CN101914192A - Mildew-proof and antibacterial sole polyurethane stock solution and production process of polyurethane sole - Google Patents
Mildew-proof and antibacterial sole polyurethane stock solution and production process of polyurethane sole Download PDFInfo
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- CN101914192A CN101914192A CN 201010264662 CN201010264662A CN101914192A CN 101914192 A CN101914192 A CN 101914192A CN 201010264662 CN201010264662 CN 201010264662 CN 201010264662 A CN201010264662 A CN 201010264662A CN 101914192 A CN101914192 A CN 101914192A
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Abstract
The invention relates to mildew-proof and antibacterial sole polyurethane stock solution and a production process of a polyurethane sole. In the invention, the polyurethane stock solution comprises the following components in percentage by weight: 60 to 65 percent of poly(ethylene adipate)glycol with a number-average molecular weight of 1,000 to 3,000, 20 to 25 percent of isocyanate, 6 to 10 percent of 1,4-butanediol, 1 to 3 percent of triethylene diamine, 0.5 to 0.8 percent of water, 0.2 to 0.6 percent of dimethyl siloxane and 0.5 to 1.5 percent of cobalt/brookite nano titanium dioxide composite, wherein the molar ratio of cobalt to titanium atoms in the cobalt/brookite nano titanium dioxide composite is 1: 9-11. The cobalt/brookite nano titanium dioxide composite of the invention has a high antibacterial property and is suitable to be added into the sole polyurethane stock solution, so that the polyurethane sole has high antibacterial and mildew-proof properties.
Description
Technical field
The invention belongs to the material technology field, be specifically related to a kind of sole polyurethane stock solution of antimildew and antibacterial and make technology at the bottom of polyurethane shoe by this stoste.
Background technology
Urethane (PU) began as material for sole of shoe in the seventies in 20th century.Its main advantage is that it is hard, pliable and tough, endurable, and all flexible in very big density range.Therefore, PU has obtained using widely in a lot of fields, to the interior end, occupies 7% the market share from outer bottom on ground market.
In the prior art, sole polyurethane stock solution can be divided into polyester type and polyether-type two big classes (polyester type PU is polyester and isocyanic ester be combined into, and polyether-type PU then is polyethers and isocyanic ester be combined into) by the type of used polyvalent alcohol.Because polyester molecule itself contains carbonyl, very easily form hydrogen bond with urethano, increase internal cohesive energy, make the many performances such as the aspects such as tensile strength, tear strength, wear resistance, anti-greasy dirt and solvent of polyester type PU sole be better than the polyether-type sole, therefore be mainly the PAUR sole on the domestic market at present.But conventional PAUR does not have the antimildew and antibacterial function, gives and uses health and snugness of fit to bring disadvantageous effect.In addition, hydrolysis and biological degradation more easily take place in conventional PAUR, especially the sole of Zhi Zuoing chap easily, fracture etc., greatly reduce work-ing life of footwear.These deficiencies are especially obvious under high temperature and high humidity situation.
Summary of the invention
Technical problem to be solved by this invention is to overcome the deficiencies in the prior art, and a kind of sole polyurethane stock solution of antimildew and antibacterial is provided.
For solving above technical problem, the present invention takes following technical scheme:
A kind of sole polyurethane stock solution by weight, has following prescription: the polyethyleneglycol adipate glycol 60wt%～65wt% of number-average molecular weight 1000～3000; Isocyanic ester 20wt%～25wt%, 1,4-butyleneglycol 6wt%～10wt%; Triethylenediamine 1wt%～3wt%; Water 0.5wt%～0.8wt%; Dimethyl siloxane 0.2wt%～0.6wt%; Cobalt/plate titanium type nano titanium oxide mixture 0.5wt%～1.5wt%; Wherein, in cobalt/plate titanium type nano titanium oxide mixture, the mol ratio of cobalt and titanium atom is 1: 9～11.
Preferably, in cobalt/plate titanium type nano titanium oxide mixture, the mol ratio of cobalt and titanium atom is 1: 9.8～10.2.
According to the present invention, described cobalt/plate titanium type nano titanium oxide mixture can adopt preparations such as two one-step hydrothermals, sol-gel method, preferably adopt two one-step hydrothermals.According to the present invention, the concrete preparation process of described cobalt/plate titanium type nano titanium oxide mixture is as follows: at first titanium dioxide powder is dispersed in the aqueous solution of dehydrated alcohol and sodium hydroxide, wherein naoh concentration is 9～11mol/L, the aqueous solution ratio of dehydrated alcohol and sodium hydroxide is 1: 0.95～1.05, under 170 ℃～190 ℃, carry out hydro-thermal reaction, behind reaction 15～20h, add 1.1～1.3mmol/L cobalt nitrate solution, behind the ultra-sonic dispersion, carry out hydro-thermal reaction at 140 ℃～160 ℃, behind reaction 7～10h, extremely neutral with dilute hydrochloric acid solution and deionized water wash product solution, dry under 70 ℃～200 ℃, promptly get described cobalt/plate titanium type nano titanium oxide mixture.Preferably, naoh concentration is 10mol/L, and the concentration of cobalt nitrate solution is 1.2mmol/L.
Preferably, the described cobalt/content of plate titanium type nano titanium oxide mixture in described sole polyurethane stock solution is 0.8%～1.2%.Described isocyanic ester is 4, the 4-diphenylmethanediisocyanate.
The another technical scheme that the present invention takes is: a kind of technology that adopts at the bottom of above-mentioned sole polyurethane stock solution is produced polyurethane shoe, described technology comprises the steps:
(1), synthesis of polyurethane performed polymer component: in reactor, add the isocyanic ester of formula ratio and the polyethyleneglycol adipate glycol of 28%～32% formula ratio successively, temperature of reaction kettle is controlled at 70 ℃～80 ℃, insulation reaction is surveyed the NCO equivalent after 3 hours, adjust NCO equivalent to 210～230, promptly get base polyurethane prepolymer for use as;
(2), synthetic polyvalent alcohol component: with the polyethyleneglycol adipate glycol of remaining 68%～72% formula ratio, the 1.4-butyleneglycol of formula ratio, water, dimethyl siloxane, triethylenediamine and cobalt/plate titanium type nano titanium oxide mixture joins in the reactor, temperature of reaction kettle is controlled at 50 ℃～60 ℃, insulated and stirred was surveyed moisture content after 1 hour, adjusted moisture content to 0.60wt%, promptly got the polyvalent alcohol component;
(3), the polyvalent alcohol component that makes of base polyurethane prepolymer for use as component that step (1) is made and step (2) is preheated to 35 ℃～45 ℃ respectively, pour into respectively then in the sole casting molding machine batch can, be labeled as the A material respectively, the B material, circulated 18～25 minutes, according to the different service requirementss at the bottom of the polyurethane shoe, expect to proper ratio by toothed gear pump adjustment A material, B, control footwear mould temperature is between 50 ℃～70 ℃, raw material in the batch can is injected the footwear mould, in 50 ℃～70 ℃ sulfurations 5 minutes, taking-up promptly got at the bottom of the described polyurethane shoe.
Preferably, in the step (1), adjust NCO equivalent to 220.
Because the employing of technique scheme, the present invention compared with prior art has the following advantages:
The cobalt that the present invention relates to/plate titanium type nano titanium oxide mixture has excellent anti-microbial property, and is suitable for being added on the antibacterial and mouldproof performance of giving excellence at the bottom of the polyurethane shoe in the sole polyurethane stock solution.
Technology of the present invention is simple, has excellent antibacterial and mouldproof performance at the bottom of the gained polyurethane shoe.
Description of drawings
Fig. 1 a and 1b are respectively the TEM figure (adopting the Hitachi27500 of HIT type transmission electron microscope) of embodiment 1 gained titanium dioxide nano thread and cobalt/plate titanium type nano titanium oxide mixture;
Fig. 1 b is the TEM figure (adopting the Japan Ricoh D/MAX23A of company type X-ray diffractometer) of embodiment 1 gained cobalt/plate titanium type nano titanium oxide mixture;
Fig. 2 is the XRD spectra of embodiment 1 gained titanium dioxide nano thread and cobalt/plate titanium type nano titanium oxide mixture, and its center line a represents titanium dioxide nano thread, and line b represents cobalt/plate titanium type nano titanium oxide mixture.
Embodiment
The present invention will be further described in detail below in conjunction with specific embodiment, but the invention is not restricted to these embodiment.
Embodiment 1
A kind of cobalt/plate titanium type nano titanium oxide mixture, it prepares as follows: at first, in clean beaker, add the 0.5g titania powder, 7.5mL dehydrated alcohol and 7.5mL10mol/L sodium hydroxide solution, be transferred in the reactor after stirring 1h, make and under 180 ℃, carry out hydro-thermal reaction, take out behind the reaction 18h, naturally cool to room temperature, the cobalt nitrate solution 0.52L that in reactor, adds 1.2mmol/L then, behind the ultra-sonic dispersion, make at 150 ℃ of following hydro-thermal reaction 8h, use HCl solution and the deionized water wash hydro-thermal reaction product of 0.1mol/L extremely neutral at last, be drying to obtain described cobalt/plate titanium type nano titanium oxide mixture under 80 ℃, wherein, the mol ratio of cobalt and titanium is 1: 10.
Get the cobalt/plate titanium type nano titanium oxide mixture of titanium dioxide nano thread (product after the hydro-thermal reaction for the first time) and preparation, carry out transmission electron microscope (TEM) analysis respectively, the result sees Fig. 1 a and Fig. 1 b respectively, from Fig. 1 a as seen, the mean diameter of titanium dioxide nano thread and length-to-diameter ratio are about 145nm and 40 respectively.From Fig. 1 b as seen, cobalt nanometer particle is entrained on the titanium dioxide nano thread equably, the cobalt nanometer particle size is less, its mean sizes only is about 51nm, the illustration in Fig. 1 b upper right corner is the TEM figure of 1 times of amplification, and cobalt nanometer particle successfully is entrained on the titanium dioxide nano thread as can be seen from the figure that amplifies.
In addition, also cobalt/plate titanium type nano titanium oxide the mixture of titanium dioxide nano thread and preparation has been carried out XRD analysis respectively, the results are shown in Figure 2.Diffraction peak is 24.9 ° shown in Fig. 2 center line a, and 29.6 °, 34.4 °, 36.7 °, 48.4 °, 52.5 °, 55.1 ° and 61.8 ° (111) that correspond respectively to brookite titania iris shape, (121), (012), (201), (231), (311), (151) and (160) crystal faces (JCPDS0320380).Fig. 2 center line b is except the diffraction peak of brookite titania iris shape, also have 39.8 °, 46.3 °, 67.6 ° and 81.3 ° of four diffraction peaks, these diffraction peaks are the face-centred cubic characteristic diffraction peak of cobalt (JCPDS 8720646), and its corresponding crystal face is respectively (110), (200), (220) and (311), illustrate that cobalt nanometer particle is entrained on the titanium dioxide nano thread.
Embodiment 2
A kind of cobalt/plate titanium type nano titanium oxide mixture, the preparation method is substantially with embodiment 1, and different is that the molar ratio of titanium dioxide and Xiao Suangu is 1: 5～6.
Adopt the technology at the bottom of the polyurethane stock solution of embodiment 1 and 2 is produced polyurethane shoe, can more specifically describe by the following examples 3～8 and Comparative Examples 1.
Embodiment 3～8 and comparative example 1 all account for the mass percent example of stoste at the bottom of the polyurethane shoe according to the raw material described in the table 1, prepare polyurethane shoe according to following steps at the bottom of:
(1), synthesis of polyurethane performed polymer component: polyethyleneglycol adipate glycol 20 weight parts that in reactor, add isocyanic ester 25 weight parts and number-average molecular weight 2000 successively, temperature of reaction kettle is controlled at 70 ℃～80 ℃, and insulation reaction is surveyed the NCO equivalent after 3 hours; Adjust NCO equivalent to 220, promptly get base polyurethane prepolymer for use as.
(2), synthetic polyvalent alcohol component: with polyethyleneglycol adipate glycol residuals weight part of number-average molecular weight 2000,1.4-butyleneglycol 7 weight parts, distilled water 0.6 weight part, dimethyl siloxane 0.4 weight part, triethylenediamine 1 weight part, cobalt/required weight part of plate titanium type nano titanium oxide mixture joins in the reactor, temperature of reaction kettle is controlled at 50 ℃～60 ℃, insulated and stirred was surveyed moisture content after 1 hour, adjust the qualified back of moisture content (moisture content is approximately 0.55wt%), promptly get the polyvalent alcohol component.
(3), the polyvalent alcohol component that makes of base polyurethane prepolymer for use as component that step (1) is made and step (2) is preheated to 40 ℃ respectively, together pours into then in the batch can of sole casting molding machine, circulates 20 minutes, makes a little test glass, the affirmation test glass is a foamed core.Footwear mould temperature is controlled at 50 ℃～70 ℃ scope, the raw material of accomplishing fluently in the batch can is injected the footwear mould, 50 ℃～70 ℃ sulfurations 5 minutes can be taken out sole.
The component of stoste embodiment and Comparative Examples at the bottom of table 1. polyurethane shoe
Unit: wt%
Carried out the germ resistance test at the bottom of the polyurethane shoe to embodiment 3-8 and Comparative Examples 1 preparation, specific as follows:
(1), testing method: according to the antibiotic standard of newest F Z/T 73023-2006, to be cut into 0.5cm * 0.5cm print through the sample after the sterilization of high pressure steam pot, take by weighing (0.75 ± 0.05) g and put into 250mL tool plug Erlenmeyer flask, cover bottle stopper through high pressure steam sterilization, add 70mLPBS and 5mL bacteria suspension behind the naturally cooling respectively, then Erlenmeyer flask is fixed on the vibration shaking table, under 25 ℃ of constant temperature, with 150r/min vibration (18 ± 1) h.After vibration finishes, from each flask, draw the 1mL test solution, put into the test tube of 9mL0.03mol/LPBS damping fluid, shake up with suction pipe.Carry out serial dilution with 10 times of dilution methods.Get 1mL dilution bacterium liquid respectively from each dilution test tube, put into two culture dish and make parallel sample, pour the about 15mL of nutrient agar again in each culture dish, room temperature is solidified, and is inverted culture dish.With culture dish be positioned in 37 ℃ of biochemical incubators cultivate 24-48h after, number goes out the colony number on each culture dish, calculates the viable bacteria concentration in the flask behind the vibration contact 18h by formula W=Z * N then. in the formula, W is the viable bacteria concentration in the sample flask, cfu/mL
-1Z is colony number (2 culture dish on mean value); N is the dilution index, N=100, and 101,102...... is calculated as follows bacteriostasis rate; Y=(1-Wc/Wb) * 100%, in the formula, Y is bacteriostasis rate (%); Wb for standard check sample vibration contact 18h after viable bacteria concentration in the flask, cfu/m
L-1Wc for antibiotic fabric sample vibration contact 18h after viable bacteria concentration in the flask, cfu/mL
-1
(2), test result: shown in table 2 and 3, it has provided the bacteriostasis rate of the cobalt/plate titanium type nano titanium oxide mixture dispersion liquid urethane test piece of different mass concentration.
Table 2 (cobalt/titanium mol ratio is 1: 10)
(cobalt/titanium mol ratio is 1 to table 3: 5-6)
From table 2 and 3 as seen, adopt the anti-microbial property that has excellence at the bottom of the polyurethane shoe of sole polyurethane stock solution production of the present invention.
More than the present invention has been done detailed description; its purpose is to allow the personage that is familiar with this art can understand content of the present invention and is implemented; can not limit protection scope of the present invention with this; all equivalences of doing according to spirit of the present invention change or modify, and all should be encompassed in protection scope of the present invention.
Claims (8)
1. a sole polyurethane stock solution is characterized in that: by weight, have following prescription: the polyethyleneglycol adipate glycol 60wt%～65wt% of number-average molecular weight 1000～3000; Isocyanic ester 20wt%～25wt%, 1,4-butyleneglycol 6wt%～10wt%; Triethylenediamine 1wt%～3wt%; Water 0.5wt%～0.8wt%; Dimethyl siloxane 0.2wt%～0.6wt%; Cobalt/plate titanium type nano titanium oxide mixture 0.5wt%～1.5wt%; Wherein, in cobalt/plate titanium type nano titanium oxide mixture, the mol ratio of cobalt and titanium atom is 1: 9～11.
2. sole polyurethane stock solution according to claim 1 is characterized in that: in cobalt/plate titanium type nano titanium oxide mixture, the mol ratio of cobalt and titanium atom is 1: 9.8～10.2.
3. sole polyurethane stock solution according to claim 1 is characterized in that: described cobalt/plate titanium type nano titanium oxide mixture adopts the preparation of two one-step hydrothermals.
4. sole polyurethane stock solution according to claim 3, it is characterized in that: the concrete preparation process of described cobalt/plate titanium type nano titanium oxide mixture is as follows: at first titanium dioxide powder is dispersed in the aqueous solution of dehydrated alcohol and sodium hydroxide, wherein naoh concentration is 9～11mol/L, the aqueous solution ratio of dehydrated alcohol and sodium hydroxide is 1: 0.95～1.05, under 170 ℃～190 ℃, carry out hydro-thermal reaction, behind reaction 15～20h, add 1.1～1.3mmol/L cobalt nitrate solution, behind the ultra-sonic dispersion, carry out hydro-thermal reaction at 140 ℃～160 ℃, behind reaction 7～10h, extremely neutral with dilute hydrochloric acid solution and deionized water wash product solution, dry under 70 ℃～200 ℃, promptly get described cobalt/plate titanium type nano titanium oxide mixture.
5. sole polyurethane stock solution according to claim 1 is characterized in that: described isocyanic ester is 4, the 4-diphenylmethanediisocyanate.
6. sole polyurethane stock solution according to claim 1 is characterized in that: the described cobalt/mass content of plate titanium type nano titanium oxide mixture in described sole polyurethane stock solution is 0.8%～1.2%.
7. one kind is adopted the technology at the bottom of each described sole polyurethane stock solution production polyurethane shoe in the claim 1 to 6, and it is characterized in that: described technology comprises the steps:
(1), synthesis of polyurethane performed polymer component: in reactor, add the isocyanic ester of formula ratio and the polyethyleneglycol adipate glycol of 28%～32% formula ratio successively, temperature of reaction kettle is controlled at 70 ℃～80 ℃, insulation reaction is surveyed the NCO equivalent after 3 hours, adjust NCO equivalent to 210～230, promptly get base polyurethane prepolymer for use as;
(2), synthetic polyvalent alcohol component: with the polyethyleneglycol adipate glycol of remaining 68%～72% formula ratio, the 1.4-butyleneglycol of formula ratio, water, dimethyl siloxane, triethylenediamine and cobalt/plate titanium type nano titanium oxide mixture joins in the reactor, temperature of reaction kettle is controlled at 50 ℃～60 ℃, insulated and stirred was surveyed moisture content after 1 hour, adjusted moisture content to 0.60wt%, promptly got the polyvalent alcohol component;
(3), the polyvalent alcohol component that makes of base polyurethane prepolymer for use as component that step (1) is made and step (2) is preheated to 35 ℃～45 ℃ respectively, pour into respectively then in the sole casting molding machine batch can, be labeled as the A material respectively, the B material, circulated 18～25 minutes, according to the different service requirementss at the bottom of the polyurethane shoe, expect to proper ratio by toothed gear pump adjustment A material, B, control footwear mould temperature is between 50 ℃～70 ℃, raw material in the batch can is injected the footwear mould, in 50 ℃～70 ℃ sulfurations 5 minutes, taking-up promptly got at the bottom of the described polyurethane shoe.
8. technology according to claim 7 is characterized in that: in the step (1), adjust NCO equivalent to 220.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103275480A (en) * | 2013-06-21 | 2013-09-04 | 苏州市景荣科技有限公司 | SPU sole material with high polymerization degree |
| CN103448267A (en) * | 2013-08-30 | 2013-12-18 | 安徽金科橡塑制品有限公司 | Manufacturing process for quic- heat-conducting mildew-proof anti-bacterial rubber insoles |
| CN104072716A (en) * | 2014-07-18 | 2014-10-01 | 浙江奥康鞋业股份有限公司 | Polyurethane elastomer and sole made from same |
| CN107501739A (en) * | 2017-09-30 | 2017-12-22 | 界首市远航织带有限公司 | A kind of method of modifying for improving polypropylene material impact strength |
| CN108864688A (en) * | 2018-06-05 | 2018-11-23 | 瑞安市吉尔康鞋业有限公司 | The production technology of antimildew and antibacterial sole polyurethane stock solution and antimildew and antibacterial sole |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103275480A (en) * | 2013-06-21 | 2013-09-04 | 苏州市景荣科技有限公司 | SPU sole material with high polymerization degree |
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| CN104072716A (en) * | 2014-07-18 | 2014-10-01 | 浙江奥康鞋业股份有限公司 | Polyurethane elastomer and sole made from same |
| CN104072716B (en) * | 2014-07-18 | 2016-05-11 | 浙江奥康鞋业股份有限公司 | Polyurethane elastomer and the sole of being made by it |
| CN107501739A (en) * | 2017-09-30 | 2017-12-22 | 界首市远航织带有限公司 | A kind of method of modifying for improving polypropylene material impact strength |
| CN108864688A (en) * | 2018-06-05 | 2018-11-23 | 瑞安市吉尔康鞋业有限公司 | The production technology of antimildew and antibacterial sole polyurethane stock solution and antimildew and antibacterial sole |
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