CN105968305B - A kind of waterproof moisture-penetrating urethane material and preparation method thereof - Google Patents
A kind of waterproof moisture-penetrating urethane material and preparation method thereof Download PDFInfo
- Publication number
- CN105968305B CN105968305B CN201610332666.6A CN201610332666A CN105968305B CN 105968305 B CN105968305 B CN 105968305B CN 201610332666 A CN201610332666 A CN 201610332666A CN 105968305 B CN105968305 B CN 105968305B
- Authority
- CN
- China
- Prior art keywords
- silicon dioxide
- nano silicon
- polyurethane
- added
- modified nano
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- 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
-
- 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
- C08G18/42—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
-
- 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
- C08G18/4825—Polyethers containing two hydroxy groups
-
- 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
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- 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
Abstract
The present invention discloses a kind of waterproof moisture-penetrating urethane material and preparation method thereof, is related to a kind of polyalcohol modified SiO 2 hybrid polyurethane material and preparation method thereof with waterproof and moisture-permeable function.Using multiple hydroxyls on polyalcohol modified Nano particles of silicon dioxide surface, react to form the polyurethane material with space net structure with the isocyanates at base polyurethane prepolymer for use as both ends.Suitable polyalcohol modified nano silicon dioxide can play the role of adjusting polyurethane soft segment glass transition temperature to realize intelligent waterproof and moisture-permeable function.Meanwhile suitable polyalcohol modified nano silicon dioxide together forms physical crosslinking point in polyurethane molecular with hard section, can increase polyurethane space net structure intensity to enhance water resistance.
Description
Technical field
The present invention relates to a kind of waterproof moisture-penetrating urethane materials and preparation method thereof, and in particular to one kind having Waterproof Breathable
Polyalcohol modified SiO 2 hybrid polyurethane material of function and preparation method thereof.
Background technology
Textile water proof performance, which refers to the fabric, has the rainwater for preventing external environment and snow-broth from exosmosis to inside
Ability；The water vapour permeability of textile refers to the fabric, and there is the sweat that human body is distributed to penetrate fabric in the form of water vapour, to
The ability of ambient enviroment diffusion.The waterproofing and moisture-penetration performances of textile refer to that external rainwater and snow-broth are impermeable in fabric,
And internal sweat can penetrate rapid transmit of fabric and be evaporated to outside, to make the microclimate between human body and clothes be adjusted
Section, keeps that wearer's is dry and comfortable and warm.
Polyurethane has unique flexibility, wearability, fungus resistance and good texture and is widely used in middle height
Hold the preparation of fabric.By the adjustment and design to polyurethane molecular structure, it can be made to have both waterproof and penetrability the two work(
Can, without losing itself original excellent physicochemical property.It, can be by the poly- ammonia of Waterproof Breathable according to Waterproof Breathable mechanism and coating performance
Ester is divided into microporous type, non-porous hydrophilic leads wet type, microporous leads wet mating type and temperature sensitive four major class such as intelligent with hydrophilic.
There is micropore on microporous type polyurethane, the diameter very little of micropore, only 10~50 μm, between a diameter of 4 ×
10-4μm vapor and diameter be about 100~300 μm water droplet between, vapor can pass through microporous membrane, and water droplet cannot lead to
It crosses, to play the purpose of waterproof and breathable.Under an electron microscope it is observed that apparent microcellular structure, its gas permeability can be with
The respiratory of human skin compares favourably.Its advantage is that water vapour permeability is good.The disadvantage is that micropore can occur after long-term use for coating
Blocking causes water vapour permeability variation or micropore that can constantly expand because of stretching, to make liquid water be easy to permeate；After micropore is formed
Specific surface area increases, and easy dust suction is adsorbed detergent and stained, or makes blockage of the micro orifice, reduces permeability；Microporous barrier and coating add
Work technique is more complex, and solvent is expensive, be easy to cause environmental pollution.
Non-porous hydrophilic leads wet type polyurethane and is continuous nonporous film or coating material, and surface and ontology are uniform cause
Close structure.Water proofing property is since the continuity of material and larger surface tension determine that penetrability is soft by polyurethane hydrophilic
What the relative molecular mass of segment type, ratio and soft segment determined, it is realized by complicated molecule diffusion mechanism.Polyurethane it is micro-
Phase separation structure provides possibility for complicated molecule diffusion, and hydrone is transmitted along intensive strand gap, by high humility
Side adsorption moisture is transmitted to low humidity side by the hydrophilic radical in polyurethane molecular chain.Its advantage is that compact structure can
Play the role of obstructing dust, bacterium；Its penetrability comes from the particularity of polyurethane molecular structure, therefore its manufacturing method can
The processing technology for substantially continuing to use pervious non-breathable polyurethane only needs slightly to improve for different applications.It is lacked
Point is compared with microporous type, and water vapour permeability is poor；Since with certain water-swellable, water proofing property is slightly poor.
Microporous leads wet combination type polyurethane combination microporous type and non-porous hydrophilic leads the respective spy of wet type with hydrophilic
Point contains some hydrophilic radicals, some micro-pores is also formed during polyurethane film-forming in the molecular structure, from
And it realizes hydrophilic radical and cooperates with Waterproof Breathable with micropore.It is compound with the lamination of trepanning fiber, can be used as advanced motion clothes and movement
The fabric of shoes etc..Its advantage is that having both the advantage of two kinds of water proof and moisture permeable materials.The disadvantage is that material price is expensive, preparation process is multiple
It is miscellaneous.
Temperature sensitive intelligent polyurethane water-proof moisture-inhibiting material is as human skin, with its water vapour permeability of the variation of human body temperature
Change therewith, is the important directions of the following water proof and moisture permeable material exploitation.Its Waterproof Breathable mechanism is based on the special of polyurethane
Design feature.There is the soft segment of polyurethane good crystallinity, hard section to be gathered into microcell and play physical crosslinking point, control
The shape of polyurethane is fixed and is restored.When the region temperatures span glass transition temperature (Tg), strand micro Brownian motion adds
Play, the gap between polymer molecule increase, and form the micropore that can penetrate vapor, its gas permeability be made to have the mutation of matter.
Using this performance of polyurethane, Tg is set in room temperature by adjusting molecular structure, then polyurethane film is in low temperature (<Tg)
When, the thermal effect of low moisture-inhibiting is presented；(> at high temperature;When Tg), the cooling effect of high moisture-inhibiting is presented.Since Brownian movement is produced
Its aperture of raw micropore is much smaller than water droplet average diameter, so film still has good waterproof effect.Although temperature sensitive intelligent
How polyurethane water-proof moisture-inhibiting material its response mechanism, coating processing technology and is improved to environment temperature by extensive concern
Response accuracy and the sensitivity for spending variation, need further to further investigate.In addition, the poly- ammonia of current solvent type intelligence Waterproof Breathable
The research of ester is more, but less for the document report of aqueous intelligent waterproof moisture-penetrating urethane.Foreign countries, the especially U.S., day
This grade country has certain history, but in the correlative study delivered, among key technology is still in secrecy.China is to this
The exploitation of class product is started late, and the starting stage is still in.
Invention content
It is poly- that the object of the present invention is to provide a kind of polyalcohol modified nano silicon dioxide hybridizations with waterproof and moisture-permeable function
Urethane material and preparation method thereof.
In order to achieve the above objectives, the technical solution adopted by the present invention includes the following steps：
（1）The synthesis of polyalcohol modified nano silicon dioxide
It is 7~200nm silica and a certain amount of diisocyanate, nitrogen that commercially available grain size is added in dry toluene
By mixture ultrasonic disperse 20min under gas shielded, then 7~10h of insulation reaction between 50 DEG C~70 DEG C.It is cooled to room temperature,
It filters, washing obtains the nano silicon dioxide of diisocyanate modification.Nano-particle obtained and a certain amount of dihydric alcohol are mixed
Close, under nitrogen protection between 50 DEG C~70 DEG C 7~10h of insulation reaction.It is cooled to room temperature, filters, washing obtains product.
Reaction equation is as follows：
（2）The synthesis of polyalcohol modified nano silicon dioxide hybridization polyurethane
The polyester polyol of metering or polyether polyol are fitted into the there-necked flask for carrying thermometer, nitrogen protection device,
Vacuum dehydration 1h under the conditions of 120 DEG C.A certain amount of diisocyanate and butanone are added after cooling, between 50 DEG C~70 DEG C
2~8h of reaction obtains performed polymer.A certain amount of dihydric alcohol, 2,2- dihydromethyl propionic acids are added in performed polymer（DMPA）With it is polynary
Alcohol modified manometer silicon dioxide, at 50 DEG C~90 DEG C（It is preferred that 70 DEG C）Lower reaction 3h.Reaction solution is cooled to 45 DEG C, is added certain
The triethylamine insulated and stirred 1h of amount.It is added in a certain amount of deionized water, mechanical agitation 1h obtains nano silicon dioxide hybridization water
Property polyaminoester emulsion.The aqueous polyurethane emulsion of preparation forms a film at room temperature, can also form a film at 80 DEG C, or in vacuum
Lower 60 DEG C of film forming.
Reaction equation is as follows：
Diisocyanate can be this field routine in the step, preferably at least have a kind of selected from toluene diisocynate
Ester（TDI）, methyl diphenylene diisocyanate（MDI）, benzene dimethylene diisocyanate（XDI）, two isocyanide of methyl cyclohexyl
Acid esters（HTDI）, two cyclohexyl methane diisocyanates（HMDI）, di-isocyanate（HDI）And isophorone diisocyanate
（IPDI）.Step（1）With step（2）In diisocyanate can be the same or different.
Dihydric alcohol can be this field routine in the step, preferably at least have a kind of selected from ethylene glycol, propylene glycol, fourth
Glycol, hexylene glycol, diglycol, triethylene-glycol.Step（1）With step（2）In dihydric alcohol identical also can may be used
With difference.
The step（1）The mass ratio of middle nano silicon dioxide and diisocyanate is 1:10~40.
The step（1）The nano silicon dioxide of middle diisocyanate modification and the mass ratio of dihydric alcohol are 1:3~10.
The step（2）Middle polyester polyol can be this field routine, preferably polybutylene glyool adipate
（PBA）.
The step（2）Middle polyether polyol can be this field routine, preferably at least have a kind of selected from polyoxyethylene
Glycol（PEG）, polyoxypropylene diols（PPG）, polytetrahydrofuran diol（PTHF）.
The step（2）Middle diisocyanate and polyester polyol or polyether polyol, dihydric alcohol, 2,2- dihydroxymethyls third
Acid（DMPA）Mass ratio be 40 ~ 70:100:2.6:10.
The step（2）The mass ratio of middle diisocyanate and polyalcohol modified nano silicon dioxide is 300 ~ 500:1.
The present invention utilizes multiple hydroxyls on polyalcohol modified Nano particles of silicon dioxide surface, with base polyurethane prepolymer for use as both ends
Isocyanates react to form the polyurethane material with space net structure.Modified nano silicon dioxide is as special friendship
Join agent, together forms physical crosslinking point with hard section in polyurethane molecular.On the one hand the hard section containing nano silicon dioxide can
To destroy the order of soft segment, the crystallinity of soft segment is caused to be greatly reduced, crystal habit systematicness be deteriorated, crystalline melt temperature with
Reduction.Under the premise of not increasing soft segment ratio, the glass transition temperature of soft segment is adjusted to room temperature section, to realize intelligence
Type waterproof and moisture-permeable function.On the other hand, compared with the polyurethane material of no addition modified manometer silicon dioxide, addition modification is received
The space net structure of its molecule of the polyurethane material of rice silica is firmer, can allow while enhancing water resistance
More violent molecule micro Brownian motion, and then generate the intermolecular distance of bigger.Therefore it when temperature is more than Tg, can show
The water vapour permeability of bigger.The additive amount of polyalcohol modified nano silicon dioxide is the pass for realizing waterproof and moisture-permeable function in the present invention
Key.If additive amount is on the low side, the physical crosslinking point being made of it is very few, influences less, macroscopically to embody on the performance of polymer
The function of Waterproof Breathable is not gone out.If additive amount is excessive, polymer crystals form systematicness can be caused to substantially change, although
Penetrability increases, but its water proofing property is remarkably decreased.It is many for the report of silicon dioxide modifying water polyurethane at present, but
Be by improved silica make water-base polyurethane material have waterproof and moisture-permeable function there is not been reported.
The beneficial effects of the invention are as follows：The waterproof moisture-penetrating urethane material provided has the following advantages that, first, containing receiving
The hard section of rice silica can destroy the order of soft segment, under the premise of not increasing soft segment ratio, you can adjust soft segment
Glass transition temperature realizes intelligent waterproof and moisture-permeable function to room temperature section.Second, polyalcohol modified nano silicon dioxide can
So that the space net structure of polyurethane is firmer, water resistance enhancing.Third, easy to process, ecological, environmental protective, production cost
It is low.
Specific implementation mode
Embodiment 1
1. the synthesis of glycol-modified nano silicon dioxide
In 100mL three-necked flasks, the commercially available grain size that 2g dryings are added is the silica of 40nm, the toluene of 20mL dryings
With 20g toluene di-isocyanate(TDI)s.In N2Under atmosphere, by mixture ultrasonic disperse 20min.In N2Lower 50 DEG C are protected to be stirred to react 10h
, then cool to room temperature, washing filters, and obtains the nano silicon dioxide of toluene di-isocyanate(TDI) modification.Take the nanometer after modification
In 100mL two mouth flasks 6g ethylene glycol is added, in N in silica 2g2It protects lower 50 DEG C to be stirred to react 10h, is subsequently cooled to
Room temperature, washing filter, and obtain product.
2. the synthesis of glycol-modified nano silicon dioxide hybridization polyurethane
100g tetramethylene adipates glycol, 2.6g 1,6- hexylene glycols, at 90 DEG C are added in 1000ml three-neck flasks
Vacuum distillation stirring 30min removes vapor.60g butanone and 43.5g toluene di-isocyanate(TDI)s are added in flask, in 70 DEG C of items
30min is reacted under part obtains performed polymer.By 60g butanone, 2,2 dihydromethyl propionic acids of 10g and the glycol-modified nano-silicas of 0.1g
SiClx is added in flask, reacts 3h at 70 DEG C, is cooled to 45 DEG C, and 7.64g triethylamines are added.By reaction solution pour into 400g go from
In sub- water, mechanical agitation 1h obtains lotion.
Lotion is equably coated in release paper, and not generate bubble in coating process.It is one day horizontal positioned, film forming
It is dried 5 hours at 80 DEG C in drying box afterwards, is removed from release paper and obtain film.
Comparative example 1
With embodiment 1, it is a difference in that and glycol-modified nano silicon dioxide is not added.The preparation method of film is the same as real
Apply example 1.
Comparative example 2
With embodiment 1, it is a difference in that glycol-modified nano silicon dioxide addition is 0.05g.The preparation side of film
Method is the same as embodiment 1.
Comparative example 3
With embodiment 1, it is a difference in that glycol-modified nano silicon dioxide addition is 0.2g.The preparation method of film
With embodiment 1.
Embodiment 2
1. the synthesis of propylene glycol modified nano silicon dioxide
In 100mL three-necked flasks, the commercially available grain size that 2g dryings are added is the silica of 100nm, the first of 20mL dryings
The methyl diphenylene diisocyanate of benzene and 70g.In N2Under atmosphere, by mixture ultrasonic disperse 20min.In N2Protect lower 50 DEG C
It is stirred to react 10h, is then cooled to room temperature, washing filters, and obtains the nanometer titanium dioxide of methyl diphenylene diisocyanate modification
Silicon.It takes the nano silicon dioxide 2g after modification in 100mL two mouth flasks, 7g 1,3-PDs is added, in N2Protect lower 90 DEG C
It is stirred to react 7h, is then cooled to room temperature, washing filters, and obtains product.
2. the synthesis of propylene glycol modified nano silicon dioxide hybridization polyurethane
100g polyoxyethylene glycols, 2.6g 1 are added in 1000ml three-neck flasks, 6- hexylene glycols are depressurized at 90 DEG C and steamed
It evaporates stirring 30min and removes vapor.60g butanone and 62.5g methyl diphenylene diisocyanates are added in flask, in 70 DEG C of items
30min is reacted under part obtains performed polymer.By 60g butanone, 2,2 dihydromethyl propionic acids of 10g and the propylene glycol modified nano-silicas of 0.2g
SiClx is added in flask, reacts 6h at 50 DEG C, is cooled to 45 DEG C, and 7.64g triethylamines are added.By reaction solution pour into 400g go from
In sub- water, mechanical agitation 1h obtains lotion.The preparation method is the same as that of Example 1 for film.
Embodiment 3
1. the synthesis of butanediol modified manometer silicon dioxide
In 100mL three-necked flasks, the commercially available grain size that 2g dryings are added is the silica of 100nm, the first of 20mL dryings
The toluene di-isocyanate(TDI) of benzene and 30g.In N2Under atmosphere, by mixture ultrasonic disperse 20min.In N2Protect lower 50 DEG C of stirrings anti-
10h is answered, is then cooled to room temperature, washing filters, and obtains the nano silicon dioxide of toluene di-isocyanate(TDI) modification.After taking modification
Nano silicon dioxide 2g in 100mL two mouth flasks, be added 20g1,4- butanediols, in N2Lower 60 DEG C are protected to be stirred to react
10h is then cooled to room temperature, and washing filters, and obtains product.
2. the synthesis of butanediol modified manometer silicon dioxide hybrid polyurethane
100g polyoxypropylene diols, 2.6g1 are added in 1000ml three-neck flasks, 6- hexylene glycols are depressurized at 90 DEG C and steamed
It evaporates stirring 30min and removes vapor.60g butanone and 55.5g isophorone diisocyanate are added in flask, in 70 DEG C of conditions
Lower reaction 30min obtains performed polymer.By 60g butanone, 2,2 dihydromethyl propionic acids of 10g and 0.15g butanediol modified nano-silicas
SiClx is added in flask, reacts 3h at 55 DEG C, is cooled to 50 DEG C, and 7.64g triethylamines are added.Reaction solution is poured into 400g deionizations
In water, mechanical agitation 1h obtains lotion.The preparation method is the same as that of Example 1 for film.
Embodiment 4
1. the synthesis of diglycol modified manometer silicon dioxide
In 100mL three-necked flasks, the commercially available grain size that 2g dryings are added is the silica of 60nm, the toluene of 20mL dryings
With the dicyclohexyl methyl hydride diisocyanate of 80g.In N2Under atmosphere, by mixture ultrasonic disperse 20min.In N2Protect lower 60 DEG C
It is stirred to react 8.5h, is then cooled to room temperature, washing filters, the nano silicon dioxide modified.Take the nanometer two after modification
In 50mL two mouth flasks 18g diglycols are added, in N in silica 2g2Lower 70 DEG C are protected to be stirred to react 8h, it is then cold
But to room temperature, washing filters, and obtains product.
2. the synthesis of diglycol modified manometer silicon dioxide hybrid polyurethane
100g polytetrahydrofuran diols, 2.6g1 are added in 1000ml three-neck flasks, 6- hexylene glycols depressurize at 90 DEG C
Distillation stirring 30min removes vapor.60g butanone and bis- cyclohexyl methane diisocyanates of 65.5g are added in flask, 70
30min is reacted under the conditions of DEG C obtains performed polymer.By 60g butanone, 2,2 dihydromethyl propionic acids of 10g and 0.22g diglycols
Modified manometer silicon dioxide is added in flask, reacts 4.5h at 60 DEG C, is cooled to 45 DEG C, and 7.64g triethylamines are added.It will reaction
Liquid pours into 400g deionized waters, and mechanical agitation 1h obtains lotion.The preparation method is the same as that of Example 1 for film.
Embodiment 5
1. the synthesis of triethylene-glycol modified manometer silicon dioxide
In 100mL three-necked flasks, the commercially available grain size that 2g dryings are added is the silica of 10nm, the toluene of 20mL dryings
With the toluene di-isocyanate(TDI) of 30g.In N2Under atmosphere, by mixture ultrasonic disperse 20min.In N2Lower 60 DEG C are protected to be stirred to react
8.5h is then cooled to room temperature, and washing filters, the nano silicon dioxide modified.Take the nano silicon dioxide 2g after modification
In 100mL two mouth flasks, 20g triethylene-glycols are added, in N2It protects lower 70 DEG C to be stirred to react 8h, is subsequently cooled to room
Temperature, washing filter, and obtain product.
2. the synthesis of triethylene-glycol modified manometer silicon dioxide hybrid polyurethane
100g polytetrahydrofuran diols, 2.6g1 are added in 1000ml three-neck flasks, 6- hexylene glycols depressurize at 90 DEG C
Distillation stirring 30min removes vapor.60g butanone and 43.5g toluene di-isocyanate(TDI)s are added in flask, under the conditions of 70 DEG C
Reaction 30min obtains performed polymer.60g butanone, 2,2 dihydromethyl propionic acids of 10g and 0.26g are modified grafting triethylene-glycol
Nano silicon dioxide be added in flask, react 6h at 50 DEG C, be cooled to 45 DEG C, 7.64g triethylamines are added.400g water is added
Mechanical agitation 1h obtains lotion.
The film prepared in above-described embodiment 1,2,3,4 and comparative example 1,2,3 is subjected to penetrability, extension at break respectively
Rate, tensile strength, water absorption rate test, test result are shown in Table 1.As can be seen from Table 1, several polyalcohol modified nano silicon dioxides
The unmodified aqueous polyurethane films of performance ratios such as hybrid polyurethane film its penetrability, elongation at break, tensile strength, water absorption rate are equal
It improves a lot.
Table 1：Polyalcohol modified nano silicon dioxide hybridization polyurethane film is compared with unmodified aqueous polyurethane film properties
| Film performance | Penetrability/mg/ (10cm2.24h) | Elongation at break/% | Tensile strength/MPa | Water absorption rate/% |
| Embodiment 1（Glycol-modified nano silicon dioxide） | 230.36 | 532.48 | 24.38 | 53.80 |
| Comparative example 1（Common water borne polyurethane film） | 127.88 | 431.52 | 19.22 | 78.71 |
| Comparative example 2（Glycol-modified nano silicon dioxide） | 129.76 | 442.53 | 19.79 | 96.51 |
| Comparative example 3（Glycol-modified nano silicon dioxide） | 207.53 | 523.65 | 22.49 | 87.22 |
| Embodiment 2（The propylene glycol modified nano silicon dioxides of 1,3-） | 235.38 | 554.36 | 28.30 | 51.52 |
| Embodiment 3（1,4-butanediol modified manometer silicon dioxide） | 228.74 | 540.25 | 29.95 | 51.24 |
| Embodiment 4（Diglycol modified manometer silicon dioxide） | 190.25 | 546.35 | 26.89 | 60.25 |
It discusses：
Embodiment 1 by table 1 and polyalcohol modified nano-silica it can be seen from comparative example 2, the test result of comparative example 3
The additive amount of SiClx is a key factor for realizing Waterproof Breathable.If additive amount is too small, such as comparative example 2, then its film
Penetrability is close with common water borne polyurethane film, shows that its water vapour permeability is poor.If additive amount is excessive, such as comparative example 3, then its
The water absorption rate of film increases considerably, and shows that its water resistance is poor.Currently preferred polyalcohol modified nano silicon dioxide
Additive amount is the step（2）The 1/300 ~ 1/500 of middle diisocyanate quality.
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to the present patent application protection domain with
Modification should all belong to the covering scope of the present invention.
Claims (2)
1. a kind of waterproof moisture-penetrating urethane material, it is characterised in that prepared by following methods：
（1）The synthesis of polyalcohol modified nano silicon dioxide
It is 7~200nm silica and a certain amount of diisocyanate that commercially available grain size is added in dry toluene, and nitrogen is protected
By mixture ultrasonic disperse under shield, then 7~10h of insulation reaction between 50 DEG C~70 DEG C；It is cooled to room temperature, filters, washing,
Obtain the nano silicon dioxide of diisocyanate modification；The nano-silicon dioxide particle that diisocyanate obtained is modified and one
Quantitative dihydric alcohol mixing, under nitrogen protection between 50 DEG C~70 DEG C 7~10h of insulation reaction；It is cooled to room temperature, filters, wash
It washs, obtains polyalcohol modified nano silicon dioxide product；
（2）The synthesis of polyalcohol modified nano silicon dioxide hybridization polyurethane
The polyester polyol of metering or polyether polyol are fitted into vacuum in the there-necked flask for carrying thermometer, nitrogen protection device to take off
Water；A certain amount of diisocyanate and butanone are added after between being cooled to 50 DEG C~70 DEG C, 2~8h of reaction obtains performed polymer；
A certain amount of dihydric alcohol, 2,2- dihydromethyl propionic acids are added in performed polymer（DMPA）With polyalcohol modified nano silicon dioxide,
Reaction obtains reaction solution at 50 DEG C~90 DEG C；Reaction solution is cooled to 45 DEG C, a certain amount of triethylamine insulated and stirred is added；Then
It is added in a certain amount of deionized water, nano silicon dioxide hybridization aqueous polyurethane emulsion is obtained after mechanical agitation；Preparation is obtained
Film is made in the nano silicon dioxide hybridization aqueous polyurethane emulsion obtained；
Step（1）With step（2）Described in dihydric alcohol it is at least a kind of selected from ethylene glycol, propylene glycol, butanediol, hexylene glycol,
Diglycol or triethylene-glycol.
2. waterproof moisture-penetrating urethane material according to claim 1, it is characterised in that：The step（2）Middle diisocyanate
The mass ratio of ester and polyalcohol modified nano silicon dioxide is 300 ~ 500:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610332666.6A CN105968305B (en) | 2016-05-19 | 2016-05-19 | A kind of waterproof moisture-penetrating urethane material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610332666.6A CN105968305B (en) | 2016-05-19 | 2016-05-19 | A kind of waterproof moisture-penetrating urethane material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105968305A CN105968305A (en) | 2016-09-28 |
| CN105968305B true CN105968305B (en) | 2018-10-26 |
Family
ID=56955267
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610332666.6A Active CN105968305B (en) | 2016-05-19 | 2016-05-19 | A kind of waterproof moisture-penetrating urethane material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105968305B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019072757A1 (en) * | 2017-10-10 | 2019-04-18 | Basf Se | Elastic membrane |
| CN109096677A (en) * | 2018-06-05 | 2018-12-28 | 太仓新宏电子科技有限公司 | A kind of high water pressure resistance, the preparation method of high moisture-inhibiting polyurethane film |
| CN108976766B (en) * | 2018-06-22 | 2020-12-18 | 中山博锐斯新材料股份有限公司 | Waterproof moisture-permeable polyurethane microporous film and preparation method thereof |
| CN110157178A (en) * | 2019-04-19 | 2019-08-23 | 苏州奥斯汀新材料科技有限公司 | A kind of low abrasion method for preparing thermoplastic polyurethane elastomer of high slip preventing |
| CN113087939A (en) * | 2021-03-02 | 2021-07-09 | 重庆中膜科技集团有限公司 | Waterproof breathable film with heat preservation performance and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0523806B1 (en) * | 1991-07-15 | 1996-05-15 | Unitika Ltd. | Moisture permeable and waterproof coated fabric and method for manufacturing same |
| CN102633977A (en) * | 2012-05-04 | 2012-08-15 | 苏州大学 | Waterproof moisture-permeable coating adhesive and preparation method and application thereof |
| CN104448220A (en) * | 2014-11-24 | 2015-03-25 | 晋江市闽高纺织科技有限公司 | Waterborne polyurethane waterproof moisture-permeable coated fabric and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009221630A (en) * | 2008-03-17 | 2009-10-01 | Unitica Fibers Ltd | Breathable-waterproof fabric |
-
2016
- 2016-05-19 CN CN201610332666.6A patent/CN105968305B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0523806B1 (en) * | 1991-07-15 | 1996-05-15 | Unitika Ltd. | Moisture permeable and waterproof coated fabric and method for manufacturing same |
| CN102633977A (en) * | 2012-05-04 | 2012-08-15 | 苏州大学 | Waterproof moisture-permeable coating adhesive and preparation method and application thereof |
| CN104448220A (en) * | 2014-11-24 | 2015-03-25 | 晋江市闽高纺织科技有限公司 | Waterborne polyurethane waterproof moisture-permeable coated fabric and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 智能防水透湿聚氨酯研究进展;王玮玲等;《聚氨酯工业》;20141231;第29卷(第6期);第5-8页 * |
| 水性聚氨酯/改性纳米二氧化硅复合涂料的研究;邵莎莎;《中国优秀硕士学位论文全文数据库 工程科技I辑》;中国学术期刊（光盘版）电子杂志社;20071215(第06（2007）期);第2.2.1.2、3.2.2.2、3.2.3.4节，图2.8，表3.4、表3.5 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105968305A (en) | 2016-09-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105968305B (en) | A kind of waterproof moisture-penetrating urethane material and preparation method thereof | |
| CN109293969B (en) | Polyurethane TPU (thermoplastic polyurethane) curtain inner liner and preparation method thereof | |
| CN108884597B (en) | Organosilicon-modified polyurethane fiber and process for producing the same | |
| KR20090024119A (en) | Microporous coating based on polyurethane polyurea | |
| CN105111724B (en) | A kind of high Waterproof Breathable TPU film and preparation method thereof | |
| Shi et al. | Robust waterproof and self-adaptive breathable membrane with heat retention property for intelligent protective cloth | |
| KR20050072792A (en) | Heat resistant high moisture vapor transmission thermoplastic polyurethane | |
| KR20090008447A (en) | Microporous coating based on polyurethane-polyurea | |
| CN105001621A (en) | Temperature-sensitive intelligent waterproof and moisture permeable TPU film and preparation method thereof | |
| KR101099791B1 (en) | Preparation method for functional fabric having antibiotic and moisture absorption properties using sliver nanopaticles incorporated mesoporous sillica | |
| KR20120036794A (en) | Process for producing porous object, and porous object, layered product, and leather-like sheet each obtained thereby | |
| CN1303124C (en) | Water base block polyurethane, its preparing method and water-proof, heat insulation and wet permeable material made thereof | |
| CN106702723B (en) | Fabric oriented moisture transfer polyurethane resin coating adhesive and preparation method thereof | |
| JP4348727B2 (en) | Method for producing polyurethane yarn | |
| CN1247697C (en) | Polyurethane porous film and its preparing method | |
| JP2004182916A (en) | Moisture-permeating resin composition and moisture-permeating elastic film | |
| KR101607496B1 (en) | Method of manufacturing polyurethane resin using isocyanated aerogel used in moisture permeable-waterproof fabric | |
| CN111764170B (en) | Waterproof moisture-permeable film and preparation method thereof | |
| CN104744664A (en) | Production method of nano-silver memory foams | |
| KR20140135394A (en) | Method of manufacturing polyurethane resin comprising airogel used in moisture permeable-waterproof fabric | |
| JP5050347B2 (en) | Urethane resin dispersion for moisture permeable and waterproof processing, its production method and moisture permeable waterproof cloth | |
| JPH1017764A (en) | Polyurethane resin composition for nonporous-type moisture-permeable waterproof fabric | |
| JP2001055628A (en) | Production of polyurethane fiber | |
| CN108059710A (en) | A kind of polyurethane shape memory high molecule material and its synthesis technology | |
| CN114622422A (en) | Preparation method of temperature-sensitive moisture-permeable composite coating fabric with super-hydrophobicity |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |