CN105566625B - A kind of polyether polyurethane material and the preparation method and application thereof - Google Patents
A kind of polyether polyurethane material and the preparation method and application thereof Download PDFInfo
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- CN105566625B CN105566625B CN201510975996.2A CN201510975996A CN105566625B CN 105566625 B CN105566625 B CN 105566625B CN 201510975996 A CN201510975996 A CN 201510975996A CN 105566625 B CN105566625 B CN 105566625B
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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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
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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
- C08G18/65—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
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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
- C08G18/65—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
- C08G18/6677—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 having at least three hydroxy groups
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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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
- C08G65/269—Mixed catalyst systems, i.e. containing more than one reactive component or catalysts formed in-situ
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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
- C08G2110/00—Foam properties
- C08G2110/0083—Foam properties prepared using water as the sole blowing agent
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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
- C08G2410/00—Soles
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The present invention provides a kind of polyether polyurethane material, preparation method is：In organic solvent, initiator polyalcohol, in reacting at room temperature 1~30h, obtains system A with alkylene oxide A under the catalytic action of alkali A；Alkylene oxide B and metal sulfate are added in system A, in reacting at room temperature 1~40h, obtain system B；Alkylene oxide C and alkali B are added in system B, in reacting at room temperature 1~60h, reaction mixture is post-treated later, finished product；Polyether polyurethane material of the present invention can be used for preparing the microporous polyurethane elastomer as sole material；Polyether polyurethane material of the present invention has stronger cryogenic property, anti-hydrolytic performance and anti-mildew performance, during which is used to prepare polyurethane elastomer, shortens reaction time and demoulding time, and can improve the physical property of product.
Description
(1) technical field
The invention belongs to polymeric material fields, and in particular to a kind of polyether polyurethane material and preparation method thereof with answer
With.
(2) background technology
Polyether polyol is the important source material of synthesis of polyurethane material.In recent years, with the rapid development of polyurethane industrial,
The reduction of the raising and production cost of domestic and international major manufacturing enterprise and scientific research institution around Contents In Polyether Polyol capability and performance,
A large amount of research-and-development activity is carried out.
Chinese shoemaking is a dark horse, and in short more than ten years, becomes the maximum footwear producing country in the whole world and exported country,
Especially after China's entry into the WTO, powerful developing state, the worlds shoes industry yield Yi Zhan total amount nearly 40% is more presented in Chinese shoemaking
~50%, in global footwear trade, China's footwear export amount has also accounted for 25%, both ranks first in the world.Currently, I
State's footwear consumption figure accounts for the 22% of world's aggregate consumption, is one of most important leather shoes country of consumption in the whole world.With people's lives
Horizontal raising, requirement of the people to shoes is also that when the river rises the boat goes up, beautiful and generous by pervious emphasis, is changed into and is focusing on beauty
While generous, focus on its safety comfort.And footwear quality quality and material for sole of shoe performance have it is extremely close
Contact, decides the functionality and comfort of sole.We were also clearly felt that the progress with production technology, sole in recent years
Material texture type is more and more abundant, and the embodiment degree of tailored version is more and more stronger, therefore continually developing by enterprise, novel
Material for sole of shoe also gradually emerges, and certain guarantee is provided for the quality of China's footwear.China is the first in the world production shoes
Big country produces about 5,000,000,000 pairs, shoes per year, accounts for the 42% of global shoes yield.But current polyurethane only has 2.8 ten thousand/a in the dosage of the industry,
Account for the 2% of shoes total raw material amount.And polyurethane material accounts for 6.8% in whole world shoe industry, and in economically developed Europe, this ratio
Example up to 20% or more.Polyurethane footwear material market potential is very big.In recent years, the development speed of China's microcellular polyurethane shoe sole is very
Soon, annual growth is 12% or more, but kind is dull, is essentially confined to leather shoe sole and athletic shoe sole.As it can be seen that in this neck
Our work of domain is compared with foreign countries, and gap is very remote.
In " 15 " of Chinese polyurethane industrial association auspices and planning proposal in 2015, research and development polyethers
The production technology of type and polyester polyethers copoly type, hydrolysis microcellular polyurethane elastomer sole material is elastic as following a period of time
One developing direction of system product is contemplated.It is led it is contemplated that Science in Future in China polyurethane shoe material market will become polyurethane
One, domain new growth engines.Therefore, the synthesis right and wrong of polyurethane shoe-sole polyethers are often with promising, but related its is ground
Study carefully and is but rarely reported.
(3) invention content
The technical purpose of the present invention is, for current polyester polyurethane facile hydrolysis and it is biodegradable the shortcomings of, and make
Sole be easy to happen the defect of cracking, fracture, the present invention provides a kind of polyether polyurethane materials and preparation method thereof, use
The sole that polyether polyurethane material of the present invention makes just overcomes the weakness of polyester polyurethane sole, has stronger low
Warm nature energy, anti-hydrolytic performance and anti-mildew performance.In addition, polyurethane elastomer is prepared with polyether polyurethane material of the present invention,
Reaction time and demoulding time are shortened, and the physical property of product can be improved.
To achieve the above object, the present invention adopts the following technical scheme that：
A kind of polyether polyurethane material, the polyether polyurethane material are prepared as follows to obtain：
In organic solvent, initiator polyalcohol and alkylene oxide A be under the catalytic action of alkali A, in reacting at room temperature 1~30h,
Obtain system A；Alkylene oxide B and metal sulfate are added in system A, in reacting at room temperature 1~40h, obtain system B；By epoxy
Alkane C and alkali B are added in system B, and in reacting at room temperature 1~60h, reaction mixture is post-treated later, and the polyether-type is made
Polyurethane material；
Wherein, the object that feeds intake of the polyalcohol and alkylene oxide A, alkali A, alkylene oxide B, metal sulfate, alkylene oxide C, alkali B
The ratio between amount of matter is 1：0.01~10：0.01~10：0.01~10：0.1~10：0.1~10：0.1~10 (preferably 1：1~2：1
~2：1~2：2~4：2~4：2~4)；
The volumetric usage of the organic solvent is calculated as 0.001~10mL/g (preferably 0.5~2mL/ with the quality of polyalcohol
g)；
The organic solvent be selected from methanol, ethyl alcohol, propyl alcohol, isopropanol, n-butanol, isobutanol, n-amyl alcohol, n-octyl alcohol,
Acetone, butanone, chloroform, dichloromethane, ether, carbon disulfide, 1-Methyl-2-Pyrrolidone, N-N- dimethylformamides, N-N-
Dimethylacetylamide, dimethyl sulfoxide, tetrahydrofuran, ethyl acetate, dioxane, acetonitrile, benzene, toluene or dimethylbenzene, preferably first
Alcohol or ethyl alcohol；
The polyalcohol is selected from ethylene glycol, 1,2- propylene glycol, 1,4- butanediols, hexylene glycol, neopentyl glycol, two contracting diethyls
Glycol, dipropylene glycol, trimethylolpropane or glycerine, preferably 1,2-PD；
The alkylene oxide A is selected from ethylene oxide, propylene oxide, epoxy butane, epoxypentane, oxepane, epoxy heptan
Alkane or octylene oxide, optimization ethylene oxide or propylene oxide；
The alkali A is selected from NaOH, KOH, Ba (OH)2Or Ca (OH)2, preferably NaOH；
The definition of the alkylene oxide B is identical as the definition of alkylene oxide A；
The metal sulfate is selected from sodium sulphate, magnesium sulfate, ferrous sulfate, ferric sulfate, barium sulfate, potassium sulfate, sulfuric acid
Aluminium potassium, calcium sulfate or sulfuric acid magnalium, preferably sulfuric acid magnalium；
The definition of the alkylene oxide C is identical as the definition of alkylene oxide A；
The definition of the alkali B is identical as the definition of alkali A.
In preparation method of the present invention, specifically, the post-processing approach of the reaction mixture is：
After reaction, reaction mixture is 1 through alcohol-water volume ratio：1 mixed liquor washing, 5000r/min centrifugations are gone
Fall clear liquid, the above washing, centrifugal process 3 times repeatedly are finally drying to obtain the polyether polyurethane material.
Above-mentioned term " system A ", " system B " not special meaning is only intended to distinguish different behaviour labeled as " A ", " B "
Make the system in step.Term " alkylene oxide A ", " alkylene oxide B ", " alkylene oxide C " also not special meaning, refer both to ordinary meaning
On alkylene oxide, be only intended to distinguish alkylene oxide used in different operation step labeled as " A ", " B ", " C "." alkali A ",
" alkali B " therewith similarly.
Specifically, polyether polyurethane material of the present invention is recommended to be prepared as follows to obtain：
In methyl alcohol, initiator 1,2-PD and propylene oxide A are anti-in room temperature under the catalytic action of sodium hydroxide A
12h is answered, system A is obtained；Propylene oxide B and sulfuric acid magnalium are added in system A, in room temperature reaction 20h, obtain system B；By ring
Oxidative ethane and sodium hydroxide B are added in system B, and for 24 hours in room temperature reaction, reaction mixture is 1 through alcohol-water volume ratio later：1
Mixed liquor washing, 5000r/min centrifugations remove clear liquid, and the above washing, centrifugal process 3 times repeatedly are finally drying to obtain described
Polyether polyurethane material；
Wherein, the 1,2-PD and propylene oxide A, sodium hydroxide A, propylene oxide B, sulfuric acid magnalium, cyclohexane,
The ratio between amount for the substance that feeds intake of sodium hydroxide B is 1：1~2：1~2：1~2：2~4：2~4：2~4；
The volumetric usage of the methanol is calculated as 0.5~2mL/g with the quality of 1,2- propylene glycol.
Above-mentioned term " propylene oxide A ", " propylene oxide B " not special meaning is only intended to area labeled as " A ", " B "
Divide propylene oxide used in different operation step." sodium hydroxide A ", " sodium hydroxide B " are therewith similarly.
The present invention also provides a kind of polyether polyurethane material answering in preparing microporous polyurethane elastomer
With the method for the application is：
(1) by 1~50 part of 1~100 part of methyl diphenylene diisocyanate and liquefied methyl diphenylene diisocyanate
It is added in reaction vessel, maintains the temperature at 70~80 DEG C, then by 1~50 part of polyether polyurethane material of the present invention and ethylene glycol
0.1~10 part of mixture is also added in reaction vessel, reacts 1~20h under inert gas protection, after curing 1~30min,
Material (foam-like) is taken out and places 1~30h, a must be formulated；
(2) 1~150 part of polyether polyurethane material of the present invention, 1~25 part of glycerine, 0.1~2 part of diethylene glycol, silicone oil are taken
0.1~4 part, 0.1~5 part of water, the mixing of 0.1~2 part of diethylene diamine, after stirring evenly, b must be formulated；
(3) formula a obtained by step (1) is poured into formula b obtained by step (2), poured into after stirring evenly surface be coated with it is de-
In the preheated mold of mould agent, mold closing is put into 1~15min of curing in 30~80 DEG C of baking ovens, and demoulding is taken out up to microporous polyurethane
Elastomer.
Wherein, the liquefied methyl diphenylene diisocyanate is prepared as follows to obtain：By solid-state diphenylmethyl
Alkane diisocyanate is placed in beaker, and 50 DEG C are heated in water bath with thermostatic control, and two isocyanide of liquefied diphenyl methane is prepared
Acid esters.
Silicone compounds, silicone oil, silicones metlyl branching silicone oil, methyl-silicone oil, breast may be used in the releasing agent
Change methyl-silicone oil, hydrogeneous methyl-silicone oil, silicone grease, silicones, silicon rubber, silicon rubber toluene solution, microcrystalline wax or polyethylene wax
Deng.
Microporous polyurethane elastomer prepared by the present invention can be used as the preparation that sole material is applied to sole.
Compared with prior art, the beneficial effects of the present invention are：
Polyether polyurethane material of the present invention has stronger cryogenic property, anti-hydrolytic performance and anti-mildew performance, the material
Material can be used for the preparation of polyurethane elastomer, and preparation process shortens reaction time and demoulding time, and can improve the object of product
Rationality energy.It is applied to the conventional polyether polyols of polyurethane shoe-sole stoste currently on the market, is by initiator and epoxide
NaOH catalysis under by anionic polymerization mechanism carry out, in the course of the polymerization process epoxide be easy to happen side reaction formed compared with
High degree of unsaturation makes the reduction of polyethers actual functionality, keeps the mechanical performance of polyurethane shoe-sole poor, cannot meet the need in market
It asks.It for 2 or 3 polyalcohol is initiator that the present invention, which uses degree of functionality, and two kinds of catalyst segments use, with Polymerization of Propylene Oxide,
It is ethylene oxide-capped, novel polyether type polyurethane material is finally made.The polyether polyurethane material activity of synthesis is high, unsaturated
Value is less than 0.04mol/kg, and relative molecular mass reaches 4000, and molecular chain structure is more regular, is a kind of high comprehensive performance
High molecular material.Using every physical index of microporous polyurethane elastomer sole prepared by polyether polyurethane material of the present invention
The universal product of existing market, intensity height, good toughness have been better than it, tensile strength can be higher than 140MPa, and elongation at break be more than
150%.
(4) it illustrates
Fig. 1 is the stretched mechanical intensity data figure of microporous polyurethane elastomer prepared by Examples 1 to 3.
(5) specific implementation mode
Below by way of specific embodiment, present invention is further described in detail, but protection scope of the present invention and not only limits
In this.
Embodiment 1
Prepare polyether polyurethane material：
In reaction bulb, 1,2-PD (7.61g, 0.1mol), propylene oxide (5.81g, 0.1mol), hydroxide is added
Sodium (4g, 0.1mol), methanol (5mL), in room temperature reaction 12h；Then propylene oxide (5.81g, 0.1mol), sulfuric acid magnalium is added
(75g, 0.1mol), in room temperature reaction 20h；Be subsequently added into ethylene oxide (8.81g, 0.2mol), sodium hydroxide (4g,
0.1mol), for 24 hours in room temperature reaction, reaction mixture 10mL alcohol-water volume ratios are 1 later：1 mixed liquor washing,
Clear liquid is removed in 5000r/min centrifugations, and the above washing, centrifugal process 3 times repeatedly are finally drying to obtain the polyether polyurethane
Material 10g.
Prepare microporous polyurethane elastomer：
(1) four mouthfuls of burnings are added in methyl diphenylene diisocyanate 60g and liquefied methyl diphenylene diisocyanate 15g
In bottle, 70 DEG C are maintained the temperature at, then the polyether polyurethane material 5g of above-mentioned preparation is added in 1g ethylene glycol, is uniformly mixed
It pours into afterwards in the four-hole boiling flask equipped with methyl diphenylene diisocyanate, reacts 2h under nitrogen protection, it, will after curing 10min
Foam-like material takes out, and places 2h, must be formulated a；
Wherein, the liquefied methyl diphenylene diisocyanate is prepared as follows to obtain：By solid-state diphenylmethyl
Alkane diisocyanate is placed in 500ml beakers, and 50 DEG C are heated in water bath with thermostatic control, and liquefied diphenyl methane two is prepared
Isocyanates；
(2) polyether polyurethane material 1g, glycerine 2g, diethylene glycol 0.2g, silicone oil 0.2g, the water of above-mentioned preparation are taken
0.3g, diethylene diamine 0.3g mixing, after stirring evenly, must be formulated b；
(3) formula a obtained by step (1) is poured into rapidly in formula b obtained by step (2), high-speed stirred is uniform, pours into rapidly
Surface is coated in the preheated mold of releasing agent silicone oil, mold closing, is put into 40 DEG C of baking ovens and is cured 10min, and demoulding is taken out up to poly- ammonia
Ester micro-pore elastomer；
The stretched mechanical intensity data figure of the above-mentioned microporous polyurethane elastomer being prepared is shown in attached drawing 1, by data in Fig. 1
It can be found that the microporous polyurethane elastomer tensile strength is up to 138MPa, elongation at break is up to 143%.
Embodiment 2
Prepare polyether polyurethane material：
In reaction bulb, 1,2-PD (7.61g, 0.1mol), propylene oxide (8.71g, 0.15mol), hydrogen-oxygen is added
Change sodium (4g, 0.1mol), methanol (5mL), in room temperature reaction 12h；Then propylene oxide (5.81g, 0.1mol), magnesium sulfate is added
Aluminium (75g, 0.1mol), in room temperature reaction 20h；Be subsequently added into ethylene oxide (6.61g, 0.15mol), sodium hydroxide (4g,
0.1mol), for 24 hours in room temperature reaction, reaction mixture 10mL alcohol-water volume ratios are 1 later：1 mixed liquor washing,
Clear liquid is removed in 5000r/min centrifugations, and the above washing, centrifugal process 3 times repeatedly are finally drying to obtain the polyether polyurethane
Material 15g.
Prepare microporous polyurethane elastomer：
(1) four mouthfuls of burnings are added in methyl diphenylene diisocyanate 70g and liquefied methyl diphenylene diisocyanate 20g
In bottle, 70 DEG C are maintained the temperature at, then the polyether polyurethane material 5g of above-mentioned preparation is added in 5g ethylene glycol, is uniformly mixed
It pours into afterwards in the four-hole boiling flask equipped with methyl diphenylene diisocyanate, reacts 3h under protection of argon gas, it, will after curing 10min
Foam-like material takes out, and places 3h, must be formulated a；
Wherein, the preparation method is the same as that of Example 1 for the liquefied methyl diphenylene diisocyanate；
(2) polyether polyurethane material 70g, glycerine 15g, diethylene glycol 0.5g, silicone oil 0.4g, the water of above-mentioned preparation are taken
0.5g, diethylene diamine 0.3g mixing, after stirring evenly, must be formulated b；
(3) formula a obtained by step (1) is poured into rapidly in formula b obtained by step (2), high-speed stirred is uniform, pours into rapidly
Surface is coated in the preheated mold of releasing agent silicones metlyl branching silicone oil, mold closing, is put into 40 DEG C of baking ovens and is cured 10min, is taken off
Mould takes out up to microporous polyurethane elastomer；
The stretched mechanical intensity data figure of the above-mentioned microporous polyurethane elastomer being prepared is shown in attached drawing 1, by data in Fig. 1
It can be found that the microporous polyurethane elastomer tensile strength is up to 132MPa, elongation at break is up to 131%.
Embodiment 3
Prepare polyether polyurethane material：
In reaction bulb, 1,2-PD (11.41g, 0.15mol), propylene oxide (5.81g, 0.1mol), hydrogen-oxygen is added
Change sodium (4g, 0.1mol), methanol (10mL), in room temperature reaction 12h；Then propylene oxide (4.41g, 0.1mol), sulfuric acid is added
Magnalium (75g, 0.1mol), in room temperature reaction 20h；Be subsequently added into ethylene oxide (6.61g, 0.15mol), sodium hydroxide (4g,
0.1mol), for 24 hours in room temperature reaction, reaction mixture 10mL alcohol-water volume ratios are 1 later：1 mixed liquor washing,
Clear liquid is removed in 5000r/min centrifugations, and the above washing, centrifugal process 3 times repeatedly are finally drying to obtain the polyether polyurethane
Material 15g.
Prepare microporous polyurethane elastomer：
(1) four mouthfuls of burnings are added in methyl diphenylene diisocyanate 80g and liquefied methyl diphenylene diisocyanate 30g
In bottle, 80 DEG C are maintained the temperature at, then the polyether polyurethane material 10g of above-mentioned preparation is added in 5g ethylene glycol, mixing is equal
It is poured into after even in the four-hole boiling flask equipped with methyl diphenylene diisocyanate, reacts 5h under nitrogen protection, after curing 10min,
Foam-like material is taken out, 5h is placed, a must be formulated；
Wherein, the preparation method is the same as that of Example 1 for the liquefied methyl diphenylene diisocyanate；
(2) polyether polyurethane material 80g, glycerine 15g, diethylene glycol 0.5g, silicone oil 0.4g, the water of above-mentioned preparation are taken
0.5g, diethylene diamine 0.3g mixing, after stirring evenly, must be formulated b；
(3) formula a obtained by step (1) is poured into rapidly in formula b obtained by step (2), high-speed stirred is uniform, pours into rapidly
Surface is coated in the preheated mold of releasing agent methyl-silicone oil, mold closing, is put into 50 DEG C of baking ovens and is cured 15min, and demoulding is taken out to obtain the final product
Microporous polyurethane elastomer；
The stretched mechanical intensity data figure of the above-mentioned microporous polyurethane elastomer being prepared is shown in attached drawing 1, by data in Fig. 1
It can be found that the microporous polyurethane elastomer tensile strength is up to 146MPa, elongation at break is up to 152%.
Embodiment 4
Prepare polyether polyurethane material：
In reaction bulb, 1,2-PD (11.41g, 0.15mol), propylene oxide (8.71g, 0.15mol), hydrogen is added
Sodium oxide molybdena (4g, 0.1mol), methanol (10mL), in room temperature reaction 12h；Then propylene oxide (5.81g, 0.1mol), sulphur is added
Sour magnalium (75g, 0.1mol), in room temperature reaction 20h；Be subsequently added into ethylene oxide (4.41g, 0.1mol), sodium hydroxide (4g,
0.1mol), for 24 hours in room temperature reaction, reaction mixture 10mL alcohol-water volume ratios are 1 later：1 mixed liquor washing,
Clear liquid is removed in 5000r/min centrifugations, and the above washing, centrifugal process 3 times repeatedly are finally drying to obtain the polyether polyurethane
Material 20 g.
Prepare microporous polyurethane elastomer：
(1) four mouthfuls of burnings are added in methyl diphenylene diisocyanate 80g and liquefied methyl diphenylene diisocyanate 15g
In bottle, 80 DEG C are maintained the temperature at, then the polyether polyurethane material 30g of above-mentioned preparation is added in 3g ethylene glycol, mixing is equal
It is poured into after even in the four-hole boiling flask equipped with methyl diphenylene diisocyanate, reacts 6h under nitrogen protection, it, will after curing 8min
Foam-like material takes out, and places 2h, must be formulated a；
Wherein, the preparation method is the same as that of Example 1 for the liquefied methyl diphenylene diisocyanate；
(2) polyether polyurethane material 65g, glycerine 12g, diethylene glycol 0.3g, silicone oil 0.3g, the water of above-mentioned preparation are taken
0.5g, diethylene diamine 0.2g mixing, after stirring evenly, must be formulated b；
(3) formula a obtained by step (1) is poured into rapidly in formula b obtained by step (2), high-speed stirred is uniform, pours into rapidly
Surface is coated in the preheated mold of the hydrogeneous methyl-silicone oil of releasing agent, mold closing, is put into 45 DEG C of baking ovens and is cured 5min, is demoulded, and is taken out
Up to microporous polyurethane elastomer；
The microporous polyurethane elastomer tensile strength of above-mentioned preparation is up to 138MPa, and elongation at break is up to 143%.
Embodiment 5
Prepare polyether polyurethane material：
In reaction bulb, 1,2-PD (15.22g, 0.2mol), propylene oxide (11.62g, 0.2mol), hydrogen-oxygen is added
Change sodium (4g, 0.1mol), methanol (20mL), in room temperature reaction 12h；Then propylene oxide (11.62g, 0.2mol), sulfuric acid is added
Magnalium (150g, 0.2mol), in room temperature reaction 20h；Be subsequently added into ethylene oxide (8.81g, 0.2mol), sodium hydroxide (4g,
0.1mol), for 24 hours in room temperature reaction, reaction mixture 20mL alcohol-water volume ratios are 1 later：1 mixed liquor washing,
Clear liquid is removed in 5000r/min centrifugations, and the above washing, centrifugal process 3 times repeatedly are finally drying to obtain the polyether polyurethane
Material 25g.
Prepare microporous polyurethane elastomer：
(1) four mouthfuls of burnings are added in methyl diphenylene diisocyanate 80g and liquefied methyl diphenylene diisocyanate 25g
In bottle, 70 DEG C are maintained the temperature at, then the polyether polyurethane material 12g of above-mentioned preparation is added in 0.8g ethylene glycol, mixing
It is poured into the four-hole boiling flask equipped with methyl diphenylene diisocyanate after uniformly, reacts 5h under protection of argon gas, after curing 7min,
Foam-like material is taken out, 6h is placed, a must be formulated；
Wherein, the preparation method is the same as that of Example 1 for the liquefied methyl diphenylene diisocyanate；
(2) polyether polyurethane material 15g, glycerine 16g, diethylene glycol 0.8g, silicone oil 0.5g, the water of above-mentioned preparation are taken
0.3g, diethylene diamine 0.5g mixing, after stirring evenly, must be formulated b；
(3) formula a obtained by step (1) is poured into rapidly in formula b obtained by step (2), high-speed stirred is uniform, pours into rapidly
Surface is coated in the preheated mold of releasing agent microcrystalline wax, mold closing, is put into 60 DEG C of baking ovens and is cured 12min, and demoulding is taken out to obtain the final product
Microporous polyurethane elastomer；
The microporous polyurethane elastomer tensile strength of above-mentioned preparation is up to 138MPa, and elongation at break is up to 149%.
Embodiment 6
Prepare polyether polyurethane material：
In reaction bulb, 1,2-PD (11.41g, 0.15mol), propylene oxide (11.62g, 0.2mol), hydrogen is added
Sodium oxide molybdena (4g, 0.1mol), methanol (20mL), in room temperature reaction 12h；Then propylene oxide (11.62g, 0.2mol), sulphur is added
Sour magnalium (150g, 0.2mol), in room temperature reaction 20h；Be subsequently added into ethylene oxide (8.81g, 0.2mol), sodium hydroxide (4g,
0.1mol), for 24 hours in room temperature reaction, reaction mixture 20mL alcohol-water volume ratios are 1 later：1 mixed liquor washing,
Clear liquid is removed in 5000r/min centrifugations, and the above washing, centrifugal process 3 times repeatedly are finally drying to obtain the polyether polyurethane
Material 20 g.
Prepare microporous polyurethane elastomer：
(1) four mouthfuls of burnings are added in methyl diphenylene diisocyanate 30g and liquefied methyl diphenylene diisocyanate 20g
In bottle, 70 DEG C are maintained the temperature at, then the polyether polyurethane material 20g of above-mentioned preparation is added in 0.5g ethylene glycol, mixing
It is poured into the four-hole boiling flask equipped with methyl diphenylene diisocyanate after uniformly, reacts 2h under nitrogen protection, cure 10min
Afterwards, foam-like material is taken out, places 12h, a must be formulated；
Wherein, the preparation method is the same as that of Example 1 for the liquefied methyl diphenylene diisocyanate；
(2) polyether polyurethane material 60g, glycerine 10g, diethylene glycol 0.5g, silicone oil 0.4g, the water of above-mentioned preparation are taken
0.5g, diethylene diamine 0.5g mixing, after stirring evenly, must be formulated b；
(3) formula a obtained by step (1) is poured into rapidly in formula b obtained by step (2), high-speed stirred is uniform, pours into rapidly
Surface is coated in the preheated mold of releasing agent polyethylene wax, mold closing, is put into 40 DEG C of baking ovens and is cured 10min, and demoulding is taken out to obtain the final product
Microporous polyurethane elastomer；
The microporous polyurethane elastomer tensile strength of above-mentioned preparation is up to 135MPa, and elongation at break is up to 140%.
Embodiment 7
Prepare polyether polyurethane material：
In reaction bulb, 1,2-PD (11.41g, 0.15mol), propylene oxide (11.62g, 0.2mol), hydrogen is added
Sodium oxide molybdena (4g, 0.1mol), methanol (20mL), in room temperature reaction 12h；Then propylene oxide (8.71g, 0.15mol), sulphur is added
Sour magnalium (75g, 0.1mol), in room temperature reaction 20h；Be subsequently added into ethylene oxide (6.61g, 0.15mol), sodium hydroxide (6g,
0.15mol), for 24 hours in room temperature reaction, reaction mixture 20mL alcohol-water volume ratios are 1 later：1 mixed liquor washing,
Clear liquid is removed in 5000r/min centrifugations, and the above washing, centrifugal process 3 times repeatedly are finally drying to obtain the polyether polyurethane
Material 20 g.
Prepare microporous polyurethane elastomer：
(1) four mouthfuls of burnings are added in methyl diphenylene diisocyanate 90g and liquefied methyl diphenylene diisocyanate 30g
In bottle, 70 DEG C are maintained the temperature at, then the polyether polyurethane material 35g of above-mentioned preparation is added in 5g ethylene glycol, mixing is equal
It is poured into after even in the four-hole boiling flask equipped with methyl diphenylene diisocyanate, reacts 10h under nitrogen protection, after curing 13min,
Foam-like material is taken out, 8h is placed, a must be formulated；
Wherein, the preparation method is the same as that of Example 1 for the liquefied methyl diphenylene diisocyanate；
(2) polyether polyurethane material 90g, glycerine 20g, diethylene glycol 0.6g, silicone oil 0.5g, the water of above-mentioned preparation are taken
2g, diethylene diamine 1g mixing, after stirring evenly, must be formulated b；
(3) formula a obtained by step (1) is poured into rapidly in formula b obtained by step (2), high-speed stirred is uniform, pours into rapidly
Surface is coated in the preheated mold of releasing agent silicone oil, mold closing, is put into 50 DEG C of baking ovens and is cured 10min, and demoulding is taken out up to poly- ammonia
Ester micro-pore elastomer；
The microporous polyurethane elastomer tensile strength of above-mentioned preparation is up to 141MPa, and elongation at break is up to 152%.
Embodiment 8
Prepare polyether polyurethane material：
In reaction bulb, 1,2-PD (11.41g, 0.15mol), propylene oxide (14.51g, 0.25mol), hydrogen is added
Sodium oxide molybdena (4g, 0.1mol), methanol (10mL), in room temperature reaction 12h；Then propylene oxide (8.71g, 0.15mol), sulphur is added
Sour magnalium (75g, 0.1mol), in room temperature reaction 20h；Be subsequently added into ethylene oxide (6.61g, 0.15mol), sodium hydroxide (6g,
0.15mol), for 24 hours in room temperature reaction, reaction mixture 20mL alcohol-water volume ratios are 1 later：1 mixed liquor washing,
Clear liquid is removed in 5000r/min centrifugations, and the above washing, centrifugal process 3 times repeatedly are finally drying to obtain the polyether polyurethane
Material 20 g.
Prepare microporous polyurethane elastomer：
(1) four mouthfuls of burnings are added in methyl diphenylene diisocyanate 40g and liquefied methyl diphenylene diisocyanate 15g
In bottle, 80 DEG C are maintained the temperature at, then the polyether polyurethane material 15g of above-mentioned preparation is added in 0.1g ethylene glycol, mixing
It is poured into the four-hole boiling flask equipped with methyl diphenylene diisocyanate after uniformly, reacts 2h under nitrogen protection, after curing 2min,
Foam-like material is taken out, 15h is placed, a must be formulated；
Wherein, the preparation method is the same as that of Example 1 for the liquefied methyl diphenylene diisocyanate；
(2) polyether polyurethane material 100g, glycerine 20g, diethylene glycol 0.5g, silicone oil 0.6g, the water of above-mentioned preparation are taken
4g, diethylene diamine 0.8g mixing, after stirring evenly, must be formulated b；
(3) formula a obtained by step (1) is poured into rapidly in formula b obtained by step (2), high-speed stirred is uniform, pours into rapidly
Surface is coated in the preheated mold of releasing agent silicone oil, mold closing, is put into 60 DEG C of baking ovens and is cured 12min, and demoulding is taken out up to poly- ammonia
Ester micro-pore elastomer；
The microporous polyurethane elastomer tensile strength of above-mentioned preparation is up to 137MPa, and elongation at break is up to 153%.
Embodiment 9
Prepare polyether polyurethane material：
In reaction bulb, 1,2-PD (11.41g, 0.15mol), propylene oxide (17.42g, 0.30mol), hydrogen is added
Sodium oxide molybdena (4g, 0.1mol), methanol (20mL), in room temperature reaction 12h；Then propylene oxide (5.81g, 0.1mol), sulphur is added
Sour magnalium (75g, 0.1mol), in room temperature reaction 20h；Be subsequently added into ethylene oxide (4.41g, 0.1mol), sodium hydroxide (4g,
0.1mol), for 24 hours in room temperature reaction, reaction mixture 20mL alcohol-water volume ratios are 1 later：1 mixed liquor washing,
Clear liquid is removed in 5000r/min centrifugations, and the above washing, centrifugal process 3 times repeatedly are finally drying to obtain the polyether polyurethane
Material 20 g.
Prepare microporous polyurethane elastomer：
(1) four mouthfuls of burnings are added in methyl diphenylene diisocyanate 20g and liquefied methyl diphenylene diisocyanate 1g
In bottle, 70 DEG C are maintained the temperature at, then the polyether polyurethane material 1g of above-mentioned preparation is added in 0.1g ethylene glycol, mixing is equal
It is poured into after even in the four-hole boiling flask equipped with methyl diphenylene diisocyanate, reacts 1h under protection of argon gas, it, will after curing 1min
Foam-like material takes out, and places 1h, must be formulated a；
Wherein, the preparation method is the same as that of Example 1 for the liquefied methyl diphenylene diisocyanate；
(2) polyether polyurethane material 1g, glycerine 1g, diethylene glycol 0.1g, silicone oil 0.1g, the water of above-mentioned preparation are taken
0.1g, diethylene diamine 0.1g mixing, after stirring evenly, must be formulated b；
(3) formula a obtained by step (1) is poured into rapidly in formula b obtained by step (2), high-speed stirred is uniform, pours into rapidly
Surface is coated in the preheated mold of releasing agent silicone oil, mold closing, is put into 50 DEG C of baking ovens and is cured 1min, and demoulding is taken out up to poly- ammonia
Ester micro-pore elastomer；
The microporous polyurethane elastomer tensile strength of above-mentioned preparation is up to 145MPa, and elongation at break is up to 146%.
Embodiment 10
Prepare polyether polyurethane material：
In reaction bulb, 1,2-PD (19.02g, 0.25mol), propylene oxide (14.52g, 0.25mol), hydrogen is added
Sodium oxide molybdena (8g, 0.2mol), methanol (20mL), in room temperature reaction 12h；Then be added propylene oxide (14.52g, 0.25mol),
Sulfuric acid magnalium (75g, 0.1mol), in room temperature reaction 20h；It is subsequently added into ethylene oxide (11.01g, 0.25mol), sodium hydroxide
(4g, 0.1mol), for 24 hours in room temperature reaction, reaction mixture 20mL alcohol-water volume ratios are 1 later：1 mixed liquor washing,
Clear liquid is removed in 5000r/min centrifugations, and the above washing, centrifugal process 3 times repeatedly are finally drying to obtain the polyether polyurethane
Material 30g.
Prepare microporous polyurethane elastomer：
(1) methyl diphenylene diisocyanate 100g and liquefied methyl diphenylene diisocyanate 50g is added four mouthfuls
In flask, 80 DEG C are maintained the temperature at, then the polyether polyurethane material 50g of above-mentioned preparation is added in 10g ethylene glycol, mixing
It is poured into the four-hole boiling flask equipped with methyl diphenylene diisocyanate after uniformly, reacts 20h under protection of argon gas, cure 30min
Afterwards, foam-like material is taken out, places 30h, a must be formulated；
Wherein, the preparation method is the same as that of Example 1 for the liquefied methyl diphenylene diisocyanate；
(2) the polyether polyurethane material 150g of above-mentioned preparation, glycerine 25g, diethylene glycol 2g, silicone oil 4g, water 5g, two are taken
Ethylene diamine 2g mixing, after stirring evenly, must be formulated b；
(3) formula a obtained by step (1) is poured into rapidly in formula b obtained by step (2), high-speed stirred is uniform, pours into rapidly
Surface is coated in the preheated mold of releasing agent emulsification methyl-silicone oil, and mold closing is put into 80 DEG C of baking ovens and cures 15min, is demoulded, and is taken out
Up to microporous polyurethane elastomer；
The microporous polyurethane elastomer tensile strength of above-mentioned preparation is up to 138MPa, and elongation at break is up to 148%.
Claims (9)
1. a kind of polyether polyurethane material, which is characterized in that the polyether polyurethane material is prepared as follows
It arrives：
In organic solvent, initiator polyalcohol, in reacting at room temperature 1~30h, is obtained with alkylene oxide A under the catalytic action of alkali A
System A；Alkylene oxide B and metal sulfate are added in system A, in reacting at room temperature 1~40h, obtain system B；By alkylene oxide C and
Alkali B is added in system B, and in reacting at room temperature 1~60h, reaction mixture is post-treated later, and the polyether polyurethane is made
Material；
Wherein, the substance that feeds intake of the polyalcohol and alkylene oxide A, alkali A, alkylene oxide B, metal sulfate, alkylene oxide C, alkali B
The ratio between amount is 1: 0.01~10: 0.01~10: 0.01~10: 0.1~10: 0.1~10: 0.1~10；
The volumetric usage of the organic solvent is calculated as 0.001~10g/mL with the quality of polyalcohol；
The organic solvent is selected from methanol；
The polyalcohol is selected from 1,2- propylene glycol；
The alkylene oxide A is selected from propylene oxide；
The alkali A is selected from NaOH；
The alkylene oxide B is selected from propylene oxide；
The metal sulfate is selected from sulfuric acid magnalium；
The alkylene oxide C is selected from ethylene oxide；
The alkali B is selected from NaOH.
2. polyether polyurethane material as described in claim 1, which is characterized in that the polyalcohol and alkylene oxide A, alkali A,
The ratio between amount for the substance that feeds intake of alkylene oxide B, metal sulfate, alkylene oxide C, alkali B is 1: 1~2: 1~2: 1~2: 2~4: 2~4:
2~4.
3. polyether polyurethane material as described in claim 1, which is characterized in that the volumetric usage of the organic solvent is with more
The quality of first alcohol is calculated as 0.5~2mL/g.
4. polyether polyurethane material as described in claim 1, which is characterized in that the post-processing approach of the reaction mixture
For：After reaction, reaction mixture is washed through the mixed liquor that alcohol-water volume ratio is 1: 1, and 5000r/min centrifugations are removed clear
Liquid, the above washing, centrifugal process 3 times repeatedly, is finally drying to obtain the polyether polyurethane material.
5. polyether polyurethane material as described in claim 1, which is characterized in that the polyether polyurethane material is by such as
Lower section method is prepared：
In methyl alcohol, initiator 1,2-PD and propylene oxide A are under the catalytic action of sodium hydroxide A, in room temperature reaction
12h obtains system A；Propylene oxide B and sulfuric acid magnalium are added in system A, in room temperature reaction 20h, obtain system B；By epoxy
Ethane and sodium hydroxide B are added in system B, and for 24 hours in room temperature reaction, reaction mixture is 1: 1 through alcohol-water volume ratio later
Mixed liquor washs, and clear liquid is removed in 5000r/min centrifugations, the above washing, centrifugal process 3 times repeatedly, is finally drying to obtain described
Polyether polyurethane material；
Wherein, the 1,2-PD and propylene oxide A, sodium hydroxide A, propylene oxide B, sulfuric acid magnalium, ethylene oxide, hydrogen
The ratio between amount for the substance that feeds intake of sodium oxide molybdena B is 1: 1~2: 1~2: 1~2: 2~4: 2~4: 2~4；
The volumetric usage of the methanol is calculated as 0.5~2mL/g with the quality of 1,2- propylene glycol.
6. a kind of application of polyether polyurethane material as described in claim 1 in preparing microporous polyurethane elastomer, institute
The method for stating application is：
(1) by 1~50 part of addition of 1~100 part of methyl diphenylene diisocyanate and liquefied methyl diphenylene diisocyanate
In reaction vessel, 70~80 DEG C are maintained the temperature at, then by 1~50 part of the polyether polyurethane material and ethylene glycol 0.1
~10 parts of mixture is also added in reaction vessel, reacts 1~20h under inert gas protection, after curing 1~30min, by object
Material, which takes out, places 1~30h, must be formulated a；
(2) 1~150 part of the polyether polyurethane material, 1~25 part of glycerine, 0.1~2 part of diethylene glycol, silicone oil 0.1 are taken
~4 parts, 0.1~5 part of water, the mixing of 0.1~2 part of diethylene diamine, after stirring evenly, b must be formulated；
(3) formula a obtained by step (1) is poured into formula b obtained by step (2), pours into surface after stirring evenly and is coated with releasing agent
Preheated mold in, mold closing is put into 30~80 DEG C of baking ovens 1~15min of curing, and demoulding is taken out up to microporous polyurethane elasticity
Body.
7. application as claimed in claim 6, which is characterized in that in the step (1), the liquefied diphenyl methane two is different
Cyanate is prepared as follows to obtain：Solid-state methyl diphenylene diisocyanate is placed in beaker, is added in water bath with thermostatic control
Liquefied methyl diphenylene diisocyanate is prepared to 50 DEG C in heat.
8. application as claimed in claim 6, which is characterized in that in the step (3), the releasing agent is silicone compound
Object, silicone oil, silicones metlyl branching silicone oil, methyl-silicone oil, emulsification methyl-silicone oil, hydrogeneous methyl-silicone oil, silicone grease, silicones, silicon
Rubber, silicon rubber toluene solution, microcrystalline wax or polyethylene wax.
9. application as claimed in claim 6, the microporous polyurethane elastomer is as sole material.
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