CN108409915A - A kind of Water-based polyurethane elastomer - Google Patents
A kind of Water-based polyurethane elastomer Download PDFInfo
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- CN108409915A CN108409915A CN201810253189.3A CN201810253189A CN108409915A CN 108409915 A CN108409915 A CN 108409915A CN 201810253189 A CN201810253189 A CN 201810253189A CN 108409915 A CN108409915 A CN 108409915A
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- C—CHEMISTRY; METALLURGY
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
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- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
- C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
- C08G18/289—Compounds containing at least one heteroatom other than oxygen or nitrogen containing silicon
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/40—High-molecular-weight compounds
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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Abstract
The invention discloses a kind of Water-based polyurethane elastomers, including following weight parts to form：20 parts of ethylene glycol；Tripropylene glycol：10 parts；2 n-pentyl propane, 1,3 glycol：5 parts；30 parts of isocyanates；1,1 dimethyl-silicon alkanol, 1 acetic acid esters：2 parts；Isocyanate group methyl formate：5 parts；Isocyanic acid acrylic ester：5 parts；1 carboxylate of methyl 2,3 diethyl 1 (trimethylsilyl) 2 cyclopropylene：3 parts；Acrylate：30 parts；Modified molecular screen：5 parts；Hydrophilic chain extender：5 parts；Reinforcing agent：5 parts；Antifoaming agent：2 parts；Levelling agent：2 parts.Integral material be ensure that under conditions of day and night temperature is big, in the state that mechanical property can be continuously maintained in one preferably.
Description
Technical field
The present invention relates to a kind of high molecular material, more particularly to a kind of Water-based polyurethane elastomer.
Background technology
Polyurethane is a kind of polymer of the main chain containing-NHCOO-constitutional repeating unit, english abbreviation PU, including hard
The variforms such as polyurethane plastics, flexibel polyurethane plastics, polyurethane elastomer, and it is divided into thermoplasticity and thermosetting property two major classes.
Its raw material is generally presented with resin state.
Due to containing highly polar carbamate groups, not dissolving in non-polar group, there is good oil resistivity, toughness, resistance to
Mill property, resistance to ag(e)ing and adhesiveness.Adaptation wide temperature range can be made with different material（- 50~150 DEG C）Material, ten
Divide and is suitable for elastomer.
Need to use the mechanical property of polyurethane on some fields, it is special at some especially on aqueous polyurethane
In occasion, such as the larger area of day and night temperature uses polyurethane, and the mechanical property of polyurethane is often caused significantly to decline
The problem of.
Invention content
In view of the deficiencies of the prior art, the present invention intends to provide a kind of day and night temperature variation major region to use
Water-based polyurethane elastomer.
To achieve the above object, the present invention provides following technical solutions：
A kind of Water-based polyurethane elastomer, including following weight parts composition：
20 parts of ethylene glycol
Tripropylene glycol：10 parts
2- n-pentyl propane -1,3- glycol：5 parts
30 parts of isocyanates
1,1- dimethyl-silane alcohol 1- acetic acid esters：2 parts
Isocyanate group methyl formate：5 parts
Isocyanic acid acrylic ester：5 parts
Methyl 2,3- diethyl -1- (trimethylsilyl) -2- cyclopropylene -1- carboxylates：3 parts
Acrylate：30 parts
Modified molecular screen：5 parts
Hydrophilic chain extender：5 parts
Reinforcing agent：5 parts；
Antifoaming agent：2 parts
Levelling agent：2 parts.
As a further improvement on the present invention：
The hydrophilic chain extender includes following weight parts composition：
Polyethylene glycol mono allyl ether：5 parts
Methyl trimethoxy base silicon substrate dimethyl ketene diethyl acetal：3 parts.
As a further improvement on the present invention：
The reinforcing agent is triacetate propyl silane triol.
As a further improvement on the present invention：
The antifoaming agent is glycerine trihydroxy polyethers.
As a further improvement on the present invention：
The levelling agent is cellulose acetate butyrate.
As a further improvement on the present invention：
The modified molecular screen includes following molar ratio compositions：
Tetrabutyl silicate：2
Tetraethyl orthosilicate：1
Titanium silicate：0.1
Silicic acid two (tert-butyl) diethylester：0.2
4- hydroxy-3-methoxy meat silicic acid：0.1
2-amino-2-methyl-1-propanol：0.4
Phenylpropyl dimethyl silane oxygroup esters of silicon acis：0.3 part
Tetrabutyl difluoro triphen ammonium silicate：0.5
N- hexyl-N- methacryloxies-N, N- dimethylamino ammonium bromides：0.3 part.
As a further improvement on the present invention：
The preparation of modified molecular screen：
By titanium silicate, 4- hydroxy-3-methoxy meat silicic acid, 2-amino-2-methyl-1-propanol, tetrabutyl difluoro triphen ammonium silicate
It is dissolved in the potassium hydroxide solution of 0.1mol/L, tetrabutyl silicate, tetraethyl orthosilicate, (the tert- fourth of silicic acid two is added after to be dissolved
Base) diethylester is stirred at room temperature 30 minutes, phenylpropyl dimethyl silane oxygroup esters of silicon acis, N- hexyl-N- methyl-props are added later
Alkene acyloxy-N, N- dimethylamino ammonium bromide reacts 100min, is dried in vacuo 12~24 hours at 80~100 DEG C, by 500
~ 600 DEG C of high-temperature calcinations, obtain modified molecular screen later.
As another goal of the invention of the present invention, a kind of preparation method of aqueous polyurethane is provided：
Step 1：Ethylene glycol and isocyanates are mixed, pre-polymerization 1 hour is carried out under conditions of 50 DEG C, obtains the first performed polymer；
Step 2：First performed polymer is divided into two parts, tripropylene glycol, 1,1- dimethyl-silane alcohol 1- are added in a copy of it
Acetic acid esters, isocyanic acid acrylic ester, carry out heat preservation 30min at 50 DEG C, obtain the second performed polymer；Add in another first performed polymer
Enter isocyanate group methyl formate, 2- n-pentyl propane -1,3- glycol carries out heat preservation 30min at 50 DEG C, obtain third performed polymer；
Step 3：Methyl 2,3- diethyl -1- (trimethylsilyl) -2- cyclopropylene -1- carboxylic acids are added in the second performed polymer
Ester keeps the temperature 20min at 50 DEG C, obtains the 4th performed polymer；
Step 4：Third performed polymer and the 4th performed polymer are mixed, and 80 DEG C are warming up to after acrylate stirring 30min is added,
30min is reacted, modified molecular screen, hydrophilic chain extender, reinforcing agent, antifoaming agent, levelling agent is eventually adding and is warming up to 110 DEG C, reaction 2
Hour, obtain Water-based polyurethane elastomer.
In the present invention, using being synthesized to polyurethane based on ethylene glycol and isocyanates, wherein being added third 32
Alcohol and 2- n-pentyl propane -1,3- glycol participate in reaction, the both ends in tripropylene glycol and 2- n-pentyl propane -1,3- glycol
For hydroxyl, hydroxyl can be reacted with isocyanates and addition, to change the molecular structure of entire polyurethane, be added simultaneously
Isocyanate group methyl formate and isocyanic acid acrylic ester can also participate in reaction, and add 1,1- dimethyl-silane alcohol
1- acetic acid esters, methyl 2,3- diethyl -1- (trimethylsilyl) -2- cyclopropylene -1- carboxylates can give birth to integral into distribution
Reaction, and by the addition of above-mentioned additive, can improve the mechanical strength of integral polyurethane elastomer, and modified molecular screen
Based on tetrabutyl silicate, tetraethyl orthosilicate, titanium silicate, silicon molecular sieve analog is formed, while adding silicic acid two (tert-butyl)
Diethylester, 4- hydroxy-3-methoxy meat silicic acid, 2-amino-2-methyl-1-propanol, phenylpropyl dimethyl silane oxygroup silicic acid
Ester, tetrabutyl difluoro triphen ammonium silicate, enable to molecular sieve surface to have active group, by active group and above-mentioned additive
Reaction is generated, to cross linked molecular structures, is filled with molecule segment so that under hot-cool environment, molecule segment will not occur greatly
Range deviates, in tripropylene glycol, 2- n-pentyl propane -1,3- glycol, isocyanate group methyl formate, isocyanic acid acrylic ester, 1,1-
Dimethyl-silane alcohol 1- acetic acid esters, methyl 2,3- diethyl -1- (trimethylsilyl) -2- cyclopropylene -1- carboxylates, modification
The addition of molecular sieve can play synergistic effect so that under conditions of day and night temperature is big, mechanical property can be held integral material
Continue in the state of being maintained at one preferably.
In addition, especially selecting polyethylene glycol mono allyl ether, methyl trimethoxy base silicon substrate dimethylvinylsiloxy in hydrophilic chain extender
In the case of ketone diethyl acetal, polyethylene glycol mono allyl ether, methyl trimethoxy base silicon substrate dimethyl ketene diethyl acetal can
It reacts with overall molecule segment, generates synergy, further ensure integral material under conditions of day and night temperature is big,
In the state that mechanical property can be continuously maintained in one preferably.
Specific implementation mode
Embodiment one：
A kind of Water-based polyurethane elastomer, including following weight parts composition：
20 parts of ethylene glycol
Tripropylene glycol：10 parts
2- n-pentyl propane -1,3- glycol：5 parts
30 parts of isocyanates
1,1- dimethyl-silane alcohol 1- acetic acid esters：2 parts
Isocyanate group methyl formate：5 parts
Isocyanic acid acrylic ester：5 parts
Methyl 2,3- diethyl -1- (trimethylsilyl) -2- cyclopropylene -1- carboxylates：3 parts
Acrylate：30 parts
Modified molecular screen：5 parts
Hydrophilic chain extender：5 parts
Reinforcing agent：5 parts；
Antifoaming agent：2 parts
Levelling agent：2 parts.
The hydrophilic chain extender includes following weight parts composition：
Polyethylene glycol mono allyl ether：5 parts
Methyl trimethoxy base silicon substrate dimethyl ketene diethyl acetal：3 parts.
The reinforcing agent is triacetate propyl silane triol.
The antifoaming agent is glycerine trihydroxy polyethers.
The levelling agent is cellulose acetate butyrate.
The modified molecular screen includes following molar ratio compositions：
Tetrabutyl silicate：2
Tetraethyl orthosilicate：1
Titanium silicate：0.1
Silicic acid two (tert-butyl) diethylester：0.2
4- hydroxy-3-methoxy meat silicic acid：0.1
2-amino-2-methyl-1-propanol：0.4
Phenylpropyl dimethyl silane oxygroup esters of silicon acis：0.3 part
Tetrabutyl difluoro triphen ammonium silicate：0.5
N- hexyl-N- methacryloxies-N, N- dimethylamino ammonium bromides：0.3 part.
The preparation of modified molecular screen：
By titanium silicate, 4- hydroxy-3-methoxy meat silicic acid, 2-amino-2-methyl-1-propanol, tetrabutyl difluoro triphen ammonium silicate
It is dissolved in the potassium hydroxide solution of 0.1mol/L, tetrabutyl silicate, tetraethyl orthosilicate, (the tert- fourth of silicic acid two is added after to be dissolved
Base) diethylester is stirred at room temperature 30 minutes, phenylpropyl dimethyl silane oxygroup esters of silicon acis, N- hexyl-N- methyl-props are added later
Alkene acyloxy-N, N- dimethylamino ammonium bromide reacts 100min, is dried in vacuo 12~24 hours at 80~100 DEG C, by 500
~ 600 DEG C of high-temperature calcinations, obtain modified molecular screen later.
Preparation method：
Step 1：Ethylene glycol and isocyanates are mixed, pre-polymerization 1 hour is carried out under conditions of 50 DEG C, obtains the first performed polymer；
Step 2：First performed polymer is divided into two parts, tripropylene glycol, 1,1- dimethyl-silane alcohol 1- are added in a copy of it
Acetic acid esters, isocyanic acid acrylic ester, carry out heat preservation 30min at 50 DEG C, obtain the second performed polymer；Add in another first performed polymer
Enter isocyanate group methyl formate, 2- n-pentyl propane -1,3- glycol carries out heat preservation 30min at 50 DEG C, obtain third performed polymer；
Step 3：Methyl 2,3- diethyl -1- (trimethylsilyl) -2- cyclopropylene -1- carboxylic acids are added in the second performed polymer
Ester keeps the temperature 20min at 50 DEG C, obtains the 4th performed polymer；
Step 4：Third performed polymer and the 4th performed polymer are mixed, and 80 DEG C are warming up to after acrylate stirring 30min is added,
30min is reacted, modified molecular screen, hydrophilic chain extender, reinforcing agent, antifoaming agent, levelling agent is eventually adding and is warming up to 110 DEG C, reaction 2
Hour, obtain Water-based polyurethane elastomer.
Embodiment two：
A kind of Water-based polyurethane elastomer, including following weight parts composition：
20 parts of ethylene glycol
Tripropylene glycol：10 parts
2- n-pentyl propane -1,3- glycol：5 parts
30 parts of isocyanates
1,1- dimethyl-silane alcohol 1- acetic acid esters：2 parts
Isocyanate group methyl formate：5 parts
Isocyanic acid acrylic ester：5 parts
Methyl 2,3- diethyl -1- (trimethylsilyl) -2- cyclopropylene -1- carboxylates：3 parts
Acrylate：30 parts
Modified molecular screen：5 parts
Hydrophilic chain extender：5 parts
Reinforcing agent：5 parts；
Antifoaming agent：2 parts
Levelling agent：2 parts.
The hydrophilic chain extender includes following weight parts composition：
Polyethylene glycol mono allyl ether：5 parts.
The reinforcing agent is triacetate propyl silane triol.
The antifoaming agent is glycerine trihydroxy polyethers.
The levelling agent is cellulose acetate butyrate.
The modified molecular screen includes following molar ratio compositions：
Tetrabutyl silicate：2
Tetraethyl orthosilicate：1
Titanium silicate：0.1
Silicic acid two (tert-butyl) diethylester：0.2
4- hydroxy-3-methoxy meat silicic acid：0.1
2-amino-2-methyl-1-propanol：0.4
Phenylpropyl dimethyl silane oxygroup esters of silicon acis：0.3 part
Tetrabutyl difluoro triphen ammonium silicate：0.5
N- hexyl-N- methacryloxies-N, N- dimethylamino ammonium bromides：0.3 part.
The preparation of modified molecular screen：
By titanium silicate, 4- hydroxy-3-methoxy meat silicic acid, 2-amino-2-methyl-1-propanol, tetrabutyl difluoro triphen ammonium silicate
It is dissolved in the potassium hydroxide solution of 0.1mol/L, tetrabutyl silicate, tetraethyl orthosilicate, (the tert- fourth of silicic acid two is added after to be dissolved
Base) diethylester is stirred at room temperature 30 minutes, phenylpropyl dimethyl silane oxygroup esters of silicon acis, N- hexyl-N- methyl-props are added later
Alkene acyloxy-N, N- dimethylamino ammonium bromide reacts 100min, is dried in vacuo 12~24 hours at 80~100 DEG C, by 500
~ 600 DEG C of high-temperature calcinations, obtain modified molecular screen later.
Preparation method：
Step 1：Ethylene glycol and isocyanates are mixed, pre-polymerization 1 hour is carried out under conditions of 50 DEG C, obtains the first performed polymer；
Step 2：First performed polymer is divided into two parts, tripropylene glycol, 1,1- dimethyl-silane alcohol 1- are added in a copy of it
Acetic acid esters, isocyanic acid acrylic ester, carry out heat preservation 30min at 50 DEG C, obtain the second performed polymer；Add in another first performed polymer
Enter isocyanate group methyl formate, 2- n-pentyl propane -1,3- glycol carries out heat preservation 30min at 50 DEG C, obtain third performed polymer；
Step 3：Methyl 2,3- diethyl -1- (trimethylsilyl) -2- cyclopropylene -1- carboxylic acids are added in the second performed polymer
Ester keeps the temperature 20min at 50 DEG C, obtains the 4th performed polymer；
Step 4：Third performed polymer and the 4th performed polymer are mixed, and 80 DEG C are warming up to after acrylate stirring 30min is added,
30min is reacted, modified molecular screen, hydrophilic chain extender, reinforcing agent, antifoaming agent, levelling agent is eventually adding and is warming up to 110 DEG C, reaction 2
Hour, obtain Water-based polyurethane elastomer.
Embodiment three：
A kind of Water-based polyurethane elastomer, including following weight parts composition：
20 parts of ethylene glycol
Tripropylene glycol：10 parts
2- n-pentyl propane -1,3- glycol：5 parts
30 parts of isocyanates
1,1- dimethyl-silane alcohol 1- acetic acid esters：2 parts
Isocyanate group methyl formate：5 parts
Isocyanic acid acrylic ester：5 parts
Methyl 2,3- diethyl -1- (trimethylsilyl) -2- cyclopropylene -1- carboxylates：3 parts
Acrylate：30 parts
Modified molecular screen：5 parts
Hydrophilic chain extender：5 parts
Reinforcing agent：5 parts；
Antifoaming agent：2 parts
Levelling agent：2 parts.
The hydrophilic chain extender includes following weight parts composition：
Methyl trimethoxy base silicon substrate dimethyl ketene diethyl acetal：3 parts.
The reinforcing agent is triacetate propyl silane triol.
The antifoaming agent is glycerine trihydroxy polyethers.
The levelling agent is cellulose acetate butyrate.
The modified molecular screen includes following molar ratio compositions：
Tetrabutyl silicate：2
Tetraethyl orthosilicate：1
Titanium silicate：0.1
Silicic acid two (tert-butyl) diethylester：0.2
4- hydroxy-3-methoxy meat silicic acid：0.1
2-amino-2-methyl-1-propanol：0.4
Phenylpropyl dimethyl silane oxygroup esters of silicon acis：0.3 part
Tetrabutyl difluoro triphen ammonium silicate：0.5
N- hexyl-N- methacryloxies-N, N- dimethylamino ammonium bromides：0.3 part.
The preparation of modified molecular screen：
By titanium silicate, 4- hydroxy-3-methoxy meat silicic acid, 2-amino-2-methyl-1-propanol, tetrabutyl difluoro triphen ammonium silicate
It is dissolved in the potassium hydroxide solution of 0.1mol/L, tetrabutyl silicate, tetraethyl orthosilicate, (the tert- fourth of silicic acid two is added after to be dissolved
Base) diethylester is stirred at room temperature 30 minutes, phenylpropyl dimethyl silane oxygroup esters of silicon acis, N- hexyl-N- methyl-props are added later
Alkene acyloxy-N, N- dimethylamino ammonium bromide reacts 100min, is dried in vacuo 12~24 hours at 80~100 DEG C, by 500
~ 600 DEG C of high-temperature calcinations, obtain modified molecular screen later.
Preparation method：
Step 1：Ethylene glycol and isocyanates are mixed, pre-polymerization 1 hour is carried out under conditions of 50 DEG C, obtains the first performed polymer；
Step 2：First performed polymer is divided into two parts, tripropylene glycol, 1,1- dimethyl-silane alcohol 1- are added in a copy of it
Acetic acid esters, isocyanic acid acrylic ester, carry out heat preservation 30min at 50 DEG C, obtain the second performed polymer；Add in another first performed polymer
Enter isocyanate group methyl formate, 2- n-pentyl propane -1,3- glycol carries out heat preservation 30min at 50 DEG C, obtain third performed polymer；
Step 3：Methyl 2,3- diethyl -1- (trimethylsilyl) -2- cyclopropylene -1- carboxylic acids are added in the second performed polymer
Ester keeps the temperature 20min at 50 DEG C, obtains the 4th performed polymer；
Step 4：Third performed polymer and the 4th performed polymer are mixed, and 80 DEG C are warming up to after acrylate stirring 30min is added,
30min is reacted, modified molecular screen, hydrophilic chain extender, reinforcing agent, antifoaming agent, levelling agent is eventually adding and is warming up to 110 DEG C, reaction 2
Hour, obtain Water-based polyurethane elastomer.
Comparative example one：
A kind of Water-based polyurethane elastomer, including following weight parts composition：
20 parts of ethylene glycol
30 parts of isocyanates
Hydrophilic chain extender：5 parts
Reinforcing agent：5 parts；
Antifoaming agent：2 parts
Levelling agent：2 parts.
The hydrophilic chain extender includes following weight parts composition：
Polyethylene glycol mono allyl ether：5 parts
Methyl trimethoxy base silicon substrate dimethyl ketene diethyl acetal：3 parts.
The reinforcing agent is triacetate propyl silane triol.
The antifoaming agent is glycerine trihydroxy polyethers.
The levelling agent is cellulose acetate butyrate.
Step 1：Ethylene glycol and isocyanates are mixed, pre-polymerization 1 hour is carried out under conditions of 50 DEG C, it is pre- to obtain first
Aggressiveness；
Step 2：First performed polymer is divided into two parts, heat preservation 30min is carried out at 50 DEG C, obtains the second performed polymer；Another
First performed polymer keeps the temperature 20min at 50 DEG C, obtains third performed polymer；
Step 3：Second performed polymer and third performed polymer are mixed, are warming up to 80 DEG C, 30min is reacted, is eventually adding hydrophilic chain extension
Agent, reinforcing agent, antifoaming agent, levelling agent are warming up to 110 DEG C, react 2 hours, obtain Water-based polyurethane elastomer.
Comparative example two：
A kind of Water-based polyurethane elastomer, including following weight parts composition：
20 parts of ethylene glycol
Tripropylene glycol：10 parts
2- n-pentyl propane -1,3- glycol：5 parts
30 parts of isocyanates
Isocyanate group methyl formate：5 parts
Methyl 2,3- diethyl -1- (trimethylsilyl) -2- cyclopropylene -1- carboxylates：3 parts
Acrylate：30 parts
Modified molecular screen：5 parts
Hydrophilic chain extender：5 parts
Reinforcing agent：5 parts；
Antifoaming agent：2 parts
Levelling agent：2 parts.
The hydrophilic chain extender includes following weight parts composition：
Polyethylene glycol mono allyl ether：5 parts
Methyl trimethoxy base silicon substrate dimethyl ketene diethyl acetal：3 parts.
The reinforcing agent is triacetate propyl silane triol.
The antifoaming agent is glycerine trihydroxy polyethers.
The levelling agent is cellulose acetate butyrate.
The modified molecular screen includes following molar ratio compositions：
Tetrabutyl silicate：2
Tetraethyl orthosilicate：1
Titanium silicate：0.1.
The preparation of modified molecular screen：
Titanium silicate is dissolved in the potassium hydroxide solution of 0.1mol/L, tetrabutyl silicate, tetraethyl orthosilicate is added after to be dissolved
It is stirred at room temperature 30 minutes, the reaction was continued 100min is dried in vacuo 12~24 hours at 80~100 DEG C, is passing through 500 ~ 600 DEG C of height
Temperature calcining, obtains modified molecular screen later.
Preparation method：
Step 1：Ethylene glycol and isocyanates are mixed, pre-polymerization 1 hour is carried out under conditions of 50 DEG C, obtains the first performed polymer；
Step 2：First performed polymer is divided into two parts, tripropylene glycol isocyanic acid acrylic ester is added in a copy of it, at 50 DEG C
Heat preservation 30min is carried out, the second performed polymer is obtained；Isocyanate group methyl formate is added in another first performed polymer, at 50 DEG C
Heat preservation 30min is carried out, third performed polymer is obtained；
Step 3：Methyl 2,3- diethyl -1- (trimethylsilyl) -2- cyclopropylene -1- carboxylic acids are added in the second performed polymer
Ester keeps the temperature 20min at 50 DEG C, obtains the 4th performed polymer；
Step 4：Third performed polymer and the 4th performed polymer are mixed, and 80 DEG C are warming up to after acrylate stirring 30min is added,
30min is reacted, modified molecular screen, hydrophilic chain extender, reinforcing agent, antifoaming agent, levelling agent is eventually adding and is warming up to 110 DEG C, reaction 2
Hour, obtain Water-based polyurethane elastomer.
Comparative example three：
A kind of Water-based polyurethane elastomer, including following weight parts composition：
20 parts of ethylene glycol
2- n-pentyl propane -1,3- glycol：5 parts
30 parts of isocyanates
1,1- dimethyl-silane alcohol 1- acetic acid esters：2 parts
Acrylate：30 parts
Modified molecular screen：5 parts
Hydrophilic chain extender：5 parts
Reinforcing agent：5 parts；
Antifoaming agent：2 parts
Levelling agent：2 parts.
The hydrophilic chain extender includes following weight parts composition：
Polyethylene glycol mono allyl ether：5 parts
Methyl trimethoxy base silicon substrate dimethyl ketene diethyl acetal：3 parts.
The reinforcing agent is triacetate propyl silane triol.
The antifoaming agent is glycerine trihydroxy polyethers.
The levelling agent is cellulose acetate butyrate.
The modified molecular screen includes following molar ratio compositions：
Tetrabutyl silicate：2
Tetraethyl orthosilicate：1
Titanium silicate：0.1
4- hydroxy-3-methoxy meat silicic acid：0.1
Phenylpropyl dimethyl silane oxygroup esters of silicon acis：0.3 part
Tetrabutyl difluoro triphen ammonium silicate：0.5.
The preparation of modified molecular screen：
Titanium silicate, 4- hydroxy-3-methoxy meat silicic acid, tetrabutyl difluoro triphen ammonium silicate are dissolved to the hydroxide of 0.1mol/L
In potassium solution, tetrabutyl silicate, tetraethyl orthosilicate are added after to be dissolved and is stirred at room temperature 30 minutes, phenylpropyl dimethyl is added later
Siloxysilicate material reacts 100min, is dried in vacuo 12~24 hours at 80~100 DEG C, is passing through 500 ~ 600 DEG C of high temperature
Calcining, obtains modified molecular screen later.
Preparation method：
Step 1：Ethylene glycol and isocyanates are mixed, pre-polymerization 1 hour is carried out under conditions of 50 DEG C, obtains the first performed polymer；
Step 2：First performed polymer is divided into two parts, 1,1- dimethyl-silane alcohol 1- acetic acid esters is added in a copy of it,
Heat preservation 30min is carried out at 50 DEG C, obtains the second performed polymer；2- n-pentyl propane -1,3- two is added in another first performed polymer
Alcohol carries out heat preservation 30min at 50 DEG C, obtains third performed polymer；
Step 3：In the second performed polymer, 20min is kept the temperature at 50 DEG C, obtains the 4th performed polymer；
Step 4：Third performed polymer and the 4th performed polymer are mixed, and 80 DEG C are warming up to after acrylate stirring 30min is added,
30min is reacted, modified molecular screen, hydrophilic chain extender, reinforcing agent, antifoaming agent, levelling agent is eventually adding and is warming up to 110 DEG C, reaction 2
Hour, obtain Water-based polyurethane elastomer.
Comparative example four：
A kind of Water-based polyurethane elastomer, including following weight parts composition：
20 parts of ethylene glycol
Tripropylene glycol：10 parts
30 parts of isocyanates
Isocyanate group methyl formate：5 parts
Isocyanic acid acrylic ester：5 parts
Methyl 2,3- diethyl -1- (trimethylsilyl) -2- cyclopropylene -1- carboxylates：3 parts
Acrylate：30 parts
Modified molecular screen：5 parts
Hydrophilic chain extender：5 parts
Reinforcing agent：5 parts；
Antifoaming agent：2 parts
Levelling agent：2 parts.
The hydrophilic chain extender includes following weight parts composition：
Polyethylene glycol mono allyl ether：5 parts
Methyl trimethoxy base silicon substrate dimethyl ketene diethyl acetal：3 parts.
The reinforcing agent is triacetate propyl silane triol.
The antifoaming agent is glycerine trihydroxy polyethers.
The levelling agent is cellulose acetate butyrate.
The modified molecular screen includes following molar ratio compositions：
Tetrabutyl silicate：2
Tetraethyl orthosilicate：1
Titanium silicate：0.1
Silicic acid two (tert-butyl) diethylester：0.2
2-amino-2-methyl-1-propanol：0.4
N- hexyl-N- methacryloxies-N, N- dimethylamino ammonium bromides：0.3 part.
The preparation of modified molecular screen：
Titanium silicate, 2-amino-2-methyl-1-propanol are dissolved in the potassium hydroxide solution of 0.1mol/L, are added after to be dissolved
Tetrabutyl silicate, tetraethyl orthosilicate, silicic acid two (tert-butyl) diethylester are stirred at room temperature 30 minutes, and N- hexyl-N- first is added later
Base acryloxy-N, N- dimethylamino ammonium bromide reacts 100min, is dried in vacuo 12~24 hours, is passing through at 80~100 DEG C
500 ~ 600 DEG C of high-temperature calcinations are crossed, obtain modified molecular screen later.
Preparation method：
Step 1：Ethylene glycol and isocyanates are mixed, pre-polymerization 1 hour is carried out under conditions of 50 DEG C, obtains the first performed polymer；
Step 2：First performed polymer is divided into two parts, tripropylene glycol, isocyanic acid acrylic ester are added in a copy of it, at 50 DEG C
Under carry out heat preservation 30min, obtain the second performed polymer；Isocyanate group methyl formate is added in another first performed polymer at 50 DEG C
Heat preservation 30min is carried out, third performed polymer is obtained；
Step 3：Methyl 2,3- diethyl -1- (trimethylsilyl) -2- cyclopropylene -1- carboxylic acids are added in the second performed polymer
Ester keeps the temperature 20min at 50 DEG C, obtains the 4th performed polymer；
Step 4：Third performed polymer and the 4th performed polymer are mixed, and 80 DEG C are warming up to after acrylate stirring 30min is added,
30min is reacted, modified molecular screen, hydrophilic chain extender, reinforcing agent, antifoaming agent, levelling agent is eventually adding and is warming up to 110 DEG C, reaction 2
Hour, obtain Water-based polyurethane elastomer.
Test one：
Measuring mechanical property is carried out to embodiment and comparative example；
Test two：
Under the conditions of material is placed on 15 DEG C, it is warming up to 35 DEG C in 2 hours, keeps the temperature 6 hours, is cooled to -10 DEG C within 2 hours later,
It is warming up to 15 DEG C within heat preservation 6 hours, then 2 hours and keeps the temperature 1 hour, then is tested.
Table one：Test a result
| Tensile strength（MPa） | Elongation at break（%） | |
| Embodiment one | 38 | 620 |
| Embodiment two | 35 | 590 |
| Embodiment three | 33 | 585 |
| Comparative example one | 19 | 480 |
| Comparative example two | 26 | 510 |
| Comparative example three | 28 | 500 |
| Comparative example four | 30 | 520 |
Table two：Test two results
| Tensile strength（MPa） | Elongation at break（%） | |
| Embodiment one | 35 | 600 |
| Embodiment two | 29 | 510 |
| Embodiment three | 29 | 520 |
| Comparative example one | 8 | 310 |
| Comparative example two | 13 | 370 |
| Comparative example three | 15 | 360 |
| Comparative example four | 18 | 360 |
The above is only a preferred embodiment of the present invention, protection scope of the present invention is not limited merely to above-described embodiment,
All technical solutions belonged under thinking of the present invention all belong to the scope of protection of the present invention.It should be pointed out that for the art
For those of ordinary skill, several improvements and modifications without departing from the principles of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (8)
1. a kind of Water-based polyurethane elastomer, it is characterised in that：It is formed including following weight parts：
20 parts of ethylene glycol
Tripropylene glycol：10 parts
2- n-pentyl propane -1,3- glycol：5 parts
30 parts of isocyanates
1,1- dimethyl-silane alcohol 1- acetic acid esters：2 parts
Isocyanate group methyl formate：5 parts
Isocyanic acid acrylic ester：5 parts
Methyl 2,3- diethyl -1- (trimethylsilyl) -2- cyclopropylene -1- carboxylates：3 parts
Acrylate：30 parts
Modified molecular screen：5 parts
Hydrophilic chain extender：5 parts
Reinforcing agent：5 parts；
Antifoaming agent：2 parts
Levelling agent：2 parts.
2. a kind of Water-based polyurethane elastomer according to claim 1, it is characterised in that：
The hydrophilic chain extender includes following weight parts composition：
Polyethylene glycol mono allyl ether：5 parts
Methyl trimethoxy base silicon substrate dimethyl ketene diethyl acetal：3 parts.
3. a kind of Water-based polyurethane elastomer according to claim 1, it is characterised in that：
The reinforcing agent is triacetate propyl silane triol.
4. a kind of Water-based polyurethane elastomer according to claim 1, it is characterised in that：
The antifoaming agent is glycerine trihydroxy polyethers.
5. a kind of Water-based polyurethane elastomer according to claim 1, it is characterised in that：
The levelling agent is cellulose acetate butyrate.
6. a kind of Water-based polyurethane elastomer according to claim 1, it is characterised in that：
The modified molecular screen includes following molar ratio compositions：
Tetrabutyl silicate：2
Tetraethyl orthosilicate：1
Titanium silicate：0.1
Silicic acid two (tert-butyl) diethylester：0.2
4- hydroxy-3-methoxy meat silicic acid：0.1
2-amino-2-methyl-1-propanol：0.4
Phenylpropyl dimethyl silane oxygroup esters of silicon acis：0.3 part
Tetrabutyl difluoro triphen ammonium silicate：0.5
N- hexyl-N- methacryloxies-N, N- dimethylamino ammonium bromides：0.3 part.
7. a kind of Water-based polyurethane elastomer according to claim 6, it is characterised in that：
The preparation of modified molecular screen：
By titanium silicate, 4- hydroxy-3-methoxy meat silicic acid, 2-amino-2-methyl-1-propanol, tetrabutyl difluoro triphen ammonium silicate
It is dissolved in the potassium hydroxide solution of 0.1mol/L, tetrabutyl silicate, tetraethyl orthosilicate, (the tert- fourth of silicic acid two is added after to be dissolved
Base) diethylester is stirred at room temperature 30 minutes, phenylpropyl dimethyl silane oxygroup esters of silicon acis, N- hexyl-N- methyl-props are added later
Alkene acyloxy-N, N- dimethylamino ammonium bromide reacts 100min, is dried in vacuo 12~24 hours at 80~100 DEG C, by 500
~ 600 DEG C of high-temperature calcinations, obtain modified molecular screen later.
8. the preparation method of the aqueous polyurethane as described in right wants 1 to 7：It is characterized in that：
Step 1：Ethylene glycol and isocyanates are mixed, pre-polymerization 1 hour is carried out under conditions of 50 DEG C, obtains the first performed polymer；
Step 2：First performed polymer is divided into two parts, tripropylene glycol, 1,1- dimethyl-silane alcohol 1- are added in a copy of it
Acetic acid esters, isocyanic acid acrylic ester, carry out heat preservation 30min at 50 DEG C, obtain the second performed polymer；Add in another first performed polymer
Enter isocyanate group methyl formate, 2- n-pentyl propane -1,3- glycol carries out heat preservation 30min at 50 DEG C, obtain third performed polymer；
Step 3：Methyl 2,3- diethyl -1- (trimethylsilyl) -2- cyclopropylene -1- carboxylic acids are added in the second performed polymer
Ester keeps the temperature 20min at 50 DEG C, obtains the 4th performed polymer；
Step 4：Third performed polymer and the 4th performed polymer are mixed, and 80 DEG C are warming up to after acrylate stirring 30min is added,
30min is reacted, modified molecular screen, hydrophilic chain extender, reinforcing agent, antifoaming agent, levelling agent is eventually adding and is warming up to 110 DEG C, reaction 2
Hour, obtain Water-based polyurethane elastomer.
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| CN109679323A (en) * | 2018-12-17 | 2019-04-26 | 浙江华峰热塑性聚氨酯有限公司 | A kind of surface does not bond soft TPU of dumb light type and preparation method thereof |
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