CN110498899A - Hydrophobic solvent resistant corrosion TPU material and preparation method thereof - Google Patents
Hydrophobic solvent resistant corrosion TPU material and preparation method thereof Download PDFInfo
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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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G18/40—High-molecular-weight compounds
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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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/61—Polysiloxanes
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
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- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
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Abstract
The present invention relates to a kind of hydrophobic solvent resistant corrosion TPU materials and preparation method thereof, belong to thermoplastic polyurethane technical field.Hydrophobic solvent resistant of the present invention corrodes TPU material, by the raw material of following mass percentage, extra catalyst is made simultaneously: polyester polyol 43.5~71.5%, diisocyanate 21~40%, chain extender 5~10%, dihydroxy silicone oil 2~6%, lubricant 0.1~0.5%, catalyst 0.02~0.06%；The chain extender is the mixture of chain extender A and chain extender B, and chain extender A is small molecule alcohol；Chain extender B is fluoro-containing group chain extender, and the mixing mass ratio of the two is 2-8:1.Hydrophobic solvent resistant of the present invention corrodes TPU material, and there is good hydrophobic performance to have both good solvent resistant corrosive nature simultaneously；Invention also provides simple and easy preparation methods.
Description
Technical field
The present invention relates to a kind of hydrophobic solvent resistant corrosion TPU materials and preparation method thereof, belong to thermoplastic polyurethane technology
Field.
Background technique
Thermoplastic polyurethane elastomer (TPU) is a kind of with high-modulus, high intensity, high elongation rate, high resiliency and Gao Nai
The polyurethane high molecule material of the desirable physicals mechanical properties such as mill.Excellent properties of the TPU due to having both rubber and plastics simultaneously, and
And easy to process, cheap, waste material reproducible utilization, it is widely used in sheet material, footwear material, automobile, cable, medical treatment, film
Etc. multiple fields.However TPU material itself does not have hydrophobic performance, and solvent can dissolve, and greatly limit it in some spies
The extensive use in different field.
Most of hydrophobically modified of TPU material method inorganic nano material modified using addition at present.Such as patent
CN108976370A " a kind of hydrophobic fire-retardant method for preparing polyurethane elastic body ", passes through surfactant cetyl front three
Base ammonium bromide is modified carbon nanotube, white carbon black, nanometer calcium carbonate, is added in polyurethane system and improves elastic polyurethane
The hydrophobic performance of body.However this method is due to being added that inorganic additive affects the transparency of material and subsequent there are auxiliary agents
The risk of precipitation limits the extensive use of material.
CN2014101011484 discloses a kind of preparation side of organic fluorinated silicone modified polyaminoester emulsion containing short fluorocarbon chain
Method, isophorone diisocyanate add as hard section, polytetrahydrofuran ether dihydric alcohol, hydroxy silicon oil mixture as soft segment
Heat arrives 70-110 DEG C of reaction 1-8h.Then dihydromethyl propionic acid and Fluorinated dihydric alcohol is added as chain extender, carries out a chain extension
React 1-6h.It is cooled to 25-60 DEG C, neutralizer is added, 0.5-1.5h is stirred, is transferred in high speed dispersion instrument, deionization is added
Water and secondary chain extension agent, high speed dispersion 0.5-3h, gained emulsion particle diameter are uniform and stable.Modified polyurethane emulsion film obtained was both
With better heatproof, water-fast, solvent resistant and corrosion resistance, and there is good water repellent, oil repellency.Although having used hydroxyl
Silicone oil and Fluorinated dihydric alcohol class chain extender, but its preparation process is excessively cumbersome, and differential responses phase temperature difference is larger,
It is easy to produce side reaction, is unfavorable for industrialized production.
Summary of the invention
The technical problem to be solved by the present invention is to overcome deficiency in the prior art, provide a kind of hydrophobic solvent resistant corrosion
TPU material has both good solvent resistant corrosive nature with good hydrophobic performance simultaneously；Invention also provides simple
Easy preparation method.
Hydrophobic solvent resistant of the present invention corrodes TPU material, by the raw material of following mass percentage, while additional urging
Agent is made:
The chain extender is the mixture of chain extender A and chain extender B, and chain extender A is small molecule alcohol；Chain extender B be containing
Fluorin radical chain extender, the mixing mass ratio of the two are 2-8:1.
The polyester polyol is polyester-diol, is polyethylene glycol adipate glycol, polyadipate ethylene glycol -1,2-
Propylene glycol ester glycol, polyadipate ethylene glycol -1,4- butyl glycol ester diol, polyadipate -1,4- butyl glycol ester diol gather oneself
One of diacid -1,6- hexylene glycol esterdiol is a variety of, and average molecular weight is 1000~3500.
The diisocyanate is 4,4'- methyl diphenylene diisocyanate (MDI), 4,4'- dicyclohexyl methyl hydride two is different
Cyanate (H12MDI), phenylene -1,4- diisocyanate (PPDI), toluene di-isocyanate(TDI) (TDI) or 1,5- naphthalene diisocyanate
Ester (NDI), preferably 4,4'- methyl diphenylene diisocyanate (MDI).
The chain extender A is 1,3- propylene glycol, 2- methyl-1,3-propanediol, 1,4- butanediol, 1,3 butylene glycol or 1,6-
One of hexylene glycol is a variety of, preferably 1,4-butanediol.
The chain extender B be the fluoro- 1,2- propylene glycol of 3-, the fluoro- 1,3- propylene glycol of 2,2- bis-, tetrafluoro butanediol or octafluoro -1,
One of 6- hexylene glycol is a variety of, preferably tetrafluoro butanediol.
The dihydroxy silicone oil is dialkyl polydimethylsiloxane (DHPDMS), average molecular weight 1000-3000.
The lubricant is glycerin monostearate, stearic amide, ethylene bis stearic acid amide, pentaerythrite stearic acid
One of ester, E wax or oleamide are a variety of.
The catalyst is organo-bismuth class or organic tin catalyst, preferably organotin catalysts stannous octoate (T-9).
The preparation method of the hydrophobic solvent resistant corrosion TPU material, comprising the following steps:
(1) polyester polyol, dihydroxy silicone oil, lubricant are added to and are reacted with the A of mechanical stirring and temperature control system
It is uniformly mixed in kettle, A temperature of reaction kettle is 95~110 DEG C；Diisocyanate is added in B reaction kettle, B temperature of reaction kettle is
65~75 DEG C；Chain extender is added in C reaction kettle, C temperature of reaction kettle is 60~70 DEG C.
(2) uniform to each reaction kettle material stirring, temperature is stablized, by having the perfusion system of accurate measurement, by A, B and
Raw material in C reaction kettle is added in the rotary blender that revolving speed is 2000~3000r/min, injects twin-screw after mixing
Extruder, while catalyst is injected into double screw extruder spout, the catalyst of accurate measurement injects double through micro-injection pump
Screw extruder spout, mixture homogeneous reaction, plasticizing in twin screw extruder barrel body, is cut into partial size through underwater pelletizer
Uniform elliptical particles.Wherein double screw extruder temperature be 150~200 DEG C, double screw extruder revolving speed be 180~
240r/min。
Siliceous, fluoro-containing group is introduced into thermoplastic polyurethane elastomer by the present invention by in-situ polymerization, is had
The polyurethane elastomer of essential hydrophobic performance.Wherein, the fluorine atom electronegativity in TPU material molecule chain is bigger, can reduce material
The surface free energy of material；At the same time, by organo-silicon compound and polyurethane reaction, hydrophobic group can be introduced in polyurethane molecular
Group, reduces the film tension of system；Make material that there is preferable hydrophobic performance by the synergistic effect of the two.If
The one kind being added thereto can not reach corresponding effect.
Compared with prior art, the invention has the following advantages:
(1) contact angle of hydrophobic solvent resistant corrosion TPU material prepared by the present invention is 95-120 °, and hydrophobic performance is good, can be
The fields such as raincoat, waterproofing membrane, medical, water polo toy, automobile decoration are widely applied；
(2) present invention introduces fluoro-containing group greatly enhance the polarity of TPU material molecule chain, to improve material
Solvent resistance solves and is swollen that obvious, rate of ageing is fast, elasticity sharply drops especially in ketone, esters solvent in polar solvent
Low problem；
(3) preparation method described in, it is simple to operation using one-step synthesis method, it is scientific and reasonable.
Specific embodiment
Below with reference to embodiment, the present invention is further illustrated, but it is not intended to limit implementation of the invention.
Embodiment 1
The hydrophobic solvent resistant corrodes TPU material, is made of the raw material of following mass percent:
Polyethylene glycol adipate glycol (M=3300): 58.56%；
4,4'- methyl diphenylene diisocyanate (MDI-100): 29.98%；
1,4- butanediol (BDO): 8.05%；
The fluoro- 1,2- propylene glycol of 3-: 1.01%；
Dialkyl polydimethylsiloxane: 2%；
Stearic amide: 0.3%；
Glycerin monostearate: 0.1%；
Wherein, the dosage of octoate catalyst stannous (T-9) is the 0.05% of total mass of raw material used above.
The preparation method comprises the following steps: by polyethylene glycol adipate glycol (M=3300), the 200g dihydroxy polydimethyl of 5856g
Siloxanes, the stearic amide of 30g, 10g glycerin monostearate be added to the A of mechanical stirring and temperature control system react
In kettle, setting temperature is 110 DEG C, and is stirred；The MDI-100 of 2998g is placed in B reaction kettle, setting temperature is 75
℃；The fluoro- 1,2-PD of the 3- of BDO, 101g of 805g is placed in C reaction kettle, setting temperature is 65 DEG C.To each reaction kettle
Material stirring is uniform, temperature is stable, and by having the perfusion system of accurate measurement, the raw material in A, B and C reaction kettle is pressed component
It is added in the rotary blender that revolving speed is 2500r/min, double screw extruder spout is injected after mixing, by the octanoic acid of 5g
Stannous (T9) injects double screw extruder spout through micro-injection pump accurate measurement, and mixture is in twin screw extruder barrel body
Homogeneous reaction, plasticizing, the elliptical particles of uniform particle sizes are cut into through underwater pelletizer, and double screw extruder temperature is 150~200
DEG C, double screw extruder revolving speed is 200r/min.
Embodiment 2
The hydrophobic solvent resistant corrodes TPU material, is made of the raw material of following mass percent:
Polyadipate ethylene glycol -1,2- propylene glycol ester glycol (M=3000): 61.82%；
4,4'- methyl diphenylene diisocyanate (MDI-100): 26.95%；
1,4- butanediol (BDO): 6.71%；
Tetrafluoro butanediol: 1.12%；
Dialkyl polydimethylsiloxane: 3%；
Oleamide: 0.2%；
E wax: 0.2%；
Wherein, the dosage of octoate catalyst stannous (T-9) is the 0.03% of total mass of raw material used above.
The preparation method comprises the following steps: by polyadipate ethylene glycol -1,2- propylene glycol ester glycol (M=3000), the 300g dihydroxy of 6182g
The E wax of base dimethyl silicone polymer, the oleamide of 20g and 20g is added to react with the A of mechanical stirring and temperature control system
In kettle, setting temperature is 100 DEG C, and is stirred；The MDI-100 of 2695g is placed in B reaction kettle, setting temperature is 70
℃；The tetrafluoro butanediol of BDO, 112g of 671g are placed in C reaction kettle, setting temperature is 60 DEG C.To each reaction kettle material
It stirs evenly, temperature stabilization, by having the perfusion system of accurate measurement, the raw material in A, B and C reaction kettle is added by component
Revolving speed is double screw extruder spout to be injected after mixing, by the stannous octoate of 3g in the rotary blender of 2800r/min
Double screw extruder spout is injected through micro-injection pump accurate measurement, mixture is uniformly anti-in twin screw extruder barrel body
It answers, be plasticized, the elliptical particles of uniform particle sizes are cut into through underwater pelletizer, double screw extruder temperature is 150~200 DEG C, double
Screw extruder revolving speed is 180r/min.
Embodiment 3
The hydrophobic solvent resistant corrodes TPU material, is made of the raw material of following mass percent:
Polyadipate -1,4- butyl glycol ester diol (M=2000): 66.33%；
4,4'- methyl diphenylene diisocyanate (MDI-100): 22.42%；
1,4- butanediol (BDO): 4.8%；
The fluoro- 1,3- propylene glycol of 2,2- bis-: 1.2%；
Dialkyl polydimethylsiloxane: 5%；
Ethylene bis stearic acid amide: 0.15%；
Pentaerythritol stearate: 0.1%；
Wherein, the dosage of octoate catalyst stannous (T-9) is the 0.04% of total mass of raw material used above.
Method is put in preparation are as follows: by the polyadipate -1,4- butyl glycol ester diol (M=2000) of 6633g, 500g dihydroxy poly- two
The pentaerythritol stearate of methylsiloxane, the ethylene bis stearic acid amide of 15g and 10g be added to mechanical stirring and
In the A reaction kettle of temperature control system, setting temperature is 95 DEG C, and is stirred；The MDI-100 of 2242g is placed in B reaction kettle
In, setting temperature is 65 DEG C；The fluoro- 1,3-PD of 2,2- bis- of BDO, 120g of 480g are placed in C reaction kettle, setting temperature
Degree is 70 DEG C., temperature uniform to each reaction kettle material stirring is stablized, by having the perfusion system of accurate measurement, by A, B and C
Raw material in reaction kettle is added in the rotary blender that revolving speed is 2200r/min by component, is injected twin-screw after mixing and is squeezed
The stannous octoate of 4g is injected double screw extruder spout through micro-injection pump accurate measurement by machine spout out, and mixture exists
Homogeneous reaction, plasticizing in twin screw extruder barrel body, the elliptical particles of uniform particle sizes are cut into through underwater pelletizer, and twin-screw squeezes
Out-of-machine temperature is 150~200 DEG C, and double screw extruder revolving speed is 180r/min.
Embodiment 4
The hydrophobic solvent resistant corrodes TPU material, is made of the raw material of following mass percent:
Polyadipate ethylene glycol -1,4- butyl glycol ester diol (M=1000): 45.89%；
4,4'- methyl diphenylene diisocyanate (MDI-100): 38.06%；
1,4- butanediol (BDO): 6.47%；
Tetrafluoro butanediol: 3.23%；
Dialkyl polydimethylsiloxane: 6%；
Oleamide: 0.2%；
Pentaerythritol stearate: 0.15%；
Wherein, the dosage of catalyst bismuth neodecanoate (C-83) is the 0.06% of total mass of raw material used above.
The preparation method comprises the following steps: by the polyadipate ethylene glycol -1,4- butyl glycol ester diol (M=1000) of 4589g, 600g dihydroxy
The pentaerythritol stearate of base dimethyl silicone polymer, the oleamide of 20g and 15g is added to mechanical stirring and temperature
In the A reaction kettle of control system, setting temperature is 110 DEG C, and is stirred；The MDI-100 of 38.06g is placed in B reaction kettle
In, setting temperature is 70 DEG C；The tetrafluoro butanediol of BDO, 323g of 647g are placed in C reaction kettle, setting temperature is 65 DEG C.
, temperature uniform to each reaction kettle material stirring is stablized, will be in A, B and C reaction kettle by having the perfusion system of accurate measurement
Raw material is added in the rotary blender that revolving speed is 3000r/min by component, injects double screw extruder spout after mixing,
The bismuth neodecanoate (C83) of 6g is injected into double screw extruder spout through micro-injection pump accurate measurement, mixture is in twin-screw
Homogeneous reaction, plasticizing, the elliptical particles of uniform particle sizes, double screw extruder temperature are cut into through underwater pelletizer in extruder barrel body
Degree is 150~200 DEG C, and double screw extruder revolving speed is 240r/min.
Comparative example 1
The TPU material of dihydroxy silicone oil, fluoro-containing group chain extender will be not added with as a comparison case, by following mass percent
Raw material be made:
Polyadipate ethylene glycol -1,2- propylene glycol ester glycol (M=3000): 63.74%；
4,4'- methyl diphenylene diisocyanate (MDI-100): 27.79%；
1,4- butanediol (BDO): 8.07%；
Oleamide: 0.2%；
E wax: 0.2%；
Wherein, the dosage of octoate catalyst stannous (T-9) is the 0.03% of total mass of raw material used above.
The preparation method comprises the following steps: by the polyadipate ethylene glycol -1,2- propylene glycol ester glycol (M=3000) of 6374g, the oil of 20g
The E wax of sour amide and 20g are added in the A reaction kettle with mechanical stirring and temperature control system, and setting temperature is 100 DEG C, and
It is stirred；The MDI-100 of 2779g is placed in B reaction kettle, setting temperature is 70 DEG C；It is anti-that the BDO of 807g is placed in C
It answers in kettle, setting temperature is 60 DEG C., temperature uniform to each reaction kettle material stirring is stablized, by the perfusion for having accurate measurement
System the raw material in A, B and C reaction kettle is added in the rotary blender that revolving speed is 2800r/min by component, after mixing
Double screw extruder spout is injected, the stannous octoate of 3g is injected into double screw extruder feeding through micro-injection pump accurate measurement
Mouthful, mixture homogeneous reaction, plasticizing in twin screw extruder barrel body are cut into the oval grain of uniform particle sizes through underwater pelletizer
Son, double screw extruder temperature are 150~200 DEG C, and double screw extruder revolving speed is 200r/min.
Comparative example 2
By be not added with dihydroxy silicone oil but add fluoro-containing group chain extender TPU material as a comparison case, by following quality
The raw material of percentage is made:
Polyadipate ethylene glycol -1,2- propylene glycol ester glycol (M=3000): 63.74%；
4,4'- methyl diphenylene diisocyanate (MDI-100): 27.79%；
1,4- butanediol (BDO): 6.92%；
Tetrafluoro butanediol: 1.15%
Oleamide: 0.2%；
E wax: 0.2%；
Wherein, the dosage of octoate catalyst stannous (T-9) is the 0.03% of total mass of raw material used above.
The preparation method comprises the following steps: by the polyadipate ethylene glycol -1,2- propylene glycol ester glycol (M=3000) of 6374g, the oil of 20g
The E wax of sour amide and 20g are added in the A reaction kettle with mechanical stirring and temperature control system, and setting temperature is 100 DEG C, and
It is stirred；The MDI-100 of 2779g is placed in B reaction kettle, setting temperature is 70 DEG C；By the four of BDO, 115g of 692g
Fluorine butanediol is placed in C reaction kettle, and setting temperature is 60 DEG C., temperature uniform to each reaction kettle material stirring is stablized, and band is passed through
There is the perfusion system of accurate measurement, the rotation that revolving speed is 2800r/min is added by component in the raw material in A, B and C reaction kettle and is mixed
In conjunction machine, double screw extruder spout is injected after mixing, the stannous octoate of 3g is infused through micro-injection pump accurate measurement
Enter double screw extruder spout, mixture homogeneous reaction, plasticizing in twin screw extruder barrel body are cut into through underwater pelletizer
The elliptical particles of uniform particle sizes, double screw extruder temperature are 150~200 DEG C, and double screw extruder revolving speed is 200r/min.
Comparative example 3
Dihydroxy silicone oil will be added, be not added with the TPU material of fluoro-containing group chain extender as a comparison case, by following quality hundred
The raw material of ratio is divided to be made:
Polyadipate ethylene glycol -1,2- propylene glycol ester glycol (M=3000): 61.82%；
4,4'- methyl diphenylene diisocyanate (MDI-100): 26.95%；
1,4- butanediol (BDO): 7.83%；
Dialkyl polydimethylsiloxane: 3%；
Oleamide: 0.2%；
E wax: 0.2%；
Wherein, the dosage of octoate catalyst stannous (T-9) is the 0.03% of total mass of raw material used above.
The preparation method comprises the following steps: by polyadipate ethylene glycol -1,2- propylene glycol ester glycol (M=3000), the 300g dihydroxy of 6182g
The E wax of base dimethyl silicone polymer, the oleamide of 20g and 20g is added to react with the A of mechanical stirring and temperature control system
In kettle, setting temperature is 100 DEG C, and is stirred；The MDI-100 of 2695g is placed in B reaction kettle, setting temperature is 70
℃；The BDO of 783g is placed in C reaction kettle, setting temperature is 60 DEG C., temperature uniform to each reaction kettle material stirring is stablized,
By having the perfusion system of accurate measurement, it is 2800r/min's that revolving speed, which is added, by component in the raw material in A, B and C reaction kettle
In rotary blender, double screw extruder spout is injected after mixing, the stannous octoate of 3g is accurate through micro-injection pump
Metering injection double screw extruder spout, mixture homogeneous reaction, plasticizing in twin screw extruder barrel body, through underwater cutpellet
Machine-cut is 150~200 DEG C at the uniform elliptical particles of partial size, double screw extruder temperature, and double screw extruder revolving speed is
180r/min。
The detection of TPU material property:
TPU material prepared by embodiment 1-4 and comparative example 1-3 is tested for the property, i.e. thermoplastic polyurethane elastic
Body shore hardness test execution GB/T531-2009 standard；With optics contact angle measurement test distilled water in the above-mentioned surface of solids
Water contact angle；Solvent resistance: impregnating in a solvent at room temperature, and measurement quality increases after impregnating 24 hours.Testing result is shown in Table
1。
Table 1
It can be seen that by above-mentioned testing result, functional Si element and F element are introduced into thermoplastic polyurethane by the present invention
In elastomer, synthesize polyurethane elastomer in itself with hydrophobic performance.The hydrophobic solvent resistant of preparation corrodes TPU material
Contact angle is up to 120 °, has preferable hydrophobic performance good；Have in ketone, esters solvent isopolarity solvent preferable
Solvent corrosion corrosion solves and is swollen that obvious, rate of ageing is fast, elasticity is anxious especially in ketone, esters solvent in polar solvent
Fall sharply low problem, can be widely applied to the fields such as mobile phone protective cover, raincoat, waterproofing membrane, medical, water polo toy, automobile decoration.
Claims (10)
1. a kind of hydrophobic solvent resistant corrodes TPU material, it is characterised in that: by the raw material of following mass percentage, and meanwhile it is additional
Catalyst is made:
The chain extender is the mixture of chain extender A and chain extender B, and chain extender A is small molecule alcohol；Chain extender B is containing fluorine-based
Group's chain extender, the mixing mass ratio of the two are 2-8:1.
2. hydrophobic solvent resistant according to claim 1 corrodes TPU material, it is characterised in that: polyester polyol is polyester-type
Glycol, be polyethylene glycol adipate glycol, polyadipate ethylene glycol -1,2-PD esterdiol, polyadipate ethylene glycol -1,
One of 4- butyl glycol ester diol, polyadipate -1,4- butyl glycol ester diol or polyadipate -1,6-HD esterdiol or
A variety of, average molecular weight is 1000~3500.
3. hydrophobic solvent resistant according to claim 1 corrodes TPU material, it is characterised in that: diisocyanate 4,4'- bis-
Methylenebis phenyl isocyanate, 4,4'- dicyclohexyl methyl hydride diisocyanate, phenylene -1,4- diisocyanate, toluene two are different
Cyanate or 1,5- naphthalene diisocyanate.
4. hydrophobic solvent resistant according to claim 1 corrodes TPU material, it is characterised in that: chain extender A is 1,3- the third two
One of alcohol, 2- methyl-1,3-propanediol, 1,4- butanediol, 1,3 butylene glycol or 1,6-HD are a variety of.
5. hydrophobic solvent resistant according to claim 1 corrodes TPU material, it is characterised in that: chain extender B is 3- fluoro- 1,2-
One of propylene glycol, the fluoro- 1,3- propylene glycol of 2,2- bis-, tetrafluoro butanediol or octafluoro -1,6-HD are a variety of.
6. hydrophobic solvent resistant according to claim 1 corrodes TPU material, it is characterised in that: dihydroxy silicone oil is dihydroxy
Dimethyl silicone polymer, average molecular weight 1000-3000.
7. hydrophobic solvent resistant according to claim 1 corrodes TPU material, it is characterised in that: lubricant is that monostearate is sweet
One of grease, stearic amide, ethylene bis stearic acid amide, pentaerythritol stearate, E wax or oleamide are more
Kind；Catalyst is organo-bismuth class or organic tin catalyst.
8. a kind of preparation method of hydrophobic solvent resistant corrosion TPU material as claimed in claim 1 to 7, it is characterised in that including
Following steps:
(1) polyester polyol, dihydroxy silicone oil, lubricant are added in A reaction kettle and are mixed, diisocyanate is added to B
In reaction kettle, chain extender is added in C reaction kettle；
(2) raw material in A, B and C reaction kettle is added to rotary blender, double screw extruder is injected after mixing, while will urge
Agent injection double screw extruder is reacted, is plasticized, and is corroded through underwater pelletizer pelletizing to get the hydrophobic solvent resistant
TPU material.
9. the preparation method of hydrophobic solvent resistant corrosion TPU material according to claim 8, it is characterised in that: in step (1)
The A temperature of reaction kettle is 95~110 DEG C, and B temperature of reaction kettle is 65~75 DEG C, and C temperature of reaction kettle is 60~70 DEG C.
10. the preparation method of hydrophobic solvent resistant corrosion TPU material according to claim 8, it is characterised in that: step (2)
Described in rotary blender revolving speed be 2000~3000r/min, the temperature of double screw extruder is 150~200 DEG C, and revolving speed is
180~240r/min.
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