CN105085857B - Waterproof and breathable antimicrobial form thermoplastic polyurethane elastomer and preparation method thereof - Google Patents
Waterproof and breathable antimicrobial form thermoplastic polyurethane elastomer and preparation method thereof Download PDFInfo
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- CN105085857B CN105085857B CN201510567272.4A CN201510567272A CN105085857B CN 105085857 B CN105085857 B CN 105085857B CN 201510567272 A CN201510567272 A CN 201510567272A CN 105085857 B CN105085857 B CN 105085857B
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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
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- 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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- 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
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- C08G18/61—Polysiloxanes
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- 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
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- 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
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- C08K3/22—Oxides; Hydroxides of metals
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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
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- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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Abstract
The present invention provides a kind of waterproof and breathable antimicrobial form thermoplastic polyurethane elastomer and preparation method thereof, and the thermoplastic polyurethane elastomer is mainly prepared by following components by weight：5~10 parts of 40~50 parts of polymerized polyalcohol, 30~40 parts of isophorone diisocyanate, 10~15 parts of 1,4 butanediol, 10~15 parts of the dihydroxy polydiphenylsiloxane of ZnO Modified and hydroxy-ethyl acrylate.The present invention is with polyether diatomic alcohol containing fluorine and adipic acid 1, the mixture of 4 butanediol ester dihydric alcohols acts synergistically as both polymerized polyalcohols to improve the waterproof and oilproof performance of target product, simultaneously, the dihydroxy polydiphenylsiloxane and hydroxy-ethyl acrylate for adding ZnO Modified improve the anti-microbial property of thermoplastic polyurethane elastomer, and make it have good mechanical property.
Description
Technical field
The invention belongs to technical field of macromolecules, it is related to a kind of thermoplastic polyurethane elastomer and preparation method thereof, especially
It is related to a kind of waterproof and breathable antimicrobial form thermoplastic polyurethane elastomer and preparation method thereof.
Background technology
Thermoplastic polyurethane (Thermoplastic Polyurethane, TPU) is a kind of fusible and solvent of heating
Soluble high molecular material.TPU molecules are linear, and intermolecular seldom crosslinking, glass transition temperature is low, therefore with high-strength
Degree, high resiliency and excellent wear-resisting, oil resistant and low temperature tolerance characteristics.
Thermoplastic polyurethane elastomer has two class of polyester-type and polyether-type, white random spherical or cylindrical particle, relatively
Density 1.10~1.25, polyether-type relative density are smaller than polyester-type.The feature that polyurethane termoplastic elastomer protrudes is wearability
It is excellent, ozone resistance is fabulous, hardness is big, intensity is high, elasticity is good, low temperature resistant, have good oil resistant, chemical-resistant resistance and resistance to environment
Performance, polyether-type ester hydrolysis stability is far more than polyester-type in wet environment.
The excellent hydrolysis resistance of water resistant thermoplastic urethane resin is widely used in waterproof coating technique.Water is to TPU
Effect there are two, first, plasticization, i.e. hydrone are got into macromolecular chain, hydrogen is formed with the polar group in polymer molecule
Key makes the reaction force attenuation between polymer molecule, tensile strength, tearing strength and polishing machine decline, this process is reversible
, through drying and dehydrating, original performance can be restored；Second is that chemical degradation has occurred in the degradation of water, i.e. TPU, which is
It is irreversible, and endanger maximum.TPU can be divided into polyester-type and polyether-type, and the hydrolytic process of the two is different.Due to ester
Base facile hydrolysis, the hydrolysis of polyester-type TPU shows as backbone breaking, molecular weight reduces, tensile strength and elongation drastically under
Drop；And polyether-type TPU, so hydrolysis shows as crosslinking and is slowly broken, is drawn due to ether and carbamate groups hydrolysis
It stretches intensity to decline slowly, then elongation, which takes the lead in increasing, just to be declined, therefore polyether-type TPU has preferable water resistance.
Patent CN 104448788A disclose a kind of Waterproof Breathable type thermoplastic polyurethane film and preparation method thereof, institute
It includes the following ingredients formed by mass percentage to state Waterproof Breathable type thermoplastic polyurethane film：80~85% thermoplastic poly
Urethane, 8~10% slipping agent and 7~10% cloudy surface agent；Wherein, the raw material for preparing of the thermoplastic polyurethane includes：It is poly-
58~63 parts of tetramethylene ether glycol, 30~35 parts of toluene di-isocyanate(TDI), 5~8 parts of ethylene glycol ether acetate and two acetic acid
1~3 part of dibutyl tin.Although thermoplastic polyurethane film prepared by the invention has waterproofing and moisture-penetration performances, it is actual
Using and preserve during, under the conditions of suitable temperature and humidity easily growth and bacterial growth, influence its use.
Antibacterial polyurethane material refers to being modified to polyurethane material by antiseptic of the introducing with antibacterial group, from
And make polyurethane material that there is a kind of new function material for inhibiting or killing its surface bacteria ability.Currently, common antibacterial
Agent mainly has natural class, inorganic and organic three categories.Organic antibacterial agent can effectively inhibit harmful bacteria, mould generation with
Breeding, it is quick.But this kind of antiseptic thermal stability poor (can only be used below at 300 DEG C), easily decomposition, persistence are poor,
And be usually more toxic, it uses for a long time harmful；The advantages of inorganic series antibacterial agent be with hypotoxicity, heat resistance,
Durability, duration, has a broad antifungal spectrum etc. are the optimum antiseptic kinds of the life products such as fiber, plastics, building materials.
Patent CN 104109332A disclose a kind of antibacterial thermoplastic elastomer (TPE) and the preparation method and application thereof, the antibacterial
Thermoplastic elastomer (TPE) includes following weight percentage components：SEBS 15~30%, rubber filling oil 10~30%, polyurethane
10~25%, antibacterial matrices 15~30%, the first inorganic filler 5~25%, the first compatilizer 5~15% and other auxiliary agents 0~
2%；Preparation method includes the steps that weighing each component and in such a way that side is fed to each component melting mixing extrusion process
The step of.The patent is prepared antibacterial thermoplastic elastomer (TPE) and although has excellent antibacterial effect, but its waterproof breathable
Can be undesirable, anti-microbial property is not lasting, and its mechanical property is also to be improved.
Therefore, a kind of thermoplastic poly ammonia having both excellent water-proof breathable properties, anti-microbial property and excellent mechanical performances is prepared
The problem of ester elastomer is urgent need to resolve.
Invention content
Water-proof breathable properties and anti-microbial property cannot be had both for thermoplastic elastomer (TPE) in the prior art, and improve its power simultaneously
The problem of learning performance, the present invention provides a kind of waterproof and breathable antimicrobial form thermoplastic polyurethane elastomer and preparation method thereof.This
Invention is cooperateed with using the mixture of polyether diatomic alcohol containing fluorine and adipic acid 1,4-butanediol ester dihydric alcohol as both polymerized polyalcohols
Effect is to improve the waterproof and oilproof performance of target product；Meanwhile the dihydroxy polydiphenylsiloxane for adding ZnO Modified carries
The anti-microbial property of high thermoplasticity polyurethane elastomer, and make it have good mechanical property.
For this purpose, the present invention uses following technical scheme：
In a first aspect, the present invention provides a kind of thermoplastic polyurethane elastomer, the thermoplastic polyurethane elastomer is pressed
Parts by weight meter is mainly prepared by following components：
Wherein, polymerized polyalcohol is the mixture of polyether diatomic alcohol containing fluorine and adipic acid 1,4-butanediol ester dihydric alcohol.
The parts by weight of polymerized polyalcohol can be 40 parts, 42 parts, 44 parts, 45 parts, 46 parts, 48 parts or 50 parts etc.；Isophorone
The parts by weight of diisocyanate can be 30 parts, 32 parts, 34 parts, 35 parts, 36 parts, 38 parts or 40 parts etc.；The weight of 1,4- butanediols
Part can be 10 parts, 11 parts, 12 parts, 13 parts, 14 parts or 15 parts etc.；The weight of the dihydroxy polydiphenylsiloxane of ZnO Modified
It can be 10 parts, 11 parts, 12 parts, 13 parts, 14 parts or 15 parts etc. to measure part；The parts by weight of hydroxy-ethyl acrylate can be 5 parts, 6 parts, 7 parts,
8 parts, 9 parts or 10 parts etc..
Preferably：
Further preferably：
In the present invention, the matter of polyether diatomic alcohol containing fluorine and adipic acid 1,4-butanediol ester dihydric alcohol in the polymerized polyalcohol
Amount is than being (3~5):1, such as 3:1、3.5:1、4:1、4.5:1 or 5:1 etc., preferably 4:1.
It is participated in using the mixture of polyether diatomic alcohol containing fluorine and adipic acid 1,4-butanediol ester dihydric alcohol as polymerized polyalcohol
Reaction, not oleophylic not hydrophilic feature high using fluorochemical surface energy, to improve the waterproof and oilproof performance of target product.
Meanwhile the hydrolysis of polyester-type and polyether thermoplastic polyurethane is different, the present invention by adjusting polyether diatomic alcohol containing fluorine and
The mixed proportion of adipic acid 1,4-butanediol ester dihydric alcohol is improving waterproof breathable performance using the synergistic effect of the two
Improve its mechanical property simultaneously.If the mass ratio of polyether diatomic alcohol containing fluorine and adipic acid 1,4-butanediol ester dihydric alcohol is less than 3:
1, the water-proof breathable properties of thermoplastic polyurethane elastomer can be reduced；If polyether diatomic alcohol containing fluorine and adipic acid 1,4-butanediol ester two
The mass ratio of first alcohol is more than 5:1, the mechanical property of thermoplastic polyurethane elastomer can be reduced, such as tensile strength and extension at break
Rate etc..
The dihydroxy polydiphenylsiloxane that ZnO Modified is added in the present invention, can replace a part of hydrophilic
TPU, and functional group therein can also with the hydroxyl reaction at the ends TPU, reduce TPU it is hydrophilic simultaneously, improve the anti-of TPU
Bacterium performance.If but the too high levels of the dihydroxy polydiphenylsiloxane of ZnO Modified, and its phase point with TPU can be caused
From making physical property decline.
In the prior art, in order to improve the anti-microbial property of material, have and divided by disperseing Nano silver grain in a solvent
Dispersion liquid, then dispersion is made to obtain antibiotic property with the matrix surface for assigning its antibiotic property is contacted.Nano inorganic anti-biotic material can be with
It is divided into two classes：First, metal oxide such as TiO with antibacterial activity itself2And ZnO；Second is that with silver zinc complex object for main antibacterial
Body, with ultra-fine SiO2And TiO2Deng the antibacterial zeolite for carrier.
However the grain size very little of nano-particle, high surface energy make it easier to reunite, bad dispersibility forms secondary grain
Son can not show surface-area effects, bulk effect and quantum size effect etc. that it is favored, prevent it from keeping lasting
Antibiotic property.The present invention makes nano-ZnO grow grafting on dihydroxy polydiphenylsiloxane surface, improves nano-ZnO surface
Wetability increases its affinity with other materials, increases antibacterial effect, while the adhesiveness of dihydroxy polydiphenylsiloxane
The Durability of antimicrobial effect of material can be improved.
In the present invention, addition hydroxy-ethyl acrylate can provide crosslinking points so that polyurethane as crosslinking agent to polyurethane
Reticular structure is formd, water and solvent molecule are all difficult to enter in macromolecular structure, to improve its water resistance gas permeability
And mechanical property.
In the present invention, the molecular structure of the polyether diatomic alcohol containing fluorine is HO- (CH2CH2O)n1-CH2-CF2O-
(CF2CF2O)m-(CF2O)n2-CF2-CH2-(OCH2CH2)n3-OH；
Wherein, m=3~6, such as 3,4,5 or 6 etc.；n1=3~6, such as 3,4,5 or 6 etc.；n2=3~6, such as 3,4,5
Or 6 etc.；n3=3~6, such as 3,4,5 or 6 etc..
The i.e. described polyether diatomic alcohol containing fluorine both ends are terminal hydroxy group polyethoxy group, and centre is that block perfluor polyethoxy is poly-
Methoxy group.
Preferably, the molecular weight of the polyether diatomic alcohol containing fluorine be 1500~2000, such as 1500,1600,1700,
1800,1900 or 2000 etc.；
In the present invention, the preparation method of the dihydroxy polydiphenylsiloxane of the ZnO Modified is：
(a) nano-ZnO is scattered in dihydroxy polydiphenylsiloxane lotion, 1~2h of ultrasonic disperse, dispersion is made
Liquid；
(b) dispersion liquid is added in the closed container with reflux condenser and blender, then heats to 40~50 DEG C,
It is stirred at reflux 5~8h, obtains the dihydroxy polydiphenylsiloxane of ZnO Modified.
Wherein, the ultrasonic disperse time can be 1h, 1.2h, 1.4h, 1.6h, 1.8h or 2h etc. in step (a)；In step (b)
40~50 DEG C are warming up to, 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.；Be stirred at reflux the time can be 5h,
6h, 7h or 8h etc..
Preferably, the nano-ZnO and the mass ratio of dihydroxy polydiphenylsiloxane lotion are 1:(6~10), such as
1:6、1:7、1:8、1:9 or 1:10 etc., preferably 1:8.
Second aspect, the present invention provides above-mentioned method for preparing thermoplastic polyurethane elastomer, the method includes with
Lower step：
(1) polymerized polyalcohol of formula ratio, 1,4-butanediol and hydroxy-ethyl acrylate are sequentially added in container, is being stirred
Under the conditions of vacuumized in 60~80 DEG C, obtain mixture A；
(2) after the isophorone diisocyanate of formula ratio being heated to 50~60 DEG C, with the mixing obtained in step (1)
Expect A mixing, the dihydroxy polydiphenylsiloxane for adding the ZnO Modified of formula ratio stirs 1 at 130~140 DEG C~
Then 3h cures 10~14h at 75~80 DEG C, obtains material B；
(3) material B is added twin-screw extrude into extruding pelletization and obtains thermoplastic polyurethane elastomer.
Wherein, vacuumized in 60~80 DEG C under stirring condition in step (1), 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.；Formula ratio is added in step (2)
The dihydroxy polydiphenylsiloxane of ZnO Modified stir 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., the time can be 1h,
1.5h, 2h, 2.5h or 3h etc.；At 75~80 DEG C cure 10~14h, wherein temperature can be 75 DEG C, 76 DEG C, 77 DEG C, 78 DEG C, 79
DEG C or 80 DEG C etc., the curing time can be 10h, 11h, 12h, 13h or 14h etc..
In the present invention, the preparation method of the dihydroxy polydiphenylsiloxane of the ZnO Modified is：
(a) nano-ZnO is scattered in dihydroxy polydiphenylsiloxane lotion, 1~2h of ultrasonic disperse, dispersion is made
Liquid；
(b) dispersion liquid is added in the closed container with reflux condenser and blender, then heats to 40~50 DEG C,
It is stirred at reflux 5~8h, obtains the dihydroxy polydiphenylsiloxane of ZnO Modified；
Preferably, the nano-ZnO and the mass ratio of dihydroxy polydiphenylsiloxane lotion are 1:(6~10), preferably
It is 1:8.
In the present invention, in step (1) vacuum condition be 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.) be 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.) be 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 of setting double screw extruder is 130~140 DEG C in the step (3), 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 of setting double screw extruder is 160~170 DEG C in step (3), 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 of setting double screw extruder is 170~180 DEG C in step (3), such as 170 DEG C,
172 DEG C, 174 DEG C, 176 DEG C, 178 DEG C or 180 etc..
Preferably, the head temperature of setting double screw extruder is 170~180 DEG C in step (3), for example, 170 DEG C, 172
DEG C, 174 DEG C, 176 DEG C, 178 DEG C or 180 etc..
Compared with prior art, the invention has the advantages that：
The present invention is using the mixture of polyether diatomic alcohol containing fluorine and adipic acid 1,4-butanediol ester dihydric alcohol as polymeric polyols
Both alcohol acts synergistically to improve the waterproof and oilproof performance of target product, makes the waterproofing and moisture-penetration performances for having excellent, can prevent
The infiltration of water droplet, and can guarantee freely penetrating for vapor, and can use in the presence of a harsh environment；Meanwhile adding ZnO Modified
Dihydroxy polydiphenylsiloxane and hydroxy-ethyl acrylate improve the anti-microbial property of thermoplastic polyurethane elastomer, and make its tool
There is good mechanical property, the water absorption rate (cold water soak 10 days)≤2% of thermoplastic polyurethane elastomer, common bacteria is made to inhibit
Rate >=95%, and tensile strength is maintained at 85MPa, elongation at break reaches 810%, and rebound degree reaches 85%.
Specific implementation mode
Of the invention for ease of understanding, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that the implementation
Example is used only for helping to understand the present invention, should not be regarded as a specific limitation of the invention.
Each embodiment is tested for the property with the following method in the present invention：
Water absorption rate test：Immersion 10d taking-ups in cold water are immersed after sample to be first placed in 60 DEG C of drying in oven constant weights, are dried
It weighs after the water of surface, by the front and back water absorption rate of poor quality for finding out sample that soaks.
Anti-microbial property test：A certain amount of bacterium solution is equably dropped on sample, sample contacts culture certain time with bacterium
Bacterium number slip, i.e. antibiotic rate are calculated afterwards.
Physical mechanical property is tested：Mechanical property is tested by GB/T 1040-1979 on LJ-500 type tension testers,
Rate of extension is 200mm/min.
Embodiment 1：
(1) the dihydroxy polydiphenylsiloxane of ZnO Modified is prepared：
Nano-ZnO is scattered in dihydroxy polydiphenylsiloxane lotion (wherein, nano-ZnO and the poly- hexichol of dihydroxy
The mass ratio of radical siloxane lotion is 1:8) dispersion liquid is made in, ultrasonic disperse 1.5h；Dispersion liquid is added and carries reflux condenser
In the closed container of blender, 45 DEG C are then heated to, 6h is stirred at reflux, obtains the poly- hexichol of dihydroxy of ZnO Modified
Radical siloxane；
(2) thermoplastic polyurethane elastomer is prepared：
45 parts of polymerized polyalcohol, 12 parts of 1,4- butanediols and 7 parts of hydroxy-ethyl acrylates are sequentially added into container (its
In, m=4, n in polyether diatomic alcohol containing fluorine1=4, n2=5, n3=4, polyether diatomic alcohol containing fluorine and adipic acid 1 in polymerized polyalcohol,
The mass ratio of 4- butanediol ester dihydric alcohols is 4:1) -0.3kPa, is evacuated in 70 DEG C with 1100r/min, obtains mixture A；
It after 35 parts of isophorone diisocyanate is heated to 55 DEG C, is mixed with mixture A, adds 12 parts of ZnO Modified
Dihydroxy polydiphenylsiloxane at 135 DEG C with 1100r/min rates stir 2h, then cure 12h at 77 DEG C, obtain
Material B；By material B add twin-screw extrude extruding pelletization obtain thermoplastic polyurethane elastomer (wherein, be respectively set it is double
Feeding section temperature, mixing section temperature, extruding zone temperature and the head temperature of screw extruder be 135 DEG C, 165 DEG C, 175 DEG C and
175℃)。
Thermoplastic polyurethane elastomer obtained is tested for the property, test result is listed in Table 1 below.
Embodiment 2：
(1) the dihydroxy polydiphenylsiloxane of ZnO Modified is prepared：
Nano-ZnO is scattered in dihydroxy polydiphenylsiloxane lotion (wherein, nano-ZnO and the poly- hexichol of dihydroxy
The mass ratio of radical siloxane lotion is 1:10) dispersion liquid is made in, ultrasonic disperse 2h；Dispersion liquid is added and carries reflux condenser
In the closed container of blender, 50 DEG C are then heated to, 5h is stirred at reflux, obtains the poly- hexichol of dihydroxy of ZnO Modified
Radical siloxane；
(2) thermoplastic polyurethane elastomer is prepared：
47 parts of polymerized polyalcohol, 13 parts of 1,4- butanediols and 8 parts of hydroxy-ethyl acrylates are sequentially added into container (its
In, m=3, n in polyether diatomic alcohol containing fluorine1=3, n2=3, n3=3, polyether diatomic alcohol containing fluorine and adipic acid 1 in polymerized polyalcohol,
The mass ratio of 4- butanediol ester dihydric alcohols is 5:1) -0.2kPa, is evacuated in 80 DEG C with 1000r/min, obtains mixture A；
It after 37 parts of isophorone diisocyanate is heated to 60 DEG C, is mixed with mixture A, adds 13 parts of ZnO Modified
Dihydroxy polydiphenylsiloxane at 130 DEG C with 1200r/min rates stir 3h, then cure 10h at 80 DEG C, obtain
Material B；By material B add twin-screw extrude extruding pelletization obtain thermoplastic polyurethane elastomer (wherein, be respectively set it is double
Feeding section temperature, mixing section temperature, extruding zone temperature and the head temperature of screw extruder be 130 DEG C, 160 DEG C, 170 DEG C and
170℃)。
Thermoplastic polyurethane elastomer obtained is tested for the property, test result is listed in Table 1 below.
Embodiment 3：
(1) the dihydroxy polydiphenylsiloxane of ZnO Modified is prepared：
Nano-ZnO is scattered in dihydroxy polydiphenylsiloxane lotion (wherein, nano-ZnO and the poly- hexichol of dihydroxy
The mass ratio of radical siloxane lotion is 1:6) dispersion liquid is made in, ultrasonic disperse 1h；Dispersion liquid is added with reflux condenser and
In the closed container of blender, 40 DEG C are then heated to, 8h is stirred at reflux, obtains the poly- diphenyl of dihydroxy of ZnO Modified
Siloxanes；
(2) thermoplastic polyurethane elastomer is prepared：
43 parts of polymerized polyalcohol, 11 parts of 1,4- butanediols and 6 parts of hydroxy-ethyl acrylates are sequentially added into container (its
In, m=6, n in polyether diatomic alcohol containing fluorine1=6, n2=6, n3=6, polyether diatomic alcohol containing fluorine and adipic acid 1 in polymerized polyalcohol,
The mass ratio of 4- butanediol ester dihydric alcohols is 3:1) -0.4kPa, is evacuated in 60 DEG C with 1200r/min, obtains mixture A；
It after 33 parts of isophorone diisocyanate is heated to 50 DEG C, is mixed with mixture A, adds 11 parts of ZnO Modified
Dihydroxy polydiphenylsiloxane at 140 DEG C with 1000r/min rates stir 1h, then cure 14h at 75 DEG C, obtain
Material B；By material B add twin-screw extrude extruding pelletization obtain thermoplastic polyurethane elastomer (wherein, be respectively set it is double
Feeding section temperature, mixing section temperature, extruding zone temperature and the head temperature of screw extruder be 140 DEG C, 170 DEG C, 180 DEG C and
180℃)。
Thermoplastic polyurethane elastomer obtained is tested for the property, test result is listed in Table 1 below.
Embodiment 4：
Except the dosage of polymerized polyalcohol in step (2) is 40 parts, the dosage of isophorone diisocyanate is 30 parts, 1,4-
The dosage of butanediol is 10 parts, the dosage of hydroxy-ethyl acrylate is 5 parts and the poly- diphenyl silica of the dihydroxy of ZnO Modified
Especially for 10, other steps are in the same manner as in Example 1 for the dosage of alkane.
Thermoplastic polyurethane elastomer obtained is tested for the property, test result is listed in Table 1 below.
Embodiment 5：
Except the dosage of polymerized polyalcohol in step (2) is 50 parts, the dosage of isophorone diisocyanate is 40 parts, 1,4-
The dosage of butanediol is 15 parts, the dosage of hydroxy-ethyl acrylate is 10 parts and the poly- diphenyl silicon of the dihydroxy of ZnO Modified
Especially for 15, other steps are in the same manner as in Example 1 for the dosage of oxygen alkane.
Thermoplastic polyurethane elastomer obtained is tested for the property, test result is listed in Table 1 below.
Comparative example 1：
In addition to polymerized polyalcohol is only with polyether diatomic alcohol containing fluorine, other steps are in the same manner as in Example 1.
Thermoplastic polyurethane elastomer obtained is tested for the property, test result is listed in Table 1 below.
Comparative example 2：
In addition to polymerized polyalcohol is only with adipic acid 1,4-butanediol ester dihydric alcohol, other steps with phase in embodiment 1
Together.
Thermoplastic polyurethane elastomer obtained is tested for the property, test result is listed in Table 1 below.
Comparative example 3：
Except the mass ratio of polyether diatomic alcohol containing fluorine in polymerized polyalcohol and adipic acid 1,4-butanediol ester dihydric alcohol is 1:1
Outside, other steps are in the same manner as in Example 1.
Thermoplastic polyurethane elastomer obtained is tested for the property, test result is listed in Table 1 below.
Comparative example 4：
Except the mass ratio of polyether diatomic alcohol containing fluorine in polymerized polyalcohol and adipic acid 1,4-butanediol ester dihydric alcohol is 10:1
Outside, other steps are in the same manner as in Example 1.
Thermoplastic polyurethane elastomer obtained is tested for the property, test result is listed in Table 1 below.
Comparative example 5：
In addition to the dihydroxy polydiphenylsiloxane for not adding ZnO Modified, other steps with phase in embodiment 1
Together.
Thermoplastic polyurethane elastomer obtained is tested for the property, test result is listed in Table 1 below.
Comparative example 6：
In addition to the dihydroxy polydiphenylsiloxane for replacing ZnO Modified with nano-ZnO, other steps are and embodiment
It is identical in 1.
Thermoplastic polyurethane elastomer obtained is tested for the property, test result is listed in Table 1 below.
Comparative example 7：
Except the additive amount of the dihydroxy polydiphenylsiloxane of ZnO Modified is that 1 especially, other steps are and embodiment
It is identical in 1.
Thermoplastic polyurethane elastomer obtained is tested for the property, test result is listed in Table 1 below.
Comparative example 8：
Except the additive amount of the dihydroxy polydiphenylsiloxane of ZnO Modified be 20 especially, other steps with implementation
It is identical in example 1.
Thermoplastic polyurethane elastomer obtained is tested for the property, test result is listed in Table 1 below.
Comparative example 9：
In addition to not adding hydroxy-ethyl acrylate, other steps are in the same manner as in Example 1.
Thermoplastic polyurethane elastomer obtained is tested for the property, test result is listed in Table 1 below.
Table 1：Embodiment 1-5 and comparative example 1-9 thermoplastic polyurethane elastomer are tested for the property table
The result of the comparative example 1-9 of integrated embodiment 1-5 can be seen that the present invention with polyether diatomic alcohol containing fluorine and adipic acid
The mixture of 1,4-butanediol ester dihydric alcohol acts synergistically as both polymerized polyalcohols to improve the waterproof and oilproof of target product
Performance makes the waterproofing and moisture-penetration performances for having excellent, can prevent the infiltration of water droplet and freely penetrating for vapor, and
It can use in the presence of a harsh environment；Meanwhile adding the dihydroxy polydiphenylsiloxane of ZnO Modified and hydroxy-ethyl acrylate carries
The anti-microbial property of high thermoplasticity polyurethane elastomer, and good mechanical property is made it have, make thermoplastic polyurethane elastomer
Water absorption rate (cold water soak 10 days)≤2%, common bacteria inhibiting rate >=95%, and tensile strength is maintained at 85MPa, fracture is stretched
Long rate reaches 810%, and rebound degree reaches 85%.
Applicant states that the present invention illustrates detailed process equipment and the technological process of the present invention by above-described embodiment,
But the invention is not limited in above-mentioned detailed process equipment and technological processes, that is, it is above-mentioned detailed not mean that the present invention has to rely on
Process equipment and technological process could be implemented.Person of ordinary skill in the field it will be clearly understood that any improvement in the present invention,
The addition of equivalence replacement and auxiliary element to each raw material of product of the present invention, the selection etc. of concrete mode all fall within the present invention's
Within protection domain and the open scope.
Claims (20)
1. a kind of thermoplastic polyurethane elastomer, which is characterized in that the thermoplastic polyurethane elastomer is main by weight
It is prepared by following components：
Wherein, polymerized polyalcohol is the mixture of polyether diatomic alcohol containing fluorine and adipic acid 1,4-butanediol ester dihydric alcohol, described poly-
It is (3~5) to close the mass ratio of polyether diatomic alcohol containing fluorine and adipic acid 1,4-butanediol ester dihydric alcohol in polyalcohol:1.
2. thermoplastic polyurethane elastomer according to claim 1, which is characterized in that the thermoplastic polyurethane elastomer
It is mainly prepared by weight by following components：
3. thermoplastic polyurethane elastomer according to claim 1, which is characterized in that the thermoplastic polyurethane elastomer
It is mainly prepared by weight by following components：
4. thermoplastic polyurethane elastomer according to claim 1, which is characterized in that fluorine-containing poly- in the polymerized polyalcohol
The mass ratio of ether dihydric alcohol and adipic acid 1,4-butanediol ester dihydric alcohol is 4:1.
5. according to claim 1-3 any one of them thermoplastic polyurethane elastomer, which is characterized in that the fluorochemical polyether two
The molecular structure of first alcohol is：
HO-(CH2CH2O)n1-CH2-CF2O-(CF2CF2O)m-(CF2O)n2-CF2-CH2-(OCH2CH2)n3-OH；
Wherein, m=3~6, n1=3~6, n2=3~6, n3=3~6.
6. according to claim 1-3 any one of them thermoplastic polyurethane elastomer, which is characterized in that the fluorochemical polyether two
The molecular weight of first alcohol is 1500~2000.
7. according to claim 1-3 any one of them thermoplastic polyurethane elastomer, which is characterized in that the nano-ZnO changes
The preparation method of the dihydroxy polydiphenylsiloxane of property is：
(a) nano-ZnO is scattered in dihydroxy polydiphenylsiloxane lotion, 1~2h of ultrasonic disperse, dispersion liquid is made；
(b) dispersion liquid is added in the closed container with reflux condenser and blender, then heats to 40~50 DEG C, stirring
Flow back 5~8h, obtains the dihydroxy polydiphenylsiloxane of ZnO Modified.
8. thermoplastic polyurethane elastomer according to claim 7, which is characterized in that the nano-ZnO and dihydroxy are poly-
The mass ratio of diphenyl siloxane lotion is 1:(6~10).
9. thermoplastic polyurethane elastomer according to claim 8, which is characterized in that the nano-ZnO and dihydroxy are poly-
The mass ratio of diphenyl siloxane lotion is 1:8.
10. according to claim 1-9 any one of them method for preparing thermoplastic polyurethane elastomer, which is characterized in that institute
The method of stating includes the following steps：
(1) polymerized polyalcohol of formula ratio, 1,4-butanediol and hydroxy-ethyl acrylate are sequentially added in container, in stirring condition
Under vacuumized in 60~80 DEG C, obtain mixture A；
(2) after the isophorone diisocyanate of formula ratio being heated to 50~60 DEG C, with the mixture A obtained in step (1)
Mixing, the dihydroxy polydiphenylsiloxane for adding the ZnO Modified of formula ratio stir 1~3h at 130~140 DEG C,
Then 10~14h is cured at 75~80 DEG C, obtains material B；
(3) material B is added twin-screw extrude into extruding pelletization and obtains thermoplastic polyurethane elastomer.
11. preparation method according to claim 10, which is characterized in that the poly- hexichol of dihydroxy of the ZnO Modified
The preparation method of radical siloxane is：
(a) nano-ZnO is scattered in dihydroxy polydiphenylsiloxane lotion, 1~2h of ultrasonic disperse, dispersion liquid is made；
(b) dispersion liquid is added in the closed container with reflux condenser and blender, then heats to 40~50 DEG C, stirring
Flow back 5~8h, obtains the dihydroxy polydiphenylsiloxane of ZnO Modified.
12. preparation method according to claim 11, which is characterized in that the nano-ZnO and the poly- diphenyl silicon of dihydroxy
The mass ratio of oxygen alkane lotion is 1:(6~10).
13. preparation method according to claim 12, which is characterized in that the nano-ZnO and the poly- diphenyl silicon of dihydroxy
The mass ratio of oxygen alkane lotion is 1:8.
14. preparation method according to claim 10, which is characterized in that in step (1) vacuum condition be pressure -0.4~-
0.2kPa。
15. preparation method according to claim 10, which is characterized in that in step (1) stir speed (S.S.) be 1000~
1200r/min。
16. preparation method according to claim 10, which is characterized in that in step (2) stir speed (S.S.) be 1000~
1200r/min。
17. preparation method according to claim 10, which is characterized in that double screw extruder is arranged in the step (3)
Feeding section temperature be 130~140 DEG C.
18. preparation method according to claim 10, which is characterized in that setting double screw extruder is mixed in step (3)
It is 160~170 DEG C to close section temperature.
19. preparation method according to claim 10, which is characterized in that setting double screw extruder squeezes in step (3)
It is 170~180 DEG C to go out section temperature.
20. preparation method according to claim 10, which is characterized in that the machine of setting double screw extruder in step (3)
Head temperature is 170~180 DEG C.
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| CN105949424A (en) * | 2016-06-08 | 2016-09-21 | 苏州市雄林新材料科技有限公司 | TPU film for food packing and preparation method thereof |
| 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 |
| 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 |
| 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 |
| 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 |
| CN112542100A (en) * | 2020-12-14 | 2021-03-23 | 安徽阿瑞斯科技有限公司 | Arc-shaped LED display screen and preparation method thereof |
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