ratio is: pearl filler: catalyzer: polyvalent alcohol blending ingredients=15: 1.5: 100 in the pearl filler and catalyst by proportion adding polyol component of 200-300nm.
Embodiment 6:
Be with the difference of embodiment 1: with molecular weight is that polyether polyol with high activity, the molecular weight of 3000 three-functionality-degrees is 5000 two functionality polyether polyol with high activity, 1,4-butyleneglycol, water, tensio-active agent (Dabco DC 3043) are squeezed into the mixing batch can, and part by weight is 50: 50: 10.0: 1.0: 0.8.With particle diameter is that the wherein wt ratio is: pearl filler: catalyzer: polyvalent alcohol blending ingredients=12: 1.0: 100 in the pearl filler and catalyst by proportion adding polyol component of 200-300nm.