CN105085857A - Waterproof breathable antibacterial thermoplastic polyurethane elastomer and preparation method thereof - Google Patents
Waterproof breathable antibacterial thermoplastic polyurethane elastomer and preparation method thereof Download PDFInfo
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- CN105085857A CN105085857A CN201510567272.4A CN201510567272A CN105085857A CN 105085857 A CN105085857 A CN 105085857A CN 201510567272 A CN201510567272 A CN 201510567272A CN 105085857 A CN105085857 A CN 105085857A
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- C—CHEMISTRY; METALLURGY
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3221—Polyhydroxy compounds hydroxylated esters of carboxylic acids other than higher fatty acids
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5003—Polyethers having heteroatoms other than oxygen having halogens
- C08G18/5015—Polyethers having heteroatoms other than oxygen having halogens having fluorine atoms
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/61—Polysiloxanes
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The present invention provides a waterproof breathable antibacterial thermoplastic polyurethane elastomer and a preparation method thereof. The thermoplastic polyurethane elastomer is prepared from the following main components by weight: 40-50 parts of polymeric polyol, 30-40 parts of isophorone isocyanate, 10-15 parts of 1,4-butanediol, 10-15 parts of nano ZnO-modified dihydroxy polydiphenylsiloxane and 5-10 parts of hydroxyethyl acrylate. The present invention uses a mixture of fluorine-containing polyether glycol and adipic acid 1,4-butanediol adipate diol as the polymeric polyol; the synergic effect of the two improves the water and oil repellency of the target product; while dihydroxy polydiphenylsiloxane and hydroxyethyl acrylate supplemented with nano ZnO increase the antibacterial properties of the thermoplastic polyurethane elastomer, and endow the elastomer with good mechanical properties.
Description
Technical field
The invention belongs to technical field of macromolecules, relate to a kind of Polyurethane Thermoplastic Elastomer and preparation method thereof, particularly relate to a kind of waterproof and breathable antimicrobial form Polyurethane Thermoplastic Elastomer and preparation method thereof.
Background technology
Thermoplastic polyurethane (ThermoplasticPolyurethane, TPU) a kind ofly heats melting and the macromolecular material of solvent-soluble solution.Linearly, intermolecular seldom have crosslinked TPU molecule, and second-order transition temperature is low, therefore has high strength, snappiness and excellent wear-resisting, oil resistant and low temperature tolerance characteristics.
Polyurethane Thermoplastic Elastomer has polyester type and polyether-type two class, and the random spherical or cylindrical particle of white, relative density 1.10 ~ 1.25, polyether-type relative density is less than polyester type.The outstanding feature of polyurethane termoplastic elastomer is excellent in abrasion resistance, ozone resistance is fabulous, hardness is large, intensity is high, good springiness, low temperature resistant, have good oil resistant, chemical-resistant resistance and environmental resistance, in wet environment, polyether-type Ester hydrolysis stability far exceedes polyester type.
The excellent hydrolysis resistance of water resistant thermoplastic urethane resin, is widely used in water-proof coating technique.The effect of water to TPU has two, one is plastification, namely water molecules gets in macromolecular chain, hydrogen bond is formed with the polar group in polymer molecule, make the reaction force attenuation between polymer molecule, tensile strength, tear strength and polishing machine decline, and this process is reversible, drying is dewatered, and can recover original performance; Two is Degradations of water, and namely TPU there occurs chemical degradation, and this process is irreversible, is also that harm is maximum.TPU can be divided into polyester type and polyether-type, and both hydrolytic processes are different.Due to ester group facile hydrolysis, the hydrolytic action of polyester type TPU shows as backbone breaking, molecular weight reduction, tensile strength and elongation and sharply declines; And polyether-type TPU, due to ether and carbamate groups hydrolysis, so hydrolytic action shows as to be cross-linked and slowly ruptures, tensile strength declines slowly, extends to take the lead in increasing then just to decline, and therefore polyether-type TPU has good water tolerance.
Patent CN104448788A discloses a kind of Waterproof Breathable type thermoplastic polyurethane film and preparation method thereof, and described Waterproof Breathable type thermoplastic polyurethane film comprises the following ingredients formed by mass percentage: the thermoplastic polyurethane of 80 ~ 85%, the slipping agent of 8 ~ 10% and 7 ~ 10% cloudy surface agent; Wherein, the raw materials of described thermoplastic polyurethane comprises: polytetramethylene ether diol 58 ~ 63 parts, tolylene diisocyanate 30 ~ 35 parts, ethylene glycol ether acetate 5 ~ 8 parts and dibutyltin diacetate 1 ~ 3 part.Although thermoplastic polyurethane film prepared by this invention has waterproofing and moisture-penetration performances, in its application in reality and preservation process, very easily Growth and reproduction bacterium under suitable temperature and humidity condition, affects it and uses.
Antibacterial polyurethane material refers to and carries out modification with the antiseptic-germicide of antibacterial group to polyurethane material by introducing, thus makes polyurethane material have the class new function material suppressing or kill its surface bacteria ability.At present, conventional antiseptic-germicide mainly contains natural class, mineral-type and organic three major types.Organic antibacterial agent effectively can suppress unwanted bacteria, the generation of mould and breeding, instant effect.But this kind of antiseptic-germicide thermostability poor (can only use below 300 DEG C), easily decompose, persistence is poor, and toxicity is comparatively large usually, and long-time use is harmful; The advantage of inorganic series antibacterial agent has hypotoxicity, thermotolerance, weather resistance, persistence, has a broad antifungal spectrum etc., is the optimum antiseptic-germicide kinds of life goods such as fiber, plastics, building materials.
Patent CN104109332A discloses a kind of antibacterial thermoplastic elastomer and preparation method thereof and application, and this antibacterial thermoplastic elastomer comprises the component of following weight percent: SEBS15 ~ 30%, rubber filling oil 10 ~ 30%, urethane 10 ~ 25%, antibacterial matrices 15 ~ 30%, first mineral filler 5 ~ 25%, first compatilizer 5 ~ 15% and other auxiliary agents 0 ~ 2%; The mode that its preparation method comprises step and the employing side charging taking each component mixes the step extruding process to each component melts.Although this patent prepares antibacterial thermoplastic elastomer possess excellent antibacterial effect, its waterproof breathable performance is undesirable, and anti-microbial property is not lasting, and its mechanical property also has much room for improvement.
Therefore, preparing a kind of Polyurethane Thermoplastic Elastomer having excellent water-proof breathable properties, anti-microbial property and excellent mechanical performances concurrently is need the problem of solution badly.
In prior art, in order to improve the anti-microbial property of material, having by disperseing Nano silver grain to obtain dispersion liquid in a solvent, then make dispersion with being contacted by the matrix surface giving its germ resistance and obtain germ resistance.Nano inorganic anti-biotic material can be divided into two classes: one be itself there is anti-microbial activity metal oxide as TiO
2and ZnO; Two is with silver zinc complex thing for main antibacterial body, with ultra-fine SiO
2and TiO
2deng the antibacterial zeolite for carrier.
But the particle diameter of nanoparticle is very little, its high surface energy makes it be easy to reunite, and bad dispersibility, forms offspring, cannot show its surface-area effects of being favored, volume effect and quantum size effects etc., make it can not keep lasting germ resistance.The present invention makes nano-ZnO in dihydroxyl polydiphenylsiloxane surface growth grafting, improve nano-ZnO wettability of the surface, increase the affinity of itself and other materials, increase antibacterial effect, the adhesivity of dihydroxyl polydiphenylsiloxane can improve the Durability of antimicrobial effect of material simultaneously.
In the present invention, add Hydroxyethyl acrylate as linking agent, can provide cross-linking set to urethane, make urethane define reticulated structure, water and solvent molecule are all difficult to enter in macromolecular structure go, thus improve its water resistance ventilation property and mechanical property.
In the present invention, the molecular structure of described polyether diatomic alcohol containing fluorine is HO-(CH
2cH
2o) n
1-CH
2-CF
2o-(CF
2cF
2o)
m-(CF
2o) n
2-CF
2-CH
2-(OCH
2cH
2) n
3-OH;
Wherein, m=3 ~ 6, such as 3,4,5 or 6 etc.; n
1=3 ~ 6, such as 3,4,5 or 6 etc.; n
2=3 ~ 6, such as 3,4,5 or 6 etc.; n
3=3 ~ 6, such as 3,4,5 or 6 etc.
Namely described polyether diatomic alcohol containing fluorine two ends are terminal hydroxy group polyethoxye group, and centre is block perfluor polyethoxye polymethoxy group.
Preferably, the molecular weight of described polyether diatomic alcohol containing fluorine is 1500 ~ 2000, such as 1500,1600,1700,1800,1900 or 2000 etc.;
In the present invention, the preparation method of the dihydroxyl polydiphenylsiloxane of described ZnO Modified is:
A nano-ZnO is scattered in dihydroxyl polydiphenylsiloxane emulsion by (), ultrasonic disperse 1 ~ 2h, obtained dispersion liquid;
B dispersion liquid adds in the encloses container with reflux exchanger and agitator by (), be then warming up to 40 ~ 50 DEG C, stirring and refluxing 5 ~ 8h, obtain the dihydroxyl polydiphenylsiloxane of ZnO Modified.
Wherein, in step (a), the ultrasonic disperse time can be 1h, 1.2h, 1.4h, 1.6h, 1.8h or 2h etc.; Be warming up to 40 ~ 50 DEG C in step (b), can be 40 DEG C, 42 DEG C, 44 DEG C, 45 DEG C, 46 DEG C, 48 DEG C or 50 DEG C etc.; The stirring and refluxing time can be 5h, 6h, 7h or 8h etc.
Preferably, the mass ratio of described nano-ZnO and dihydroxyl polydiphenylsiloxane emulsion is 1:(6 ~ 10), such as 1:6,1:7,1:8,1:9 or 1:10 etc., be preferably 1:8.
Second aspect, the invention provides above-mentioned method for preparing thermoplastic polyurethane elastomer, said method comprising the steps of:
(1) polymerized polyalcohol of formula ratio, BDO and Hydroxyethyl acrylate are added in container successively, vacuumize in 60 ~ 80 DEG C under agitation, obtain compound A;
(2) after the isophorone diisocyanate of formula ratio being heated to 50 ~ 60 DEG C, mix with the compound A obtained in step (1), the dihydroxyl polydiphenylsiloxane adding the ZnO Modified of formula ratio again stirs 1 ~ 3h at 130 ~ 140 DEG C, then slaking 10 ~ 14h at 75 ~ 80 DEG C, obtains material B;
(3) material B is added extruding pelletization in twin screw extruder and obtain Polyurethane Thermoplastic Elastomer.
Wherein, vacuumize in 60 ~ 80 DEG C under agitation condition in step (1), its temperature can be 60 DEG C, 63 DEG C, 65 DEG C, 67 DEG C, 70 DEG C, 73 DEG C, 75 DEG C, 77 DEG C or 80 DEG C etc.; Isophorone diisocyanate is heated to 50 ~ 60 DEG C in step (2), such as 50 DEG C, 51 DEG C, 52 DEG C, 53 DEG C, 54 DEG C, 55 DEG C, 56 DEG C, 57 DEG C, 58 DEG C, 59 DEG C or 60 DEG C etc.; The dihydroxyl polydiphenylsiloxane adding the ZnO Modified of formula ratio in step (2) stirs 1 ~ 3h at 130 ~ 140 DEG C, wherein temperature can be 130 DEG C, 131 DEG C, 132 DEG C, 133 DEG C, 134 DEG C, 135 DEG C, 136 DEG C, 137 DEG C, 138 DEG C, 139 DEG C or 140 DEG C etc., and the time can be 1h, 1.5h, 2h, 2.5h or 3h etc.; Slaking 10 ~ 14h at 75 ~ 80 DEG C, wherein temperature can be 75 DEG C, 76 DEG C, 77 DEG C, 78 DEG C, 79 DEG C or 80 DEG C etc., and the curing time can be 10h, 11h, 12h, 13h or 14h etc.
In the present invention, the preparation method of the dihydroxyl polydiphenylsiloxane of described ZnO Modified is:
A nano-ZnO is scattered in dihydroxyl polydiphenylsiloxane emulsion by (), ultrasonic disperse 1 ~ 2h, obtained dispersion liquid;
B dispersion liquid adds in the encloses container with reflux exchanger and agitator by (), be then warming up to 40 ~ 50 DEG C, stirring and refluxing 5 ~ 8h, obtain the dihydroxyl polydiphenylsiloxane of ZnO Modified;
Preferably, the mass ratio of described nano-ZnO and dihydroxyl polydiphenylsiloxane emulsion is 1:(6 ~ 10), be preferably 1:8.
In the present invention, in step (1), vacuum condition is pressure-0.4 ~-0.2kPa, such as-0.4kPa ,-0.35kPa ,-0.3kPa ,-0.25kPa or-0.2kPa etc.
Preferably, in step (1), stir speed (S.S.) is 1000 ~ 1200r/min, such as 1000r/min, 1050r/min, 1100r/min, 1150r/min or 1200r/min etc.
Preferably, in step (2), stir speed (S.S.) is 1000 ~ 1200r/min, such as 1000r/min, 1050r/min, 1100r/min, 1150r/min or 1200r/min etc.
In the present invention, the feeding section temperature arranging twin screw extruder in described step (3) is 130 ~ 140 DEG C, such as 130 DEG C, 132 DEG C, 134 DEG C, 136 DEG C, 138 DEG C or 140 DEG C etc.
Preferably, the mixing section temperature arranging twin screw extruder in step (3) is 160 ~ 170 DEG C, such as 160 DEG C, 162 DEG C, 164 DEG C, 166 DEG C, 168 DEG C or 170 DEG C etc.
Preferably, the extruding zone temperature arranging twin screw extruder in step (3) is 170 ~ 180 DEG C, such as 170 DEG C, 172 DEG C, 174 DEG C, 176 DEG C, 178 DEG C or 180 etc.
Preferably, the head temperature arranging twin screw extruder in step (3) is 170 ~ 180 DEG C, such as 170 DEG C, 172 DEG C, 174 DEG C, 176 DEG C, 178 DEG C or 180 etc.
Compared with prior art, the present invention has following beneficial effect:
The present invention is with polyether diatomic alcohol containing fluorine and hexanodioic acid 1, the mixture of 4-butanediol ester dibasic alcohol acts synergistically as both polymerized polyalcohols the waterproof and oilproof performance improving target product, make to possess excellent waterproofing and moisture-penetration performances, the infiltration of water droplet can be prevented, can ensure again water vapour freely through, and can to use in the presence of a harsh environment; Simultaneously, add the dihydroxyl polydiphenylsiloxane of ZnO Modified and the anti-microbial property of Hydroxyethyl acrylate raising Polyurethane Thermoplastic Elastomer, and make it have good mechanical property, make the water-intake rate (cold water soak 10 days)≤2% of Polyurethane Thermoplastic Elastomer, common bacteria inhibiting rate >=95%, and tensile strength remains on 85MPa, elongation at break reaches 810%, and rebound degree reaches 85%.
Summary of the invention
Water-proof breathable properties and anti-microbial property can not be had concurrently for thermoplastic elastomer in prior art, and improve the problem of its mechanical property simultaneously, the invention provides a kind of waterproof and breathable antimicrobial form Polyurethane Thermoplastic Elastomer and preparation method thereof.The present invention acts synergistically as both polymerized polyalcohols the waterproof and oilproof performance improving target product using the mixture of polyether diatomic alcohol containing fluorine and hexanodioic acid BDO ester dibasic alcohol; Meanwhile, the dihydroxyl polydiphenylsiloxane adding ZnO Modified improves the anti-microbial property of Polyurethane Thermoplastic Elastomer, and makes it have good mechanical property.
For reaching this object, the present invention by the following technical solutions:
First aspect, the invention provides a kind of Polyurethane Thermoplastic Elastomer, and described Polyurethane Thermoplastic Elastomer prepares primarily of following component by weight:
Wherein, polymerized polyalcohol is the mixture of polyether diatomic alcohol containing fluorine and hexanodioic acid BDO ester dibasic alcohol.
The weight part of polymerized polyalcohol can be 40 parts, 42 parts, 44 parts, 45 parts, 46 parts, 48 parts or 50 parts etc.; The weight part of isophorone diisocyanate can be 30 parts, 32 parts, 34 parts, 35 parts, 36 parts, 38 parts or 40 parts etc.; The weight part of BDO can be 10 parts, 11 parts, 12 parts, 13 parts, 14 parts or 15 parts etc.; The weight part of the dihydroxyl polydiphenylsiloxane of ZnO Modified can be 10 parts, 11 parts, 12 parts, 13 parts, 14 parts or 15 parts etc.; The weight part of Hydroxyethyl acrylate can be 5 parts, 6 parts, 7 parts, 8 parts, 9 parts or 10 parts etc.
Be preferably:
More preferably:
In the present invention, in described polymerized polyalcohol, the mass ratio of polyether diatomic alcohol containing fluorine and hexanodioic acid BDO ester dibasic alcohol is (3 ~ 5): 1, such as 3:1,3.5:1,4:1,4.5:1 or 5:1 etc., is preferably 4:1.
Participate in reaction using the mixture of polyether diatomic alcohol containing fluorine and hexanodioic acid BDO ester dibasic alcohol as polymerized polyalcohol, utilize fluorochemicals surface energy high, the feature that oleophylic is not hydrophilic, to improve the waterproof and oilproof performance of target product.Simultaneously, polyester type is different with the hydrolytic action of polyether thermoplastic's urethane, and the present invention is by adjusting the blending ratio of polyether diatomic alcohol containing fluorine and hexanodioic acid BDO ester dibasic alcohol, the synergy of both utilizations, improves its mechanical property while raising waterproof breathable performance.If the mass ratio of polyether diatomic alcohol containing fluorine and hexanodioic acid BDO ester dibasic alcohol, for being less than 3:1, can reduce the water-proof breathable properties of Polyurethane Thermoplastic Elastomer; If the mass ratio of polyether diatomic alcohol containing fluorine and hexanodioic acid BDO ester dibasic alcohol, for being greater than 5:1, can reduce the mechanical property of Polyurethane Thermoplastic Elastomer, as tensile strength and elongation at break etc.
Add the dihydroxyl polydiphenylsiloxane of ZnO Modified in the present invention, it can replace the hydrophilic TPU of a part, and the hydroxyl reaction that functional group wherein can also hold with TPU, the while of reducing TPU hydrophilic, and the anti-microbial property of raising TPU.If but the too high levels of the dihydroxyl polydiphenylsiloxane of ZnO Modified, being separated of itself and TPU can be caused again, physicals is declined.
Embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art should understand, described embodiment only understands the present invention for helping, and should not be considered as concrete restriction of the present invention.
In the present invention, each embodiment is adopted and is carried out performance test with the following method:
Water-intake rate is tested: immerse cold water after sample being first placed in 60 DEG C of drying in oven constant weights and soak 10d taking-up, weigh, by the water-intake rate obtaining sample of poor quality before and after immersion after drying surface water.
Anti-microbial property is tested: a certain amount of bacterium liquid is dropped on sample equably, and sample calculates bacterium number decrement, i.e. antibiotic rate after contacting with bacterium and cultivating certain hour.
Physical and mechanical properties is tested: mechanical property is tested on LJ-500 type tension tester by GB/T1040-1979, and rate of extension is 200mm/min.
Embodiment 1:
(1) the dihydroxyl polydiphenylsiloxane of ZnO Modified is prepared:
Nano-ZnO is scattered in (wherein, the mass ratio of nano-ZnO and dihydroxyl polydiphenylsiloxane emulsion is 1:8) in dihydroxyl polydiphenylsiloxane emulsion, ultrasonic disperse 1.5h, obtained dispersion liquid; Dispersion liquid is added in the encloses container with reflux exchanger and agitator, be then warming up to 45 DEG C, stirring and refluxing 6h, obtain the dihydroxyl polydiphenylsiloxane of ZnO Modified;
(2) Polyurethane Thermoplastic Elastomer is prepared:
The polymerized polyalcohol of 45 parts, 12 parts of BDOs and 7 parts of Hydroxyethyl acrylates are added (wherein, m=4, n in polyether diatomic alcohol containing fluorine in container successively
1=4, n
2=5, n
3=4, in polymerized polyalcohol, the mass ratio of polyether diatomic alcohol containing fluorine and hexanodioic acid BDO ester dibasic alcohol is 4:1), be evacuated to-0.3kPa with 1100r/min in 70 DEG C, obtain compound A; After the isophorone diisocyanate of 35 parts is heated to 55 DEG C, mix with compound A, the dihydroxyl polydiphenylsiloxane adding the ZnO Modified of 12 parts again stirs 2h with 1100r/min speed at 135 DEG C, and then slaking 12h at 77 DEG C, obtains material B; Material B is added extruding pelletization in twin screw extruder and obtain Polyurethane Thermoplastic Elastomer (wherein, arranging the feeding section temperature of twin screw extruder, mixing section temperature, extruding zone temperature and head temperature is respectively 135 DEG C, 165 DEG C, 175 DEG C and 175 DEG C).
Carry out performance test to obtained Polyurethane Thermoplastic Elastomer, test result is listed in table 1.
Embodiment 2:
(1) the dihydroxyl polydiphenylsiloxane of ZnO Modified is prepared:
Nano-ZnO is scattered in (wherein, the mass ratio of nano-ZnO and dihydroxyl polydiphenylsiloxane emulsion is 1:10) in dihydroxyl polydiphenylsiloxane emulsion, ultrasonic disperse 2h, obtained dispersion liquid; Dispersion liquid is added in the encloses container with reflux exchanger and agitator, be then warming up to 50 DEG C, stirring and refluxing 5h, obtain the dihydroxyl polydiphenylsiloxane of ZnO Modified;
(2) Polyurethane Thermoplastic Elastomer is prepared:
The polymerized polyalcohol of 47 parts, 13 parts of BDOs and 8 parts of Hydroxyethyl acrylates are added (wherein, m=3, n in polyether diatomic alcohol containing fluorine in container successively
1=3, n
2=3, n
3=3, in polymerized polyalcohol, the mass ratio of polyether diatomic alcohol containing fluorine and hexanodioic acid BDO ester dibasic alcohol is 5:1), be evacuated to-0.2kPa with 1000r/min in 80 DEG C, obtain compound A; After the isophorone diisocyanate of 37 parts is heated to 60 DEG C, mix with compound A, the dihydroxyl polydiphenylsiloxane adding the ZnO Modified of 13 parts again stirs 3h with 1200r/min speed at 130 DEG C, and then slaking 10h at 80 DEG C, obtains material B; Material B is added extruding pelletization in twin screw extruder and obtain Polyurethane Thermoplastic Elastomer (wherein, arranging the feeding section temperature of twin screw extruder, mixing section temperature, extruding zone temperature and head temperature is respectively 130 DEG C, 160 DEG C, 170 DEG C and 170 DEG C).
Carry out performance test to obtained Polyurethane Thermoplastic Elastomer, test result is listed in table 1.
Embodiment 3:
(1) the dihydroxyl polydiphenylsiloxane of ZnO Modified is prepared:
Nano-ZnO is scattered in (wherein, the mass ratio of nano-ZnO and dihydroxyl polydiphenylsiloxane emulsion is 1:6) in dihydroxyl polydiphenylsiloxane emulsion, ultrasonic disperse 1h, obtained dispersion liquid; Dispersion liquid is added in the encloses container with reflux exchanger and agitator, be then warming up to 40 DEG C, stirring and refluxing 8h, obtain the dihydroxyl polydiphenylsiloxane of ZnO Modified;
(2) Polyurethane Thermoplastic Elastomer is prepared:
The polymerized polyalcohol of 43 parts, 11 parts of BDOs and 6 parts of Hydroxyethyl acrylates are added (wherein, m=6, n in polyether diatomic alcohol containing fluorine in container successively
1=6, n
2=6, n
3=6, in polymerized polyalcohol, the mass ratio of polyether diatomic alcohol containing fluorine and hexanodioic acid BDO ester dibasic alcohol is 3:1), be evacuated to-0.4kPa with 1200r/min in 60 DEG C, obtain compound A; After the isophorone diisocyanate of 33 parts is heated to 50 DEG C, mix with compound A, the dihydroxyl polydiphenylsiloxane adding the ZnO Modified of 11 parts again stirs 1h with 1000r/min speed at 140 DEG C, and then slaking 14h at 75 DEG C, obtains material B; Material B is added extruding pelletization in twin screw extruder and obtain Polyurethane Thermoplastic Elastomer (wherein, arranging the feeding section temperature of twin screw extruder, mixing section temperature, extruding zone temperature and head temperature is respectively 140 DEG C, 170 DEG C, 180 DEG C and 180 DEG C).
Carry out performance test to obtained Polyurethane Thermoplastic Elastomer, test result is listed in table 1.
Embodiment 4:
Except the consumption of polymerized polyalcohol in step (2) be 40 parts, the consumption of isophorone diisocyanate is 30 parts, 1, the consumption of the dihydroxyl polydiphenylsiloxane that the consumption of 4-butyleneglycol is 10 parts, the consumption of Hydroxyethyl acrylate is 5 parts and ZnO Modified is 10 especially, and other steps are all in the same manner as in Example 1.
Carry out performance test to obtained Polyurethane Thermoplastic Elastomer, test result is listed in table 1.
Embodiment 5:
Except the consumption of polymerized polyalcohol in step (2) be 50 parts, the consumption of isophorone diisocyanate is 40 parts, 1, the consumption of the dihydroxyl polydiphenylsiloxane that the consumption of 4-butyleneglycol is 15 parts, the consumption of Hydroxyethyl acrylate is 10 parts and ZnO Modified is 15 especially, and other steps are all in the same manner as in Example 1.
Carry out performance test to obtained Polyurethane Thermoplastic Elastomer, test result is listed in table 1.
Comparative example 1:
Except polymerized polyalcohol only adopts polyether diatomic alcohol containing fluorine, other steps are all in the same manner as in Example 1.
Carry out performance test to obtained Polyurethane Thermoplastic Elastomer, test result is listed in table 1.
Comparative example 2:
Except polymerized polyalcohol only adopts hexanodioic acid BDO ester dibasic alcohol, other steps are all in the same manner as in Example 1.
Carry out performance test to obtained Polyurethane Thermoplastic Elastomer, test result is listed in table 1.
Comparative example 3:
Except the mass ratio of polyether diatomic alcohol containing fluorine in polymerized polyalcohol and hexanodioic acid BDO ester dibasic alcohol is except 1:1, other steps are all in the same manner as in Example 1.
Carry out performance test to obtained Polyurethane Thermoplastic Elastomer, test result is listed in table 1.
Comparative example 4:
Except the mass ratio of polyether diatomic alcohol containing fluorine in polymerized polyalcohol and hexanodioic acid BDO ester dibasic alcohol is except 10:1, other steps are all in the same manner as in Example 1.
Carry out performance test to obtained Polyurethane Thermoplastic Elastomer, test result is listed in table 1.
Comparative example 5:
Except the dihydroxyl polydiphenylsiloxane not adding ZnO Modified, other steps are all in the same manner as in Example 1.
Carry out performance test to obtained Polyurethane Thermoplastic Elastomer, test result is listed in table 1.
Comparative example 6:
Replace except the dihydroxyl polydiphenylsiloxane of ZnO Modified except with nano-ZnO, other steps are all in the same manner as in Example 1.
Carry out performance test to obtained Polyurethane Thermoplastic Elastomer, test result is listed in table 1.
Comparative example 7:
Addition except the dihydroxyl polydiphenylsiloxane of ZnO Modified is 1 especially, and other steps are all in the same manner as in Example 1.
Carry out performance test to obtained Polyurethane Thermoplastic Elastomer, test result is listed in table 1.
Comparative example 8:
Addition except the dihydroxyl polydiphenylsiloxane of ZnO Modified is 20 especially, and other steps are all in the same manner as in Example 1.
Carry out performance test to obtained Polyurethane Thermoplastic Elastomer, test result is listed in table 1.
Comparative example 9:
Except not adding except Hydroxyethyl acrylate, other steps are all in the same manner as in Example 1.
Carry out performance test to obtained Polyurethane Thermoplastic Elastomer, test result is listed in table 1.
Table 1: embodiment 1-5 and comparative example 1-9 Polyurethane Thermoplastic Elastomer carry out performance test chart
The result of the comparative example 1-9 of integrated embodiment 1-5 can be found out, the present invention is with polyether diatomic alcohol containing fluorine and hexanodioic acid 1, the mixture of 4-butanediol ester dibasic alcohol acts synergistically as both polymerized polyalcohols the waterproof and oilproof performance improving target product, make to possess excellent waterproofing and moisture-penetration performances, the infiltration of water droplet can be prevented, can ensure again water vapour freely through, and can to use in the presence of a harsh environment; Simultaneously, add the dihydroxyl polydiphenylsiloxane of ZnO Modified and the anti-microbial property of Hydroxyethyl acrylate raising Polyurethane Thermoplastic Elastomer, and make it have good mechanical property, make the water-intake rate (cold water soak 10 days)≤2% of Polyurethane Thermoplastic Elastomer, common bacteria inhibiting rate >=95%, and tensile strength remains on 85MPa, elongation at break reaches 810%, and rebound degree reaches 85%.
Applicant states, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, namely do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of ancillary component, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.
Claims (10)
1. a Polyurethane Thermoplastic Elastomer, is characterized in that, described Polyurethane Thermoplastic Elastomer prepares primarily of following component by weight:
Wherein, polymerized polyalcohol is the mixture of polyether diatomic alcohol containing fluorine and hexanodioic acid BDO ester dibasic alcohol.
2. Polyurethane Thermoplastic Elastomer according to claim 1, is characterized in that, described Polyurethane Thermoplastic Elastomer prepares primarily of following component by weight:
3. Polyurethane Thermoplastic Elastomer according to claim 1 and 2, is characterized in that, described Polyurethane Thermoplastic Elastomer prepares primarily of following component by weight:
4. the Polyurethane Thermoplastic Elastomer according to any one of claim 1-3, is characterized in that, in described polymerized polyalcohol, the mass ratio of polyether diatomic alcohol containing fluorine and hexanodioic acid BDO ester dibasic alcohol is (3 ~ 5): 1, is preferably 4:1.
5. the Polyurethane Thermoplastic Elastomer according to any one of claim 1-4, is characterized in that, the molecular structure of described polyether diatomic alcohol containing fluorine is:
Wherein, m=3 ~ 6, n
1=3 ~ 6, n
2=3 ~ 6, n
3=3 ~ 6;
Preferably, the molecular weight of described polyether diatomic alcohol containing fluorine is 1500 ~ 2000.
6. the Polyurethane Thermoplastic Elastomer according to any one of claim 1-5, is characterized in that, the preparation method of the dihydroxyl polydiphenylsiloxane of described ZnO Modified is:
A nano-ZnO is scattered in dihydroxyl polydiphenylsiloxane emulsion by (), ultrasonic disperse 1 ~ 2h, obtained dispersion liquid;
B dispersion liquid adds in the encloses container with reflux exchanger and agitator by (), be then warming up to 40 ~ 50 DEG C, stirring and refluxing 5 ~ 8h, obtain the dihydroxyl polydiphenylsiloxane of ZnO Modified;
Preferably, the mass ratio of described nano-ZnO and dihydroxyl polydiphenylsiloxane emulsion is 1:(6 ~ 10), be preferably 1:8.
7. the method for preparing thermoplastic polyurethane elastomer according to any one of claim 1-6, is characterized in that, said method comprising the steps of:
(1) polymerized polyalcohol of formula ratio, BDO and Hydroxyethyl acrylate are added in container successively, vacuumize in 60 ~ 80 DEG C under agitation, obtain compound A;
(2) after the isophorone diisocyanate of formula ratio being heated to 50 ~ 60 DEG C, mix with the compound A obtained in step (1), the dihydroxyl polydiphenylsiloxane adding the ZnO Modified of formula ratio again stirs 1 ~ 3h at 130 ~ 140 DEG C, then slaking 10 ~ 14h at 75 ~ 80 DEG C, obtains material B;
(3) material B is added extruding pelletization in twin screw extruder and obtain Polyurethane Thermoplastic Elastomer.
8. preparation method according to claim 7, is characterized in that, the preparation method of the dihydroxyl polydiphenylsiloxane of described ZnO Modified is:
A nano-ZnO is scattered in dihydroxyl polydiphenylsiloxane emulsion by (), ultrasonic disperse 1 ~ 2h, obtained dispersion liquid;
B dispersion liquid adds in the encloses container with reflux exchanger and agitator by (), be then warming up to 40 ~ 50 DEG C, stirring and refluxing 5 ~ 8h, obtain the dihydroxyl polydiphenylsiloxane of ZnO Modified;
Preferably, the mass ratio of described nano-ZnO and dihydroxyl polydiphenylsiloxane emulsion is 1:(6 ~ 10), be preferably 1:8.
9. the preparation method according to claim 7 or 8, is characterized in that, in step (1), vacuum condition is pressure-0.4 ~-0.2kPa;
Preferably, in step (1), stir speed (S.S.) is 1000 ~ 1200r/min;
Preferably, in step (2), stir speed (S.S.) is 1000 ~ 1200r/min.
10. the preparation method according to any one of claim 7-9, is characterized in that, the feeding section temperature arranging twin screw extruder in described step (3) is 130 ~ 140 DEG C;
Preferably, the mixing section temperature arranging twin screw extruder in step (3) is 160 ~ 170 DEG C;
Preferably, the extruding zone temperature arranging twin screw extruder in step (3) is 170 ~ 180 DEG C;
Preferably, the head temperature arranging twin screw extruder in step (3) is 170 ~ 180 DEG C.
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| CN106117510A (en) * | 2016-07-30 | 2016-11-16 | 山东科力美实业有限公司 | Antibacterial do not separate out Polyurethane Thermoplastic Elastomer and preparation method thereof |
| CN106234439A (en) * | 2016-08-09 | 2016-12-21 | 北京赛特瑞科技发展有限公司 | A kind of superbacteria antibiosis and sterilization agent and its production and use |
| CN106234439B (en) * | 2016-08-09 | 2019-08-06 | 北京赛特瑞科技发展有限公司 | A kind of superbacteria antibiosis and sterilization agent and its preparation method and application |
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| CN110760180B (en) * | 2018-07-26 | 2021-10-12 | 浙江华峰热塑性聚氨酯有限公司 | Waterproof moisture-permeable thermoplastic polyurethane polymer and preparation method thereof |
| CN111154064A (en) * | 2020-01-03 | 2020-05-15 | 万华化学集团股份有限公司 | Fluorine-silicon type thermoplastic polyurethane elastomer and preparation method thereof |
| CN111154064B (en) * | 2020-01-03 | 2022-02-18 | 万华化学集团股份有限公司 | Fluorine-silicon type thermoplastic polyurethane elastomer and preparation method thereof |
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