CN105566625A - Polyether urethane material, method for preparing same and application of polyether urethane material - Google Patents
Polyether urethane material, method for preparing same and application of polyether urethane material Download PDFInfo
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- CN105566625A CN105566625A CN201510975996.2A CN201510975996A CN105566625A CN 105566625 A CN105566625 A CN 105566625A CN 201510975996 A CN201510975996 A CN 201510975996A CN 105566625 A CN105566625 A CN 105566625A
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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 invention provides a polyether urethane material. A method for preparing the polyether urethane material includes carrying out room-temperature reaction on polyhydric alcohol of initiators and alkylene oxide A in organic solvents under catalytic actions of alkali A for 1-30 h to obtain systems A; adding alkylene oxide B and metal sulfate into the systems A and carrying out room-temperature reaction on the alkylene oxide B, the metal sulfate and the systems A for 1-40 h to obtain systems B; adding alkylene oxide C and alkali B into the systems B, carrying out room-temperature reaction on the alkylene oxide C, the alkali B and the systems B for 1-60 h to obtain reaction mixtures and carrying out after-treatment on the reaction mixtures to obtain a finished product. The polyether urethane material and the method have the advantages that the polyether urethane material can be used for preparing polyurethane cellular elastomers which are used as shoe sole materials; the polyether urethane material is high in low-temperature performance, hydrolysis resistance and mildew resistance, the reaction time and the mold release time can be shortened when the polyether urethane material is used for preparing the polyurethane cellular elastomers, and the physical performance of the product can be improved.
Description
(1) technical field
The invention belongs to polymeric material field, be specifically related to a kind of polyether polyurethane material and preparation method thereof and application.
(2) background technology
Polyether glycol is the important source material of synthesis of polyurethane material.In recent years, along with the develop rapidly of polyurethane industrial, the raising around Contents In Polyether Polyol capability and performance of domestic and international Ge great manufacturing enterprise and scientific research institution and the reduction of production cost, carried out a large amount of research-and-development activitys.
Chinese shoemaking is a dark horse, in short more than ten years, become the maximum footwear producing country in the whole world and export State, particularly after China's entry into the WTO, Chinese shoemaking more presents powerful developing state, and footwear industry output Yi Zhan world total amount nearly 40% ~ 50%, in global footwear trade, China's footwear export amount also accounts for 25%, and both all rank first in the world.At present, China's footwear consumption accounts for 22% of world's aggregate consumption, is one of most important leather shoes country of consumption in the whole world.Along with the raising of living standards of the people, people are also that when the river rises the boat goes up to the requirement of footwear, only focus on elegant in appearance, change into while emphasis is elegant in appearance, focus on its security comfort by former.And the quality of footwear quality and the performance of material for sole of shoe have extremely close contact, decide the functional of sole and comfortableness.We also obviously felt the progress along with production technology in recent years, material for sole of shoe material kind is more and more abundanter, and the embodiment degree of tailored version is more and more stronger, continually developing therefore through enterprise, sole of shoe material also emerges gradually, and the quality for China's footwear provides certain guarantee.China is the first in the world Chan Xie big country, produces about 5,000,000,000 pairs, footwear per year, accounts for 42% of global footwear output.But urethane only has 2.8 ten thousand/a at the consumption of this industry at present, accounts for 2% of footwear total raw material amount.And polyurethane material accounts for 6.8% in whole world shoe industry, in economically developed Europe, this ratio is up to more than 20%.Polyurethane shoe material market potential is very large.In recent years, the tempo of China's microcellular polyurethane shoe sole is very fast, and annual growth is more than 12%, but kind is dull, is substantially confined to leather shoe sole and athletic shoe sole.Visible, our work of this field with abroad compare, gap is very far away.
In " 15 " and planning proposal in 2015 of Chinese polyurethane industrial association auspices, the production technique of research and development polyether-type and polyester polyethers copoly type, hydrolysis microcellular polyurethane elastomer sole material is carried out as a developing direction of following for some time elastomeric article.It is expected to, Science in Future in China polyurethane shoe material market will become polyurethane field new growth engines.Therefore, the synthesis of polyurethane shoe-sole polyethers very has future, but its research relevant but rarely has report.
(3) summary of the invention
Technical purpose of the present invention is, for shortcomings such as current PAUR facile hydrolysis and biological degradations, and the defect that the sole made easily chaps, ruptures, the invention provides a kind of polyether polyurethane material and preparation method thereof, just in time overcome the weakness of PAUR sole with the sole that polyether polyurethane material of the present invention makes, there is stronger low-temperature performance, anti-hydrolytic performance and anti-mildew sex change energy.In addition, prepare polyurethane elastomer by polyether polyurethane material of the present invention, shorten reaction times and demould time, and the physicals of product can be improved.
For achieving the above object, the present invention adopts following technical scheme:
A kind of polyether polyurethane material, described polyether polyurethane material prepares as follows:
In organic solvent, initiator polyvalent alcohol and oxirane A, under the katalysis of alkali A, in room temperature reaction 1 ~ 30h, obtain system A; Oxirane B and metal sulfate are added in system A, in room temperature reaction 1 ~ 40h, obtain system B; Be added in system B by oxirane C and alkali B, in room temperature reaction 1 ~ 60h, reaction mixture is through aftertreatment afterwards, obtained described polyether polyurethane material;
Wherein, described polyvalent alcohol and the ratio of the amount of substance that feeds intake of oxirane A, alkali A, oxirane B, metal sulfate, oxirane C, alkali B are 1:0.01 ~ 10:0.01 ~ 10:0.01 ~ 10:0.1 ~ 10:0.1 ~ 10:0.1 ~ 10 (preferred 1:1 ~ 2:1 ~ 2:1 ~ 2:2 ~ 4:2 ~ 4:2 ~ 4);
The volumetric usage of described organic solvent counts 0.001 ~ 10mL/g (preferably 0.5 ~ 2mL/g) with the quality of polyvalent alcohol;
Described organic solvent is selected from methyl alcohol, ethanol, propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, Pentyl alcohol, n-Octanol, acetone, butanone, chloroform, methylene dichloride, ether, dithiocarbonic anhydride, 1-Methyl-2-Pyrrolidone, N-N-dimethyl formamide, N-N-N,N-DIMETHYLACETAMIDE, methyl-sulphoxide, tetrahydrofuran (THF), ethyl acetate, dioxane, acetonitrile, benzene, toluene or dimethylbenzene, particular methanol or ethanol;
Described polyvalent alcohol is selected from ethylene glycol, 1,2-PD, BDO, hexylene glycol, neopentyl glycol, Diethylene Glycol, dipropylene glycol, TriMethylolPropane(TMP) or glycerine, preferred 1,2-PD;
Described oxirane A is selected from oxyethane, propylene oxide, butylene oxide ring, epoxypentane, oxepane, oxepane or octylene oxide, optimization ethylene oxide or propylene oxide;
Described alkali A is selected from NaOH, KOH, Ba (OH)
2or Ca (OH)
2, preferred NaOH;
The definition of described oxirane B is identical with the definition of oxirane A;
Described metal sulfate is selected from sodium sulfate, magnesium sulfate, ferrous sulfate, ferric sulfate, barium sulfate, potassium sulfate, potassium aluminium sulfate, calcium sulfate or sulfuric acid magnalium, preferably sulfuric acid magnalium;
The definition of described oxirane C is identical with the definition of oxirane A;
The definition of described alkali B is identical with the definition of alkali A.
In preparation method of the present invention, concrete, the post-treating method of described reaction mixture is:
After reaction terminates, reaction mixture is the mixed solution washing of 1:1 through alcohol-water volume ratio, and 5000r/min is centrifugal removes clear liquid, and above washing, centrifugal process 3 times repeatedly, namely final drying obtains described polyether polyurethane material.
Above-mentioned term " system A ", " system B " do not have special implication, are labeled as " A ", " B " just for distinguishing the system in different operating step.Term " oxirane A ", " oxirane B ", " oxirane C " do not have special implication yet, all refer to the oxirane on ordinary meaning, are labeled as " A ", " B ", " C " just for distinguishing oxirane used in different operating step." alkali A ", " alkali B " are with it in like manner.
Concrete, recommend polyether polyurethane material of the present invention to prepare as follows:
In methyl alcohol, initiator 1,2-PD and propylene oxide A, under the katalysis of sodium hydroxide A, in room temperature reaction 12h, obtain system A; Propylene oxide B and sulfuric acid magnalium are added in system A, in room temperature reaction 20h, obtain system B; Oxyethane and sodium hydroxide B are added in system B, in room temperature reaction 24h, reaction mixture is the mixed solution washing of 1:1 through alcohol-water volume ratio afterwards, and 5000r/min is centrifugal removes clear liquid, more than washing, centrifugal process 3 times repeatedly, namely final drying obtains described polyether polyurethane material;
Wherein, described 1,2-PD is 1:1 ~ 2:1 ~ 2:1 ~ 2:2 ~ 4:2 ~ 4:2 ~ 4 with the ratio of the amount of substance that feeds intake of propylene oxide A, sodium hydroxide A, propylene oxide B, sulfuric acid magnalium, cyclohexane, sodium hydroxide B;
The volumetric usage of described methyl alcohol counts 0.5 ~ 2mL/g with the quality of 1,2-PD.
Above-mentioned term " propylene oxide A ", " propylene oxide B " do not have special implication, are labeled as " A ", " B " just for distinguishing propylene oxide used in different operating step." sodium hydroxide A ", " sodium hydroxide B " are with it in like manner.
Present invention also offers a kind of described polyether polyurethane material and preparing the application in microporous polyurethane elastomer, the method for described application is:
(1) diphenylmethanediisocyanate 1 ~ 50 part of diphenylmethanediisocyanate 1 ~ 100 part and liquefaction is added in reaction vessel, maintain the temperature at 70 ~ 80 DEG C, then the mixture of polyether polyurethane material of the present invention 1 ~ 50 part and ethylene glycol 0.1 ~ 10 part is also added in reaction vessel, 1 ~ 20h is reacted under protection of inert gas, after slaking 1 ~ 30min, material (spumescence) is taken out placement 1 ~ 30h, and must fill a prescription a;
(2) get polyether polyurethane material of the present invention 1 ~ 150 part, glycerine 1 ~ 25 part, Diethylene Glycol 0.1 ~ 2 part, silicone oil 0.1 ~ 4 part, 0.1 ~ 5 part, water, diethylene diamine 0.1 ~ 2 part mixing, after stirring, must fill a prescription b;
(3) step (1) gained formula a is poured in step (2) gained formula b, pouring surface after stirring into scribbles in the preheated mold of releasing agent, mold closing, puts into 30 ~ 80 DEG C of baking oven slaking 1 ~ 15min, the demoulding, takes out and obtains microporous polyurethane elastomer.
Wherein, the diphenylmethanediisocyanate of described liquefaction prepares as follows: be placed in beaker by solid-state diphenylmethanediisocyanate, is heated to 50 DEG C in water bath with thermostatic control, prepares the diphenylmethanediisocyanate of liquefaction.
Described releasing agent can adopt silicone compounds, silicone oil, silicone resin metlyl branching silicone oil, methyl-silicone oil, emulsification methyl-silicone oil, hydrogeneous methyl-silicone oil, silicone grease, silicone resin, silicon rubber, silicon rubber toluene solution, microcrystalline wax or polyethylene wax etc.
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, beneficial effect of the present invention is:
Polyether polyurethane material of the present invention has stronger low-temperature performance, anti-hydrolytic performance and anti-mildew sex change energy, and this material can be used for the preparation of polyurethane elastomer, and preparation process shortens reaction times and demould time, and can improve the physicals of product.Be applied to the conventional polyether polyols of polyurethane shoe-sole stoste in the market, undertaken by anionic polymerization mechanism under NaOH catalysis by initiator and epoxy compounds, easily there is the higher degree of unsaturation of side reaction formation in epoxy compounds in the course of the polymerization process, polyethers actual functionality is reduced, make the mechanical property of polyurethane shoe-sole poor, the demand in market can not be met.The present invention adopt functionality be 2 or 3 polyvalent alcohol be initiator, two kinds of catalyst segments use, with Polymerization of Propylene Oxide, ethylene oxide-capped, final obtained novel polyether type polyurethane material.The polyether polyurethane material activity of synthesis is high, and 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 macromolecular material of high comprehensive performance.Every physical index of the microporous polyurethane elastomer sole adopting polyether polyurethane material of the present invention to prepare has been better than the universal product of existing market, and intensity is high, good toughness, and tensile strength can higher than 140MPa, and elongation at break is greater than 150%.
(4) accompanying drawing explanation
Fig. 1 is the stretched mechanical intensity data figure of microporous polyurethane elastomer prepared by embodiment 1 ~ 3.
(5) embodiment
Below by way of specific embodiment, the present invention is described in further detail, but protection scope of the present invention is not limited in this.
Embodiment 1
Preparation polyether polyurethane material:
In reaction flask, add 1,2-PD (7.61g, 0.1mol), propylene oxide (5.81g, 0.1mol), sodium hydroxide (4g, 0.1mol), methyl alcohol (5mL), in room temperature reaction 12h; Then propylene oxide (5.81g, 0.1mol), sulfuric acid magnalium (75g, 0.1mol) is added, in room temperature reaction 20h; Then oxyethane (8.81g is added, 0.2mol), sodium hydroxide (4g, 0.1mol), in room temperature reaction 24h, reaction mixture 10mL alcohol-water volume ratio is the mixed solution washing of 1:1 afterwards, 5000r/min is centrifugal removes clear liquid, and above washing, centrifugal process 3 times repeatedly, namely final drying obtains described polyether polyurethane material 10g.
Prepare microporous polyurethane elastomer:
(1) the diphenylmethanediisocyanate 15g of diphenylmethanediisocyanate 60g and liquefaction is added in four-hole boiling flask, maintain the temperature at 70 DEG C, then the polyether polyurethane material 5g of above-mentioned preparation is added in 1g ethylene glycol, pour into after mixing and be equipped with in the four-hole boiling flask of diphenylmethanediisocyanate, react 2h under nitrogen protection, after slaking 10min, spumescence material is taken out, place 2h, must fill a prescription a;
Wherein, the diphenylmethanediisocyanate of described liquefaction prepares as follows: be placed in by solid-state diphenylmethanediisocyanate in 500ml beaker, be heated to 50 DEG C in water bath with thermostatic control, prepare the diphenylmethanediisocyanate of liquefaction;
(2) get the polyether polyurethane material 1g of above-mentioned preparation, glycerine 2g, Diethylene Glycol 0.2g, silicone oil 0.2g, water 0.3g, diethylene diamine 0.3g mix, after stirring, must fill a prescription b;
(3) step (1) gained formula a is poured into rapidly in step (2) gained formula b, high-speed stirring is even, pouring rapidly surface into scribbles in the preheated mold of releasing agent silicone oil, mold closing, put into 40 DEG C of baking oven slaking 10min, the demoulding, takes out and obtains microporous polyurethane elastomer;
The stretched mechanical intensity data figure of the above-mentioned microporous polyurethane elastomer prepared is shown in accompanying drawing 1, can be found by data in Fig. 1, and this microporous polyurethane elastomer tensile strength can reach 138MPa, and elongation at break reaches 143%.
Embodiment 2
Preparation polyether polyurethane material:
In reaction flask, add 1,2-PD (7.61g, 0.1mol), propylene oxide (8.71g, 0.15mol), sodium hydroxide (4g, 0.1mol), methyl alcohol (5mL), in room temperature reaction 12h; Then propylene oxide (5.81g, 0.1mol), sulfuric acid magnalium (75g, 0.1mol) is added, in room temperature reaction 20h; Then oxyethane (6.61g is added, 0.15mol), sodium hydroxide (4g, 0.1mol), in room temperature reaction 24h, reaction mixture 10mL alcohol-water volume ratio is the mixed solution washing of 1:1 afterwards, 5000r/min is centrifugal removes clear liquid, and above washing, centrifugal process 3 times repeatedly, namely final drying obtains described polyether polyurethane material 15g.
Prepare microporous polyurethane elastomer:
(1) the diphenylmethanediisocyanate 20g of diphenylmethanediisocyanate 70g and liquefaction is added in four-hole boiling flask, maintain the temperature at 70 DEG C, then the polyether polyurethane material 5g of above-mentioned preparation is added in 5g ethylene glycol, pour into after mixing and be equipped with in the four-hole boiling flask of diphenylmethanediisocyanate, under argon shield, react 3h, after slaking 10min, spumescence material is taken out, place 3h, must fill a prescription a;
Wherein, the preparation method of the diphenylmethanediisocyanate of described liquefaction is with embodiment 1;
(2) get the polyether polyurethane material 70g of above-mentioned preparation, glycerine 15g, Diethylene Glycol 0.5g, silicone oil 0.4g, water 0.5g, diethylene diamine 0.3g mix, after stirring, must fill a prescription b;
(3) step (1) gained formula a is poured into rapidly in step (2) gained formula b, high-speed stirring is even, pouring rapidly surface into scribbles in the preheated mold of releasing agent silicone resin metlyl branching silicone oil, mold closing, put into 40 DEG C of baking oven slaking 10min, the demoulding, takes out and obtains microporous polyurethane elastomer;
The stretched mechanical intensity data figure of the above-mentioned microporous polyurethane elastomer prepared is shown in accompanying drawing 1, can be found by data in Fig. 1, and this microporous polyurethane elastomer tensile strength can reach 132MPa, and elongation at break reaches 131%.
Embodiment 3
Preparation polyether polyurethane material:
In reaction flask, add 1,2-PD (11.41g, 0.15mol), propylene oxide (5.81g, 0.1mol), sodium hydroxide (4g, 0.1mol), methyl alcohol (10mL), in room temperature reaction 12h; Then propylene oxide (4.41g, 0.1mol), sulfuric acid magnalium (75g, 0.1mol) is added, in room temperature reaction 20h; Then oxyethane (6.61g is added, 0.15mol), sodium hydroxide (4g, 0.1mol), in room temperature reaction 24h, reaction mixture 10mL alcohol-water volume ratio is the mixed solution washing of 1:1 afterwards, 5000r/min is centrifugal removes clear liquid, and above washing, centrifugal process 3 times repeatedly, namely final drying obtains described polyether polyurethane material 15g.
Prepare microporous polyurethane elastomer:
(1) the diphenylmethanediisocyanate 30g of diphenylmethanediisocyanate 80g and liquefaction is added in four-hole boiling flask, maintain the temperature at 80 DEG C, then the polyether polyurethane material 10g of above-mentioned preparation is added in 5g ethylene glycol, pour into after mixing and be equipped with in the four-hole boiling flask of diphenylmethanediisocyanate, react 5h under nitrogen protection, after slaking 10min, spumescence material is taken out, place 5h, must fill a prescription a;
Wherein, the preparation method of the diphenylmethanediisocyanate of described liquefaction is with embodiment 1;
(2) get the polyether polyurethane material 80g of above-mentioned preparation, glycerine 15g, Diethylene Glycol 0.5g, silicone oil 0.4g, water 0.5g, diethylene diamine 0.3g mix, after stirring, must fill a prescription b;
(3) step (1) gained formula a is poured into rapidly in step (2) gained formula b, high-speed stirring is even, pouring rapidly surface into scribbles in the preheated mold of releasing agent methyl-silicone oil, mold closing, put into 50 DEG C of baking oven slaking 15min, the demoulding, takes out and obtains microporous polyurethane elastomer;
The stretched mechanical intensity data figure of the above-mentioned microporous polyurethane elastomer prepared is shown in accompanying drawing 1, can be found by data in Fig. 1, and this microporous polyurethane elastomer tensile strength can reach 146MPa, and elongation at break reaches 152%.
Embodiment 4
Preparation polyether polyurethane material:
In reaction flask, add 1,2-PD (11.41g, 0.15mol), propylene oxide (8.71g, 0.15mol), sodium hydroxide (4g, 0.1mol), methyl alcohol (10mL), in room temperature reaction 12h; Then propylene oxide (5.81g, 0.1mol), sulfuric acid magnalium (75g, 0.1mol) is added, in room temperature reaction 20h; Then oxyethane (4.41g is added, 0.1mol), sodium hydroxide (4g, 0.1mol), in room temperature reaction 24h, reaction mixture 10mL alcohol-water volume ratio is the mixed solution washing of 1:1 afterwards, 5000r/min is centrifugal removes clear liquid, and above washing, centrifugal process 3 times repeatedly, namely final drying obtains described polyether polyurethane material 20g.
Prepare microporous polyurethane elastomer:
(1) the diphenylmethanediisocyanate 15g of diphenylmethanediisocyanate 80g and liquefaction is added in four-hole boiling flask, maintain the temperature at 80 DEG C, then the polyether polyurethane material 30g of above-mentioned preparation is added in 3g ethylene glycol, pour into after mixing and be equipped with in the four-hole boiling flask of diphenylmethanediisocyanate, react 6h under nitrogen protection, after slaking 8min, spumescence material is taken out, place 2h, must fill a prescription a;
Wherein, the preparation method of the diphenylmethanediisocyanate of described liquefaction is with embodiment 1;
(2) get the polyether polyurethane material 65g of above-mentioned preparation, glycerine 12g, Diethylene Glycol 0.3g, silicone oil 0.3g, water 0.5g, diethylene diamine 0.2g mix, after stirring, must fill a prescription b;
(3) step (1) gained formula a is poured into rapidly in step (2) gained formula b, high-speed stirring is even, pouring rapidly surface into scribbles in the preheated mold of the hydrogeneous methyl-silicone oil of releasing agent, mold closing, put into 45 DEG C of baking oven slaking 5min, the demoulding, takes out and obtains microporous polyurethane elastomer;
The microporous polyurethane elastomer tensile strength of above-mentioned preparation can reach 138MPa, and elongation at break reaches 143%.
Embodiment 5
Preparation polyether polyurethane material:
In reaction flask, add 1,2-PD (15.22g, 0.2mol), propylene oxide (11.62g, 0.2mol), sodium hydroxide (4g, 0.1mol), methyl alcohol (20mL), in room temperature reaction 12h; Then propylene oxide (11.62g, 0.2mol), sulfuric acid magnalium (150g, 0.2mol) is added, in room temperature reaction 20h; Then oxyethane (8.81g is added, 0.2mol), sodium hydroxide (4g, 0.1mol), in room temperature reaction 24h, reaction mixture 20mL alcohol-water volume ratio is the mixed solution washing of 1:1 afterwards, 5000r/min is centrifugal removes clear liquid, and above washing, centrifugal process 3 times repeatedly, namely final drying obtains described polyether polyurethane material 25g.
Prepare microporous polyurethane elastomer:
(1) the diphenylmethanediisocyanate 25g of diphenylmethanediisocyanate 80g and liquefaction is added in four-hole boiling flask, maintain the temperature at 70 DEG C, then the polyether polyurethane material 12g of above-mentioned preparation is added in 0.8g ethylene glycol, pour into after mixing and be equipped with in the four-hole boiling flask of diphenylmethanediisocyanate, under argon shield, react 5h, after slaking 7min, spumescence material is taken out, place 6h, must fill a prescription a;
Wherein, the preparation method of the diphenylmethanediisocyanate of described liquefaction is with embodiment 1;
(2) get the polyether polyurethane material 15g of above-mentioned preparation, glycerine 16g, Diethylene Glycol 0.8g, silicone oil 0.5g, water 0.3g, diethylene diamine 0.5g mix, after stirring, must fill a prescription b;
(3) step (1) gained formula a is poured into rapidly in step (2) gained formula b, high-speed stirring is even, pouring rapidly surface into scribbles in the preheated mold of releasing agent microcrystalline wax, mold closing, put into 60 DEG C of baking oven slaking 12min, the demoulding, takes out and obtains microporous polyurethane elastomer;
The microporous polyurethane elastomer tensile strength of above-mentioned preparation can reach 138MPa, and elongation at break reaches 149%.
Embodiment 6
Preparation polyether polyurethane material:
In reaction flask, add 1,2-PD (11.41g, 0.15mol), propylene oxide (11.62g, 0.2mol), sodium hydroxide (4g, 0.1mol), methyl alcohol (20mL), in room temperature reaction 12h; Then propylene oxide (11.62g, 0.2mol), sulfuric acid magnalium (150g, 0.2mol) is added, in room temperature reaction 20h; Then oxyethane (8.81g is added, 0.2mol), sodium hydroxide (4g, 0.1mol), in room temperature reaction 24h, reaction mixture 20mL alcohol-water volume ratio is the mixed solution washing of 1:1 afterwards, 5000r/min is centrifugal removes clear liquid, and above washing, centrifugal process 3 times repeatedly, namely final drying obtains described polyether polyurethane material 20g.
Prepare microporous polyurethane elastomer:
(1) the diphenylmethanediisocyanate 20g of diphenylmethanediisocyanate 30g and liquefaction is added in four-hole boiling flask, maintain the temperature at 70 DEG C, then the polyether polyurethane material 20g of above-mentioned preparation is added in 0.5g ethylene glycol, pour into after mixing and be equipped with in the four-hole boiling flask of diphenylmethanediisocyanate, react 2h under nitrogen protection, after slaking 10min, spumescence material is taken out, place 12h, must fill a prescription a;
Wherein, the preparation method of the diphenylmethanediisocyanate of described liquefaction is with embodiment 1;
(2) get the polyether polyurethane material 60g of above-mentioned preparation, glycerine 10g, Diethylene Glycol 0.5g, silicone oil 0.4g, water 0.5g, diethylene diamine 0.5g mix, after stirring, must fill a prescription b;
(3) step (1) gained formula a is poured into rapidly in step (2) gained formula b, high-speed stirring is even, pouring rapidly surface into scribbles in the preheated mold of releasing agent polyethylene wax, mold closing, put into 40 DEG C of baking oven slaking 10min, the demoulding, takes out and obtains microporous polyurethane elastomer;
The microporous polyurethane elastomer tensile strength of above-mentioned preparation can reach 135MPa, and elongation at break reaches 140%.
Embodiment 7
Preparation polyether polyurethane material:
In reaction flask, add 1,2-PD (11.41g, 0.15mol), propylene oxide (11.62g, 0.2mol), sodium hydroxide (4g, 0.1mol), methyl alcohol (20mL), in room temperature reaction 12h; Then propylene oxide (8.71g, 0.15mol), sulfuric acid magnalium (75g, 0.1mol) is added, in room temperature reaction 20h; Then oxyethane (6.61g is added, 0.15mol), sodium hydroxide (6g, 0.15mol), in room temperature reaction 24h, reaction mixture 20mL alcohol-water volume ratio is the mixed solution washing of 1:1 afterwards, 5000r/min is centrifugal removes clear liquid, and above washing, centrifugal process 3 times repeatedly, namely final drying obtains described polyether polyurethane material 20g.
Prepare microporous polyurethane elastomer:
(1) the diphenylmethanediisocyanate 30g of diphenylmethanediisocyanate 90g and liquefaction is added in four-hole boiling flask, maintain the temperature at 70 DEG C, then the polyether polyurethane material 35g of above-mentioned preparation is added in 5g ethylene glycol, pour into after mixing and be equipped with in the four-hole boiling flask of diphenylmethanediisocyanate, react 10h under nitrogen protection, after slaking 13min, spumescence material is taken out, place 8h, must fill a prescription a;
Wherein, the preparation method of the diphenylmethanediisocyanate of described liquefaction is with embodiment 1;
(2) get the polyether polyurethane material 90g of above-mentioned preparation, glycerine 20g, Diethylene Glycol 0.6g, silicone oil 0.5g, water 2g, diethylene diamine 1g mix, after stirring, must fill a prescription b;
(3) step (1) gained formula a is poured into rapidly in step (2) gained formula b, high-speed stirring is even, pouring rapidly surface into scribbles in the preheated mold of releasing agent silicone oil, mold closing, put into 50 DEG C of baking oven slaking 10min, the demoulding, takes out and obtains microporous polyurethane elastomer;
The microporous polyurethane elastomer tensile strength of above-mentioned preparation can reach 141MPa, and elongation at break reaches 152%.
Embodiment 8
Preparation polyether polyurethane material:
In reaction flask, add 1,2-PD (11.41g, 0.15mol), propylene oxide (14.51g, 0.25mol), sodium hydroxide (4g, 0.1mol), methyl alcohol (10mL), in room temperature reaction 12h; Then propylene oxide (8.71g, 0.15mol), sulfuric acid magnalium (75g, 0.1mol) is added, in room temperature reaction 20h; Then oxyethane (6.61g is added, 0.15mol), sodium hydroxide (6g, 0.15mol), in room temperature reaction 24h, reaction mixture 20mL alcohol-water volume ratio is the mixed solution washing of 1:1 afterwards, 5000r/min is centrifugal removes clear liquid, and above washing, centrifugal process 3 times repeatedly, namely final drying obtains described polyether polyurethane material 20g.
Prepare microporous polyurethane elastomer:
(1) the diphenylmethanediisocyanate 15g of diphenylmethanediisocyanate 40g and liquefaction is added in four-hole boiling flask, maintain the temperature at 80 DEG C, then the polyether polyurethane material 15g of above-mentioned preparation is added in 0.1g ethylene glycol, pour into after mixing and be equipped with in the four-hole boiling flask of diphenylmethanediisocyanate, react 2h under nitrogen protection, after slaking 2min, spumescence material is taken out, place 15h, must fill a prescription a;
Wherein, the preparation method of the diphenylmethanediisocyanate of described liquefaction is with embodiment 1;
(2) get the polyether polyurethane material 100g of above-mentioned preparation, glycerine 20g, Diethylene Glycol 0.5g, silicone oil 0.6g, water 4g, diethylene diamine 0.8g mix, after stirring, must fill a prescription b;
(3) step (1) gained formula a is poured into rapidly in step (2) gained formula b, high-speed stirring is even, pouring rapidly surface into scribbles in the preheated mold of releasing agent silicone oil, mold closing, put into 60 DEG C of baking oven slaking 12min, the demoulding, takes out and obtains microporous polyurethane elastomer;
The microporous polyurethane elastomer tensile strength of above-mentioned preparation can reach 137MPa, and elongation at break reaches 153%.
Embodiment 9
Preparation polyether polyurethane material:
In reaction flask, add 1,2-PD (11.41g, 0.15mol), propylene oxide (17.42g, 0.30mol), sodium hydroxide (4g, 0.1mol), methyl alcohol (20mL), in room temperature reaction 12h; Then propylene oxide (5.81g, 0.1mol), sulfuric acid magnalium (75g, 0.1mol) is added, in room temperature reaction 20h; Then oxyethane (4.41g is added, 0.1mol), sodium hydroxide (4g, 0.1mol), in room temperature reaction 24h, reaction mixture 20mL alcohol-water volume ratio is the mixed solution washing of 1:1 afterwards, 5000r/min is centrifugal removes clear liquid, and above washing, centrifugal process 3 times repeatedly, namely final drying obtains described polyether polyurethane material 20g.
Prepare microporous polyurethane elastomer:
(1) the diphenylmethanediisocyanate 1g of diphenylmethanediisocyanate 20g and liquefaction is added in four-hole boiling flask, maintain the temperature at 70 DEG C, then the polyether polyurethane material 1g of above-mentioned preparation is added in 0.1g ethylene glycol, pour into after mixing and be equipped with in the four-hole boiling flask of diphenylmethanediisocyanate, under argon shield, react 1h, after slaking 1min, spumescence material is taken out, place 1h, must fill a prescription a;
Wherein, the preparation method of the diphenylmethanediisocyanate of described liquefaction is with embodiment 1;
(2) get the polyether polyurethane material 1g of above-mentioned preparation, glycerine 1g, Diethylene Glycol 0.1g, silicone oil 0.1g, water 0.1g, diethylene diamine 0.1g mix, after stirring, must fill a prescription b;
(3) step (1) gained formula a is poured into rapidly in step (2) gained formula b, high-speed stirring is even, pouring rapidly surface into scribbles in the preheated mold of releasing agent silicone oil, mold closing, put into 50 DEG C of baking oven slaking 1min, the demoulding, takes out and obtains microporous polyurethane elastomer;
The microporous polyurethane elastomer tensile strength of above-mentioned preparation can reach 145MPa, and elongation at break reaches 146%.
Embodiment 10
Preparation polyether polyurethane material:
In reaction flask, add 1,2-PD (19.02g, 0.25mol), propylene oxide (14.52g, 0.25mol), sodium hydroxide (8g, 0.2mol), methyl alcohol (20mL), in room temperature reaction 12h; Then propylene oxide (14.52g, 0.25mol), sulfuric acid magnalium (75g, 0.1mol) is added, in room temperature reaction 20h; Then oxyethane (11.01g is added, 0.25mol), sodium hydroxide (4g, 0.1mol), in room temperature reaction 24h, reaction mixture 20mL alcohol-water volume ratio is the mixed solution washing of 1:1 afterwards, 5000r/min is centrifugal removes clear liquid, and above washing, centrifugal process 3 times repeatedly, namely final drying obtains described polyether polyurethane material 30g.
Prepare microporous polyurethane elastomer:
(1) the diphenylmethanediisocyanate 50g of diphenylmethanediisocyanate 100g and liquefaction is added in four-hole boiling flask, maintain the temperature at 80 DEG C, then the polyether polyurethane material 50g of above-mentioned preparation is added in 10g ethylene glycol, pour into after mixing and be equipped with in the four-hole boiling flask of diphenylmethanediisocyanate, under argon shield, react 20h, after slaking 30min, spumescence material is taken out, place 30h, must fill a prescription a;
Wherein, the preparation method of the diphenylmethanediisocyanate of described liquefaction is with embodiment 1;
(2) get the polyether polyurethane material 150g of above-mentioned preparation, glycerine 25g, Diethylene Glycol 2g, silicone oil 4g, water 5g, diethylene diamine 2g mix, after stirring, must fill a prescription b;
(3) step (1) gained formula a is poured into rapidly in step (2) gained formula b, high-speed stirring is even, pouring rapidly surface into scribbles in the preheated mold of releasing agent emulsification methyl-silicone oil, mold closing, put into 80 DEG C of baking oven slaking 15min, the demoulding, takes out and obtains microporous polyurethane elastomer;
The microporous polyurethane elastomer tensile strength of above-mentioned preparation can reach 138MPa, and elongation at break reaches 148%.
Claims (9)
1. a polyether polyurethane material, is characterized in that, described polyether polyurethane material prepares as follows:
In organic solvent, initiator polyvalent alcohol and oxirane A, under the katalysis of alkali A, in room temperature reaction 1 ~ 30h, obtain system A; Oxirane B and metal sulfate are added in system A, in room temperature reaction 1 ~ 40h, obtain system B; Be added in system B by oxirane C and alkali B, in room temperature reaction 1 ~ 60h, reaction mixture is through aftertreatment afterwards, obtained described polyether polyurethane material;
Wherein, described polyvalent alcohol is 1:0.01 ~ 10:0.01 ~ 10:0.01 ~ 10:0.1 ~ 10:0.1 ~ 10:0.1 ~ 10 with the ratio of the amount of substance that feeds intake of oxirane A, alkali A, oxirane B, metal sulfate, oxirane C, alkali B;
The volumetric usage of described organic solvent counts 0.001 ~ 10g/mL with the quality of polyvalent alcohol;
Described organic solvent is selected from methyl alcohol, ethanol, propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, Pentyl alcohol, n-Octanol, acetone, butanone, chloroform, methylene dichloride, ether, dithiocarbonic anhydride, 1-Methyl-2-Pyrrolidone, N-N-dimethyl formamide, N-N-N,N-DIMETHYLACETAMIDE, methyl-sulphoxide, tetrahydrofuran (THF), ethyl acetate, dioxane, acetonitrile, benzene, toluene or dimethylbenzene;
Described polyvalent alcohol is selected from ethylene glycol, 1,2-PD, BDO, hexylene glycol, neopentyl glycol, Diethylene Glycol, dipropylene glycol, TriMethylolPropane(TMP) or glycerine;
Described oxirane A is selected from oxyethane, propylene oxide, butylene oxide ring, epoxypentane, oxepane, oxepane or octylene oxide;
Described alkali A is selected from NaOH, KOH, Ba (OH)
2or Ca (OH)
2;
Described oxirane B is selected from oxyethane, propylene oxide, butylene oxide ring, epoxypentane, oxepane, oxepane or octylene oxide;
Described metal sulfate is selected from sodium sulfate, magnesium sulfate, ferrous sulfate, ferric sulfate, barium sulfate, potassium sulfate, potassium aluminium sulfate, calcium sulfate or sulfuric acid magnalium;
Described oxirane C is selected from oxyethane, propylene oxide, butylene oxide ring, epoxypentane, oxepane, oxepane or octylene oxide;
Described alkali B is selected from NaOH, KOH, Ba (OH)
2or Ca (OH)
2.
2. polyether polyurethane material as claimed in claim 1, it is characterized in that, described polyvalent alcohol is 1:1 ~ 2:1 ~ 2:1 ~ 2:2 ~ 4:2 ~ 4:2 ~ 4 with the ratio of the amount of substance that feeds intake of oxirane A, alkali A, oxirane B, metal sulfate, oxirane C, alkali B.
3. polyether polyurethane material as claimed in claim 1, it is characterized in that, the volumetric usage of described organic solvent counts 0.5 ~ 2mL/g with the quality of polyvalent alcohol.
4. polyether polyurethane material as claimed in claim 1, it is characterized in that, the post-treating method of described reaction mixture is: after reaction terminates, reaction mixture is the mixed solution washing of 1:1 through alcohol-water volume ratio, 5000r/min is centrifugal removes clear liquid, more than washing, centrifugal process 3 times repeatedly, namely final drying obtains described polyether polyurethane material.
5. polyether polyurethane material as claimed in claim 1, it is characterized in that, described polyether polyurethane material prepares as follows:
In methyl alcohol, initiator 1,2-PD and propylene oxide A, under the katalysis of sodium hydroxide A, in room temperature reaction 12h, obtain system A; Propylene oxide B and sulfuric acid magnalium are added in system A, in room temperature reaction 20h, obtain system B; Oxyethane and sodium hydroxide B are added in system B, in room temperature reaction 24h, reaction mixture is the mixed solution washing of 1:1 through alcohol-water volume ratio afterwards, and 5000r/min is centrifugal removes clear liquid, more than washing, centrifugal process 3 times repeatedly, namely final drying obtains described polyether polyurethane material;
Wherein, described 1,2-PD is 1:1 ~ 2:1 ~ 2:1 ~ 2:2 ~ 4:2 ~ 4:2 ~ 4 with the ratio of the amount of substance that feeds intake of propylene oxide A, sodium hydroxide A, propylene oxide B, sulfuric acid magnalium, oxyethane, sodium hydroxide B;
The volumetric usage of described methyl alcohol counts 0.5 ~ 2mL/g with the quality of 1,2-PD.
6. polyether polyurethane material as claimed in claim 1 is preparing the application in microporous polyurethane elastomer, and the method for described application is:
(1) diphenylmethanediisocyanate 1 ~ 50 part of diphenylmethanediisocyanate 1 ~ 100 part and liquefaction is added in reaction vessel, maintain the temperature at 70 ~ 80 DEG C, then described polyether polyurethane material 1 ~ 50 part is also added in reaction vessel with the mixture of ethylene glycol 0.1 ~ 10 part, 1 ~ 20h is reacted under protection of inert gas, after slaking 1 ~ 30min, material is taken out placement 1 ~ 30h, must fill a prescription a;
(2) get described polyether polyurethane material 1 ~ 150 part, glycerine 1 ~ 25 part, Diethylene Glycol 0.1 ~ 2 part, silicone oil 0.1 ~ 4 part, 0.1 ~ 5 part, water, diethylene diamine 0.1 ~ 2 part mixing, after stirring, must fill a prescription b;
(3) step (1) gained formula a is poured in step (2) gained formula b, pouring surface after stirring into scribbles in the preheated mold of releasing agent, mold closing, puts into 30 ~ 80 DEG C of baking oven slaking 1 ~ 15min, the demoulding, takes out and obtains microporous polyurethane elastomer.
7. apply as claimed in claim 6, it is characterized in that, in described step (1), the diphenylmethanediisocyanate of described liquefaction prepares as follows: be placed in beaker by solid-state diphenylmethanediisocyanate, in water bath with thermostatic control, be heated to 50 DEG C, prepare the diphenylmethanediisocyanate of liquefaction.
8. apply as claimed in claim 6, it is characterized in that, in described step (3), described releasing agent is silicone compounds, silicone oil, silicone resin metlyl branching silicone oil, methyl-silicone oil, emulsification methyl-silicone oil, hydrogeneous methyl-silicone oil, silicone grease, silicone resin, silicon rubber, silicon rubber toluene solution, microcrystalline wax or polyethylene wax.
9. apply as claimed in claim 6, described microporous polyurethane elastomer is as sole material.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106831358A (en) * | 2017-01-18 | 2017-06-13 | 东营市海科新源化工有限责任公司 | A kind of preparation method of dipropylene glycol |
| CN110607123A (en) * | 2019-10-04 | 2019-12-24 | 汤杰 | Room-temperature self-repairing coating and preparation method thereof |
| CN112876668A (en) * | 2021-04-29 | 2021-06-01 | 江苏火凤凰线缆系统技术股份有限公司 | Automobile sensor wire and preparation process thereof |
| CN116199855A (en) * | 2023-05-06 | 2023-06-02 | 成都瑞吉龙科技有限责任公司 | Polyether-polyester mixed polyurethane and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101486834A (en) * | 2008-12-30 | 2009-07-22 | 浙江华峰新材料股份有限公司 | High performance nano polyurethane micropore elastomer composite material and preparation thereof |
| CN101492533A (en) * | 2008-01-27 | 2009-07-29 | 吴安 | Novel polyether containing styrene oxide opened loop repetitive units and method for preparing the same |
| CN103709391A (en) * | 2013-11-28 | 2014-04-09 | 山东蓝星东大化工有限责任公司 | Method for synthesis of low-unsaturation degree, high-molecular weight and high-activity polyether polyol |
-
2015
- 2015-12-22 CN CN201510975996.2A patent/CN105566625B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101492533A (en) * | 2008-01-27 | 2009-07-29 | 吴安 | Novel polyether containing styrene oxide opened loop repetitive units and method for preparing the same |
| CN101486834A (en) * | 2008-12-30 | 2009-07-22 | 浙江华峰新材料股份有限公司 | High performance nano polyurethane micropore elastomer composite material and preparation thereof |
| CN103709391A (en) * | 2013-11-28 | 2014-04-09 | 山东蓝星东大化工有限责任公司 | Method for synthesis of low-unsaturation degree, high-molecular weight and high-activity polyether polyol |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106831358A (en) * | 2017-01-18 | 2017-06-13 | 东营市海科新源化工有限责任公司 | A kind of preparation method of dipropylene glycol |
| CN106831358B (en) * | 2017-01-18 | 2020-03-03 | 东营市海科新源化工有限责任公司 | Preparation method of dipropylene glycol |
| CN110607123A (en) * | 2019-10-04 | 2019-12-24 | 汤杰 | Room-temperature self-repairing coating and preparation method thereof |
| CN110607123B (en) * | 2019-10-04 | 2021-08-10 | 韶关长悦高分子材料有限公司 | Room-temperature self-repairing coating and preparation method thereof |
| CN112876668A (en) * | 2021-04-29 | 2021-06-01 | 江苏火凤凰线缆系统技术股份有限公司 | Automobile sensor wire and preparation process thereof |
| CN116199855A (en) * | 2023-05-06 | 2023-06-02 | 成都瑞吉龙科技有限责任公司 | Polyether-polyester mixed polyurethane and preparation method thereof |
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