CN107286310A - A kind of response type antistatic urethane elastomer of the nanometer class fluid containing epoxy type and preparation method thereof - Google Patents

A kind of response type antistatic urethane elastomer of the nanometer class fluid containing epoxy type and preparation method thereof Download PDF

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CN107286310A
CN107286310A CN201710315451.8A CN201710315451A CN107286310A CN 107286310 A CN107286310 A CN 107286310A CN 201710315451 A CN201710315451 A CN 201710315451A CN 107286310 A CN107286310 A CN 107286310A
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preparation
nano
class fluid
urethane elastomer
response type
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CN107286310B (en
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邱志明
何厚刚
严玉蓉
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South China University of Technology SCUT
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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
    • C08G18/48—Polyethers
    • 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
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • 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
    • C08G18/65—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
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • 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
    • C08G18/65—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
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/6696—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/36 or hydroxylated esters of higher fatty acids of C08G18/38
    • 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
    • C08G18/70—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
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group

Abstract

The present invention relates to a kind of response type antistatic urethane elastomer of the nanometer class fluid containing epoxy type and preparation method thereof, first use silane coupler γ glycidyl ether oxygen propyl trimethoxy Si modification nano-particles, activate it, then the salified product for obtaining carrying abundant hydroxyl side chains of nano-particle activated, the product continues to obtain epoxy nano class fluid with organic salt progress ion exchange.Then 8 10g oligomer polyols and 4 5g isocyanates are weighed, the regular hour is reacted at specific temperature and specific stir speed (S.S.), obtain base polyurethane prepolymer for use as, then epoxy nano class fluid is used as cross-linking reaction agent by 2wt.% 8wt.%, chain extender is added in performed polymer, carries out cross-linking reaction, finally reacted thick liquid is coated in glass board mould, solidification is dried under vacuum, final response type antistatic urethane elastomer is obtained.

Description

It is a kind of containing epoxy type nanometer class fluid response type antistatic urethane elastomer and its Preparation method
Technical field
The invention belongs to macromolecule material preparation area, and in particular to a kind of response type of the nanometer class fluid containing epoxy type resists Electrostatic polyurethane elastomer and preparation method thereof.
Background technology
Being developed so far for polyurethane is existing 70 years, and a kind of tool has been widely used, the outstanding macromolecule of combination property Material.It can synthesize that hardness range is very wide according to the different ratio of performed polymer polyethers and isocyanates, the high polyurethane of elasticity.Together When, polyurethane has high intensity, high abrasion, oil resistant and the ability radiated so that it is used in automobile, building, pavement material, ore deposit In terms of mountain, exploitation, electronics and space flight.The major class that polyurethane elastomer belongs in polyurethane material, its performance range is very wide, It is that, to the family macromolecule material between plastics, can be applicable to solid tyre, adhesive tape, rubber roll lining, oil sealing, sealing between rubber In terms of circle, die-cushion, electric elements embedding, adhesive and coating.
But, the specific insulation of polyurethane is typically in the range of 1013-1015Between Ω, belong to dielectric insulation material.Insulation Body material easily accumulates electrostatic, therefore causes the equipment work of correlation not normal, such as reduces or damage the accuracy of precision instrument, To electronic device using interfering.Polyurethane electrostatic resistance material due to its superior electric conductivity and exclude electrostatic ability, And be used in different fields, such as aviation fuel storage tank, electronic product or household electronic products and chemical work Journey.According to the occupation mode of antistatic additive, polyurethane electrostatic resistance material can be divided into two classes, a class is the poly- ammonia to machine-shaping Ester material is surface-treated, and such as impregnates, applies or be grafted appropriate functional group.Another kind of is to include compound addition type and reaction The inside addition type anti-static material of type.Compound addition type antistatic additive includes graphite, carbon black, metal oxide and metal dust Or functional polymer etc..Response type anti-static material is that the existing antistatic group of addition has hydroxyl, amino or isocyanide again The antistatic additive of perester radical isoreactivity group, can be chemically crosslinked with polyurethane prepolymer, and permanence antistatic material is made.But It is that the polyurethane electrostatic resistance performance duration being surface-treated is shorter, antistatic coating is easy to be washed away, it is simply a kind of temporary transient Type antistatic additive.Compound antistatic polyurethane static behaviour is good, and cost is low, but such antistatic additive addition is larger, but adds Dosage is big, has considerable influence to the mechanical performance of material.Response type anti-static material advantage is obvious, because of antistatic additive and macromolecule Matrix is chemically crosslinked, therefore with permanent antistatic property, it is also insensitive to humidity.But about the report of such antistatic additive Seldom, so this kind of antistatic additive is urgently researched and developed, following focus will can also be turned into.
Nanometer class fluid has an ambient temperature mobility because of it, zero vapour pressure, high heat endurance and electrical conductivity can by with In different field, such as antistatic additive, lubricant, electrolyte etc..
The content of the invention
In place of shortcoming and defect in order to solve above prior art, primary and foremost purpose of the invention is to provide a kind of containing epoxy The preparation method (abbreviation NSiF-Hs) of the response type antistatic urethane elastomer of type nanometer class fluid；
Second purpose of the invention is to provide a kind of response type antistatic polyurethane elasticity of nanometer class fluid containing epoxy type Body, this method can effectively carry the comprehensive mechanical property and antistatic property of polyurethane elastomer.
The object of the invention is achieved through the following technical solutions：
A kind of response type antistatic urethane elastomer preparation method of the nanometer class fluid containing epoxy type, including following preparation Step：
Silane coupler γ-glycidyl ether oxygen propyl trimethoxy Si modification nano-particle is first used, activates it, then The nano-particle of activation is salified to obtain the product with abundant hydroxyl side chains, and the product continues to carry out ion exchange with organic salt Obtain epoxy nano class fluid.Then 8-10g oligomer polyols and 4-5g isocyanates are weighed, in specific temperature and The regular hour is reacted under specific stir speed (S.S.), base polyurethane prepolymer for use as is obtained.Then epoxy nano class fluid presses 2wt.%- 8wt.% is added in performed polymer as cross-linking reaction agent, chain extender, carries out cross-linking reaction.Finally by reacted thick liquid It is coated in glass board mould, solidification is dried under vacuum, obtains final response type antistatic urethane elastomer.
Comprise the following steps that：
The preparation of step one hydroxyl epoxy nano class fluid
The ultrasonic disperse nano-particle aqueous solution first, then in molar ratio 1:1, with γ-glycidyl ether oxygen propyl trimethoxy The coupling agent modified nano-particle of base silane activates it, and activation condition is reacted 24 hours at 70 DEG C in ethanol water；
Reaction is that silane coupler hydrolysis obtains activity hydroxy first, is then further contracted with nano-particle hydroxyls dehydrate Close；
Secondly, the nano-particle of activation and tri-n-butylamine, concentrated hydrochloric acid mol ratio 1:1:1 reaction, it is further salified, obtain Organic chain with abundant activity hydroxy；
Finally, above-mentioned salified product and poly- (ethylene glycol) 4- nonyl phenyls -3- sulfopropyls ether sylvite ion of organic salt Exchange reaction obtains epoxy nano class fluid, and after having reacted, rotary evaporation falls solvent, and obtained thick liquid is added tetrahydrochysene furan Mutter, remove the potassium chloride precipitation insoluble in tetrahydrofuran, obtained product is finally permeated into 7d in 3A molecular sieves, fully to remove Small molecular weight impurity is removed, clean product is finally given；
The preparation of step 2 reaction type polyurethane elastomer performed polymer
8-10g oligomer polyols and 4-5g isocyanates are weighed, 80-100ml DMFs are added In 250mL three-necked flasks, at a certain temperature, nitrogen protection, with special speed mechanical agitation, when reacting specific under condensing reflux Between, naturally cool to room temperature after having reacted；
The preparation process of step 3 reaction type polyurethane elastomer
0.32-1.36g prepared by 0.4-0.6g chain extenders and step one hydroxyl epoxy nano class fluid is weighed, is used 20ml DMF dissolving, is added in step two prepolymer after cooling, continues stirring at low speed 3h, finally To thick liquid be coated in glass board mould, react 12h at 60 DEG C in vacuum drying chamber, and 80 DEG C of vacuum continues to solidify 12h, the mass content for finally obtaining epoxy nano class fluid in transparent polyurethane elastomer film, film is respectively 2wt%, 4wt%, 6wt%, 8wt%.
Preferably, the nano-particle described in step yi'zho'g is the inorganic nuclear structure of nanometer class fluid, quality accounting one As selection 5-20% between, nano-particle include SiO2、TiO2、ZnO、Fe3O4, graphene, one in CNT and quantum dot More than kind.
Preferably, organic salt includes organic sulfate or sulfonate in the step one.
Preferably, the oligomer polyol includes PEPA, PPG, poly- 6-caprolactone polyalcohol, its Middle PEPA be specially polyethylene glycol adipate glycol, gather many polyethylene glycol adipate glycol propylene glycol ester glycol, Gather many polybutylene glyool adipates, gather in many polydiethylene glycol adipate glycol and polyadipate castor oil ester glycol More than one, PPG includes polyoxypropyleneglycol, PPOX triol, PPOX tetrol, polyoxygenated third More than one combinations of alkene pentol and polytetrahydrofuran diol.
Preferably, described isocyanates includes diphenylmethane diisocyanate vinegar, toluene di-isocyanate(TDI), hexa-methylene More than one combinations of diisocyanate and 1,5- naphthalene diisocyanates.
Preferably, the chain extender include glycols, Diamines, monoethanolamine, such as ethylene glycol, propane diols, butanediol, 3, More than one in 3 '-two chloro- 4,4- diphenylmethanediamiands and allyl ether series.
Preferably, described specified temp is 70-95 DEG C.
Preferably, described special time is 2-3.5h.
Preferably, described stir speed (S.S.) is 200-300rpm.
Preferably, the glass board mould is 10cm × 10cm × 0.3cm square plates.
A kind of response type antistatic urethane elastomer of the nanometer class fluid containing epoxy type, is prepared into by the above method Arrive, molecular formula：
The epoxy nano class fluid obtained has inorganic core and has the nanostructured of casing, there is abundant activity hydroxy, Belong to third generation ionic liquid, with ambient temperature mobility.Room-temperature ion conductance reaches 10-5S/cm, as shown in Figure 1.Obtained The tensile strength of polyurethane electrostatic resistance material is up to 30.1MPa (the pure PU of non-plus nano class fluid is 16.7MPa), and hardness is protected Hold in 80 shore A, such as Fig. 2, its surface resistivity is 7.35 × 10 to the maximum7Ω/sp, anti-static high efficiency is lasting.
The preparation method and resulting product of the present invention has the following advantages that and beneficial effect：
(1) the synthesis overall process of epoxy type nanometer class fluid uses ethanol and water mixed solvent in the present invention, green Pollution-free, three steps of simultaneous reactions are continuous one, and the almost waste without raw material, synthesis technique is simple, does not pollute；
(2) present invention is used as coupling agent by choosing γ-glycidyl ether oxygen propyl trimethoxy silicane, then with three positive fourths Amine, the quaterisation of hydrochloric acid is successfully made the nanometer class fluid containing abundant hydroxyl, is then used as polyurethane electrostatic resistance agent, this Nanometer class fluid member is not only increased newly, has opened the road of functionalized nano class fluid, also widened the reality of nanometer class fluid Apply on border；
(3) preparation method technique of the invention is simple, does not pollute, while obtained antistatic urethane elastomer is stretched It is slight high than same system, and sheet resistance resist it is also having with similar system and too late.
Brief description of the drawings
Fig. 1 is epoxy nano class fluid ionic conductivity figure at different temperatures；
Fig. 2 is the response type antistatic polyurethane mechanical property figure of different epoxy nano class fluid contents.
Embodiment
With reference to embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited In this.
Embodiment 1
(1) preparation of reaction type polyurethane elastomer performed polymer：Because polyurethane reaction need to strictly control moisture, instead Ying Qian, by the molecular sieve drying one week of the solvent DMF used in reaction, molecular sieve under high temperature furnace in advance 400 DEG C of processing 4h.In order to remove the moisture of polyurethane synthon ethers, then its 120 DEG C of dry 2h before the reaction weighs 10.0g PTMEG and 5.0g diphenylmethane diisocyanate vinegar MDI, add tri- mouthfuls of 100ml DMFs 250mL In flask.At 90 DEG C, nitrogen is protected, 300rpm speed mechanical agitations, and 3h is reacted under condensing reflux.Rear natural cooling is reacted To room temperature..
(2) preparation process of reaction type polyurethane elastomer：On the basis of (1), 0.56g ethylene glycol is weighed, with 20ml's DMF dissolves, and is added in the prepolymer after cooling, continues to stir 3h with 150rpm speed.Finally obtain Thick liquid is coated on glass plate, and 12h is reacted at 60 DEG C, and 80 DEG C are continued to solidify 12h.It finally obtained transparent film
(3) it is to carry out Mechanics Performance Testing on UT-208 universal testing machines in the INSTRUMENT MODEL from U-CAN companies. Rate of extension：30mm/min.10cm × 1cm sample strip is cut in advance.Each percentage tests three samples.Use ACL-800 Sheet resistance instrument tests the surface resistivity of polyurethane elastomer.
Polyurethane elastomer film made from the present embodiment is the film of the pure class of epoxy nano containing 0wt.% fluid, and it stretches strong Spend for 16.3MPa, elongation at break is 525%, and shore hardness is 78.8, as shown in Figure 1.Surface resistivity is 2.25 × 1013 Ω/sq, as shown in table 1.Molecular formula is as follows：
Wherein PEG-SO3 -For poly- (ethylene glycol) 4- nonyl phenyls -3- sulfopropyl ether anions.
Embodiment 2
A kind of preparation method of the response type antistatic urethane elastomer of the nanometer class fluid containing epoxy type, including following step Suddenly：
(1) epoxy nano class fluid preparation：2.000g aqueous silica solutions are weighed first, add 40ml pure water ultrasound point Dissipate 30 minutes.Then it is 0.15 by silica and organic chain mass ratio:0.85 ratio calculates the quality of silane modifier, claims 0.794g γ-glycidyl ether oxygen propyl trimethoxy silicane modifying agent is taken, is dissolved with 50ml ethanol and is added to ultrasonic disperse Aqueous silica solution in, react 24h under the protection of 70 DEG C of nitrogen.Then by silane modifier and tri-n-butylamine, concentrated hydrochloric acid Mol ratio 1：1：1 weighs 0.190g tri-n-butylamines and 0.370g concentrated hydrochloric acids, is added in above-mentioned reacted solvent, at 70 DEG C after Continuous reaction 24h.Obtained organic chain is with abundant activity hydroxy.Finally weigh poly- (ethylene glycol) the 4- nonyl phenyls of 4.233g- 3- sulfopropyl ether sylvite, is added in above-mentioned solution, continues to react 24 hours, and temperature is 70 DEG C.After having reacted, rotary evaporation Fall solvent, obtained thick liquid is added 70ml tetrahydrofurans, after stirring one hour, filter out potassium chloride precipitation.Finally will Obtained product permeates 7d in 3A molecular sieves, fully to remove small molecular weight impurity, finally give pure epoxy nano class stream Body.This nanometer of class fluid belongs to ionic liquid, and its ionic conductivity varies with temperature relation as shown in figure 1, room temperature is up to 10-5S/ Cm, the ionic conductance of itself and abundant hydrophilic hydroxyl groups both contribute to reduce the surface resistivity of polyurethane.
(2) preparation of reaction type polyurethane elastomer performed polymer：It is identical with embodiment 1 (1).
(3) prepared by the reaction type polyurethane elastomer of the class of epoxy nano containing 2wt.% fluid：On the basis of embodiment 2 (2) 0.56g ethylene glycol and the epoxy nano class fluid 0.32g (2wt.%) obtained by (1) are weighed, with 20ml N, N- dimethyl formyls Amine solvent, is added in the prepolymer after cooling.
(4) it is identical with embodiment 1 (3).
Polyurethane elastomer film made from the present embodiment is the film of the pure class of epoxy nano containing 2wt.% fluid, and it stretches strong Spend for 27.0MPa, elongation at break is 644%, and shore hardness is 79.6, as shown in Figure 1.Surface resistivity is 2.46 × 1012 Ω/sq, as shown in table 1, relative to embodiment 1, sheet resistance reduces an order of magnitude.
Embodiment 3
A kind of preparation method of the response type antistatic urethane elastomer of the nanometer class fluid containing epoxy type：
(1) it is identical with (1) in embodiment 2.
(2) it is identical with (2) in embodiment 2.
(3) identical with (3) in embodiment 2, difference is the epoxy nano class fluid 0.66g (4wt.%) added, uses 20ml DMF dissolving, is added in the prepolymer after cooling.
(4) it is identical with (3) in embodiment 1.
Polyurethane elastomer film made from the present embodiment is the film of the pure class of epoxy nano containing 4wt.% fluid, and it stretches strong Spend for 30.7MPa, reach maximum, and it is better than other similar system performances.Elongation at break is 625%, and shore hardness is 79.1, as shown in Figure 1.Surface resistivity is 4.34 × 1011Ω/sq, as shown in table 1, relative to embodiment 2, sheet resistance drop Low an order of magnitude.
Embodiment 4
A kind of preparation method of the response type antistatic urethane elastomer of the nanometer class fluid containing epoxy type：
(1) it is identical with (1) in embodiment 2.
(2) it is identical with (2) in embodiment 2.
(3) identical with (3) in embodiment 2, difference is the epoxy nano class fluid 1.00g (6wt.%) added, uses 20ml DMF dissolving, is added in the prepolymer after cooling.
(4) it is identical with (3) in embodiment 1.
Polyurethane elastomer film made from the present embodiment is the film of the pure class of epoxy nano containing 6wt.% fluid, and it stretches strong Spend for 15.3MPa, elongation at break is 606%, and shore hardness is 80.4, as shown in Figure 1.Surface resistivity is 1.59 × 109 Ω/sq, as shown in table 1, relative to embodiment 2, sheet resistance reduces two orders of magnitude.
Embodiment 5
A kind of preparation method of the response type antistatic urethane elastomer of the nanometer class fluid containing epoxy type：
(1) it is identical with embodiment 2 (1).
(2) it is identical with embodiment 2 (2).
(3) identical with embodiment 2 (3), difference is the epoxy nano class fluid 1.36g (8wt.%) added, uses 20ml DMF dissolving, be added to cooling after prepolymer in.
(4) it is identical with embodiment 1 (3).
Polyurethane elastomer film made from the present embodiment is the film of the pure class of epoxy nano containing 8wt.% fluid, and it stretches strong Spend for 11.9MPa, elongation at break is 508%, and shore hardness is 74.3, as shown in Figure 1.Surface resistivity is 7.35 × 107 Ω/sq, as shown in table 1, relative to embodiment 2, sheet resistance reduces four orders of magnitude.
Table 1 is the surface resistivity of the response type antistatic polyurethane of different epoxy nano class fluid contents
Sample ID Surface resistivity/(Ω/sq)
PU/0wt% 2.25×1013
PU/2wt%NSiF-Hs 2.46×1012
PU/4wt%NSiF-Hs 4.34×1011
PU/6wt%NSiF-Hs 1.59×109
PU/8wt%NSiF-Hs 7.35×107
Above-described embodiment is preferably embodiment, but embodiments of the present invention are not by above-described embodiment of the invention Limitation, other any Spirit Essences without departing from the present invention and the change made under principle, modification, replacement, combine, simplification, Equivalent substitute mode is should be, is included within protection scope of the present invention.

Claims (10)

1. a kind of preparation method of the response type antistatic urethane elastomer of the nanometer class fluid containing epoxy type, including following preparation Step：
The preparation of step one hydroxyl epoxy nano class fluid
The ultrasonic disperse nano-particle aqueous solution first, by certain mol proportion γ-glycidyl ether oxygen propyl trimethoxy silicane Coupling agent modified nano-particle activates it, and activation condition is reacted 24 hours at 70 DEG C in ethanol water；
Secondly, the nano-particle of activation and tri-n-butylamine, concentrated hydrochloric acid mol ratio 1:1:1 reaction, obtained organic chain is with abundant Activity hydroxy；
Finally, epoxy nano class stream is obtained with poly- (ethylene glycol) 4- nonyl phenyls -3- sulfopropyl ether sylvite ion-exchange reactions Body；
The preparation of step 2 reaction type polyurethane elastomer performed polymer
8-10g oligomer polyols and 4-5g isocyanates are weighed, 80-100ml DMFs 250mL tri- is added In mouth flask, at a certain temperature, nitrogen protection with special speed mechanical agitation, is reacted special time, reacted under condensing reflux Room temperature is naturally cooled to after complete；
The preparation process of step 3 reaction type polyurethane elastomer
0.32-1.36g prepared by 0.4-0.6g chain extenders and step one hydroxyl epoxy nano class fluid is weighed, with 20ml's DMF dissolves, and is added in step two prepolymer after cooling, continues to stir 3h, the viscous fluid finally obtained Body is coated in glass board mould, reacts 12h at 60 DEG C in vacuum drying chamber, and 80 DEG C of vacuum continues to solidify 12h, finally To transparent polyurethane elastomer film.
2. a kind of system of the response type antistatic urethane elastomer of nanometer class fluid containing epoxy type according to claim 1 Preparation Method, it is characterised in that：Nano-particle described in step one is the inorganic nuclear structure of nanometer class fluid, the selection of quality accounting Between 5-20%, nano-particle includes SiO2、TiO2、ZnO、Fe3O4, graphene, in CNT and quantum dot it is a kind of with On.
3. a kind of system of the response type antistatic urethane elastomer of nanometer class fluid containing epoxy type according to claim 1 Preparation Method, it is characterised in that：In step one, the organic salt includes organic sulfate or sulfonate.
4. a kind of system of the response type antistatic urethane elastomer of nanometer class fluid containing epoxy type according to claim 1 Preparation Method, it is characterised in that：Specified temp described in step 2 is 70-95 DEG C, and described special time is 2-3.5h.
5. preparation method according to claim 1, it is characterised in that：Oligomer polyol described in step 2 includes polyester Polyalcohol, PPG, poly- 6-caprolactone polyalcohol, wherein PEPA be specially polyethylene glycol adipate glycol, Gather many polyethylene glycol adipate glycol propylene glycol ester glycol, gather many polybutylene glyool adipates, gather many polyadipates two One or more of glycol ester glycol and polyadipate castor oil ester glycol, PPG include polyoxypropyleneglycol, More than one combinations of PPOX triol, PPOX tetrol, PPOX pentol and polytetrahydrofuran diol.
6. preparation method according to claim 1, it is characterised in that：Isocyanates described in step 2 includes diphenyl The isocyanate of methane two, toluene di-isocyanate(TDI), hexamethylene diisocyanate and 1,5- naphthalene diisocyanates more than one Combination.
7. preparation method according to claim 1, it is characterised in that：In step 3, the chain extender includes glycols, two Amine, monoethanolamine.
8. preparation method according to claim 1, it is characterised in that：Stir speed (S.S.) described in step 3 is 200- 300rpm；
The glass board mould is 10cm × 10cm × 0.3cm square plates.
9. a kind of response type antistatic urethane elastomer of the nanometer class fluid containing epoxy type, it is characterised in that：Will by right The method described in 1~8 any one is asked to prepare, its molecular formula：
10. response type antistatic urethane elastomer according to claim 9, it is characterised in that the polyurethane resists quiet The tensile strength of electric material is up to 30.1MPa, and hardness is maintained at 80 shore A, and its surface resistivity is 7.35 × 10 to the maximum7 Ω/sp。
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CN108948720A (en) * 2018-06-25 2018-12-07 董小琳 A kind of preparation method of TPU ventilated membrane
CN109880050A (en) * 2019-03-11 2019-06-14 浙江圆融科技有限公司 A kind of elastomeric material and preparation method thereof that graphene substance is modified
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CN108329679A (en) * 2018-02-02 2018-07-27 江苏洛基木业有限公司 A kind of preparation method of solvent-free graphene electric-heating thin film
CN108948720A (en) * 2018-06-25 2018-12-07 董小琳 A kind of preparation method of TPU ventilated membrane
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CN111138631B (en) * 2020-01-21 2021-08-31 福州大学 Preparation method of high-strength high-barrier TPU composite material

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