CN107353386A - High-strength aqueous polyurethane of the low mould of selfreparing and preparation method thereof - Google Patents
High-strength aqueous polyurethane of the low mould of selfreparing and preparation method thereof Download PDFInfo
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- CN107353386A CN107353386A CN201710574925.0A CN201710574925A CN107353386A CN 107353386 A CN107353386 A CN 107353386A CN 201710574925 A CN201710574925 A CN 201710574925A CN 107353386 A CN107353386 A CN 107353386A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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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
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
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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
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0828—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing sulfonate groups or groups forming them
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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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
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
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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
- C08G18/6625—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/34
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
Abstract
The invention discloses high-strength aqueous polyurethane of the low mould of a kind of selfreparing and preparation method thereof, the polyurethane, which is adopted, to be prepared by the following steps：Macromolecule dihydric alcohol I, macromolecular polyol II and di-isocyanate reaction, obtain polyurethane prepolymer a1；Small molecule chain extender, hydrophilic chain extender I, solvent, catalyst are added thereto, and reaction obtains Waterborne Polyurethane Prepolymer a2；Solvent and hydrophilic chain extender II are added, reaction obtains Waterborne Polyurethane Prepolymer a3；Solvent is added, salt forming agent is added under high speed shear, adds 3~5 times of water-reducible rear chain extenders after being stirring evenly and then adding into water high speed dispersion and emulsion, then desolvation produces under vacuo.The present invention introduces disulfide bond by the soft segment and hard section in aqueous polyurethane, the introducing of the disulfide bond can significantly reduce the modulus of aqueous polyurethane, improve the intensity of aqueous polyurethane, it can also cause aqueous polyurethane that there are self-healing properties so that selfreparing can be achieved in polyurethane under conditions of no any renovation agent.
Description
Technical field
The present invention relates to field of waterborne polyurethane, more particularly to a kind of high-strength aqueous polyurethane of the low mould of selfreparing and its preparation
Method.
Background technology
Polyurethane is the general name for the high-molecular compound that a kind of main chain contains carbamate groups unit, be by polyalcohol,
Small molecule chain extender and polyisocyanates progressively polymerize the multi-block polymer of formation.Polyalcohol forms soft segment, small molecule chain extension
Agent and polyisocyanates form hard section, and polyurethane can be efficiently controlled by adjusting constituent in soft and hard segments and ratio
Molecular structure and physical and chemical performance.The polarity of hard section is stronger, easily aggregation；The incompatibility of hard section and soft segment thermodynamically
Microphase-separated can be formed.This micro phase separation structure of polyurethane makes polyurethane have more preferable biology than other high polymer materials
Compatibility, it can be used as the surface of medicine equipment or articles for use.In addition, polyurethane is excellent, regulatable physical and mechanical properties also makes
It can be widely used in top finishing.However, polyurethane especially its during use inevitably by
Collision scrapes, and directly affecting makes its security and service life.
The content of the invention
In view of this, it is an object of the invention to provide high-strength aqueous polyurethane of the low mould of a kind of selfreparing and preparation method thereof,
With self-healing properties so that selfreparing can be achieved in polyurethane under conditions of no any renovation agent.
To achieve these goals, the present invention provides following technical scheme：
A kind of preparation method of the low high-strength aqueous polyurethane of mould of selfreparing, comprises the following steps：
A) macromolecule dihydric alcohol I, macromolecular polyol II and diisocyanate are reacted into 2~4h in 90~100 DEG C, obtained
Polyurethane prepolymer a1；The macromolecule dihydric alcohol I is the polyester diol that disulphide and adipic acid are esterified to obtain；
B) the polyurethane prepolymer a obtained to step a)1Middle addition small molecule chain extender, hydrophilic chain extender I, solvent, urge
Agent, 4~7h is reacted in 60~80 DEG C, obtains Waterborne Polyurethane Prepolymer a2；
C) the Waterborne Polyurethane Prepolymer a obtained to step b)2Middle addition solvent and hydrophilic chain extender II, in 50~60 DEG C
0.5~1h is reacted, obtains Waterborne Polyurethane Prepolymer a3；
D) the Waterborne Polyurethane Prepolymer a obtained to step c)3Middle addition solvent, salt forming agent is added under high speed shear, is stirred
Mix to add after 1~5min after 2~5min of water high speed dispersion and emulsion and add 3~5 times of water-reducible rear chain extenders, stirring 20~
40min, then desolvation under vacuo, produces aqueous polyurethane；The rear chain extender is 2- amino-ethyl disulphide.
Preferably, the macromolecular polyol II is PolyTHF dihydric alcohol.
Preferably, the diisocyanate is toluene di-isocyanate(TDI), IPDI, 4,4`- diphenyl
Methane diisocyanate or 4,4'- dicyclohexyl methyl hydride diisocyanates.
Preferably, the small molecule chain extender be 1,2-PD, 2- methyl isophthalic acids, ammediol, neopentyl glycol or front three
Base pentanediol.
Preferably, the hydrophilic chain extender I is dihydromethyl propionic acid or dimethylolpropionic acid.
Preferably, the hydrophilic chain extender II is ethylenediamine base sodium sulfonate.
Preferably, the catalyst is selected from stannous octoate, tin dilaurate normal-butyl tin, organic Bi salt catalysts, organic Zn
One or more in salt catalyst.
Preferably, the salt forming agent be triethylamine, N, N dimethyl monoethanolamine, sodium hydroxide or potassium hydroxide.
Preferably, in step b), step c) and step d), the solvent is independently selected from acetone or butanone.
Preferably, the rear chain extender is 2- amino-ethyl disulphide.
The low high-strength aqueous polyurethane of mould of a kind of selfreparing, using the preparation side of the high-strength aqueous polyurethane of the low mould of above-mentioned selfreparing
Method is made.
Low high-strength aqueous polyurethane of mould of a kind of selfreparing provided by the invention and preparation method thereof, the polyurethane is using following
Step is made：By macromolecule dihydric alcohol I, macromolecular polyol II and diisocyanate react 2~4h in 90~100 DEG C, obtain
Polyurethane prepolymer a1；Macromolecule dihydric alcohol I is the polyester diol that disulphide and adipic acid are esterified to obtain；B) to step a)
Obtained polyurethane prepolymer a1Middle addition small molecule chain extender, hydrophilic chain extender I, solvent, catalyst, in 60~80 DEG C of reactions
4~7h, obtain Waterborne Polyurethane Prepolymer a2；C) the Waterborne Polyurethane Prepolymer a obtained to step b)2Middle addition solvent and parent
Water chain extender II, 0.5~1h is reacted in 50~60 DEG C, obtains Waterborne Polyurethane Prepolymer a3；D) obtained to step c) water-based
Base polyurethane prepolymer for use as a3Middle addition solvent, salt forming agent is added under high speed shear, water high speed dispersion and emulsion is added after stirring 1~5min
3~5 times of water-reducible rear chain extenders are added after 2~5min, 20~40min is stirred, then desolvation under vacuo, produces water
Property polyurethane；Rear chain extender is 2- amino-ethyl disulphide.The present invention in aqueous polyurethane in soft segment and hard section by introducing
Disulfide bond, the introducing of the disulfide bond can significantly reduce the modulus of aqueous polyurethane, improve the intensity of aqueous polyurethane,
It can also cause aqueous polyurethane that there are self-healing properties so that polyurethane can be achieved certainly under conditions of no any renovation agent
Repair.
Embodiment
In order to further appreciate that the present invention, the preferred embodiments of the invention are described with reference to embodiment, but
It is it should be appreciated that these descriptions are simply for further explanation the features and advantages of the present invention rather than to patent requirements of the present invention
Limitation.
The invention provides a kind of preparation method of the high-strength aqueous polyurethane of the low mould of selfreparing, comprise the following steps：
A) macromolecule dihydric alcohol I, macromolecular polyol II and diisocyanate are reacted into 2~4h in 90~100 DEG C, obtained
Polyurethane prepolymer a1；Macromolecule dihydric alcohol I is the polyester diol that disulphide and adipic acid are esterified to obtain；
B) the polyurethane prepolymer a obtained to step a)1Middle addition small molecule chain extender, hydrophilic chain extender I, solvent, urge
Agent, 4~7h is reacted in 60~80 DEG C, obtains Waterborne Polyurethane Prepolymer a2；
C) the Waterborne Polyurethane Prepolymer a obtained to step b)2Middle addition solvent and hydrophilic chain extender II, in 50~60 DEG C
0.5~1h is reacted, obtains Waterborne Polyurethane Prepolymer a3；
D) the Waterborne Polyurethane Prepolymer a obtained to step c)3Middle addition solvent, salt forming agent is added under high speed shear, is stirred
Mix to add after 1~5min after 2~5min of water high speed dispersion and emulsion and add 3~5 times of water-reducible rear chain extenders, stirring 20~
40min, then desolvation under vacuo, produces aqueous polyurethane；Rear chain extender is 2- amino-ethyl disulphide.
In above-mentioned technical proposal, by introducing disulfide bond in soft segment and hard section in aqueous polyurethane, the disulfide bond draws
The modulus of aqueous polyurethane can be significantly reduced by entering, and improve the intensity of aqueous polyurethane, additionally it is possible to so that aqueous polyurethane
With self-healing properties so that selfreparing can be achieved in polyurethane under conditions of no any renovation agent.
In the present invention, macromolecule dihydric alcohol I, macromolecular polyol II and di-isocyanate reaction, it is pre- to obtain polyurethane
Polymers a1。
In an embodiment of the present invention, macromolecule dihydric alcohol I is the polyester binary that disulphide and adipic acid are esterified to obtain
Alcohol；In other embodiments, macromolecule dihydric alcohol I relative molecular weight is 1000~4000；In a further embodiment, big point
Sub- dihydric alcohol I relative molecular weight is 3000.
Wherein, disulphide is diphenyl disulfide or 2- HEDSs.
In an embodiment of the present invention, macromolecular polyol II is PolyTHF dihydric alcohol；In other embodiments, greatly
Molecular polylol II relative molecular weight is 2000~3000；In a further embodiment, relative point of macromolecular polyol II
Son amount is 3000.
In an embodiment of the present invention, diisocyanate is toluene di-isocyanate(TDI), IPDI, 4,4
`- methyl diphenylene diisocyanates or 4,4'- dicyclohexyl methyl hydride diisocyanates.
Obtain polyurethane prepolymer a1Afterwards, small molecule chain extender, hydrophilic chain extender I, solvent, catalyst are added thereto,
4~7h is reacted in 60~80 DEG C, obtains Waterborne Polyurethane Prepolymer a2。
In an embodiment of the present invention, small molecule chain extender be 1,2-PD, 2- methyl isophthalic acids, ammediol, new penta 2
Alcohol or TMPD；In other embodiments, small molecule chain extender is 2- methyl isophthalic acids, ammediol.
In an embodiment of the present invention, hydrophilic chain extender I is dihydromethyl propionic acid or dimethylolpropionic acid；In other implementations
In example, hydrophilic chain extender I is dihydromethyl propionic acid.
In an embodiment of the present invention, catalyst is selected from stannous octoate, tin dilaurate normal-butyl tin, the catalysis of organic Bi salt
One or more in agent, organic Zn salt catalysts；In other embodiments, organic Bi salt catalysts are isooctyl acid bismuth, bay
Jiao acid bismuth or bismuth neodecanoate；Organic Zn salt catalysts are zinc methide or diethyl zinc.
In an embodiment of the present invention, in step b), solvent is acetone or butanone.
Obtained Waterborne Polyurethane Prepolymer a2Afterwards, solvent and hydrophilic chain extender II are added thereto, it is anti-in 50~60 DEG C
0.5~1h is answered, obtains Waterborne Polyurethane Prepolymer a3。
In an embodiment of the present invention, solvent is same as above, will not be repeated here.
In an embodiment of the present invention, hydrophilic chain extender II is ethylenediamine base sodium sulfonate.
Obtained Waterborne Polyurethane Prepolymer a3Middle addition solvent, salt forming agent is added under high speed shear, after stirring 1~5min
3~5 times of water-reducible rear chain extenders are added after adding 2~5min of water high speed dispersion and emulsion, 20~40min are stirred, then true
The lower desolvation of sky, produces aqueous polyurethane；Rear chain extender is 2- amino-ethyl disulphide.
In an embodiment of the present invention, solvent is same as above, will not be repeated here.
In an embodiment of the present invention, salt forming agent be triethylamine, N, N dimethyl monoethanolamine, sodium hydroxide or potassium hydroxide；
In other embodiments, salt forming agent is triethylamine.
In an embodiment of the present invention, rear chain extender is 2- amino-ethyl disulphide.
In an embodiment of the present invention, macromolecule dihydric alcohol I：Macromolecule dihydric alcohol II：Diisocyanate：Small molecule chain extension
Agent：Hydrophilic chain extender I：Catalyst：Hydrophilic chain extender II：Salt forming agent：The mass ratio of rear chain extender is (20~40)：(40~
60)：(50~200)：(2~10)：(3~10)：(0.1~0.2)：(1~6)：(0.5~8)：(1.5~8).
In an embodiment of the present invention, solvent and diisocyanate in solvent, step d) in solvent, step c) in step b)
Mass ratio be (2~3)：(0.8~1.2)：(0.6~2.8)：1.
Present invention also offers a kind of low high-strength aqueous polyurethane of mould of above-mentioned selfreparing, it is made using above-mentioned preparation method.
Selfreparing can be achieved in the aqueous polyurethane of the present invention under conditions of no any renovation agent.
Illustrate the present invention, with reference to embodiment to the high-strength aqueous polyurethane of the low mould of selfreparing provided by the invention and its system
Preparation Method is described in detail, but they can not be interpreted as into limiting the scope of the present invention.
Embodiment 1
A) it is 1000 macromolecule dihydric alcohol I by relative molecular weight, relative molecular weight is 2000 PolyTHF dihydric alcohol
4h is reacted in 90 DEG C with IPDI, obtains polyurethane prepolymer a1；Macromolecule dihydric alcohol I is 2- ethoxys two
Sulfide and adipic acid are esterified obtained polyester diol；
B) the polyurethane prepolymer a obtained to step a)1Middle addition 1,2- propane diols, dihydromethyl propionic acid, acetone, octanoic acid
Stannous, 7h is reacted in 60 DEG C, obtains Waterborne Polyurethane Prepolymer a2；
C) the Waterborne Polyurethane Prepolymer a obtained to step b)2Middle addition acetone and ethylenediamine base sodium sulfonate, it is anti-in 50 DEG C
1h is answered, obtains Waterborne Polyurethane Prepolymer a3；
D) the Waterborne Polyurethane Prepolymer a obtained to step c)3Middle addition butanone, N, N dimethyl are added under high speed shear
Monoethanolamine, 3 times of water-reducible 2- amino-ethyls disulphide of addition after water high speed dispersion and emulsion 5min are added after stirring 5min, are stirred
40min is mixed, then desolvation under vacuo, produce the high-strength aqueous polyurethane of the low mould of selfreparing；
Macromolecule dihydric alcohol I：PolyTHF dihydric alcohol：IPDI：1,2- propane diols：Dihydroxymethyl
Propionic acid：Stannous octoate：Ethylenediamine base sodium sulfonate：N, N dimethyl monoethanolamine：The mass ratio of 2- amino-ethyl disulphide is 20：
60：50：10：10：0.2：6：8：8；
The mass ratio of butanone and IPDI is in acetone, step d) in acetone, step c) in step b)
2：0.8：2.4：1.
Embodiment 2
A) it is 2000 macromolecule dihydric alcohol I by relative molecular weight, relative molecular weight is 3000 PolyTHF dihydric alcohol
2h is reacted in 100 DEG C with 4,4'- dicyclohexyl methyl hydride diisocyanates, obtains polyurethane prepolymer a1；Macromolecule dihydric alcohol I is
2- HEDSs and adipic acid are esterified obtained polyester diol；
B) the polyurethane prepolymer a obtained to step a)1Middle addition 2- methyl-1,3-propanediols, dimethylolpropionic acid, fourth
Ketone, tin dilaurate normal-butyl tin, 4h is reacted in 80 DEG C, obtains Waterborne Polyurethane Prepolymer a2；
C) the Waterborne Polyurethane Prepolymer a obtained to step b)2Middle addition acetone and ethylenediamine base sodium sulfonate, it is anti-in 60 DEG C
0.5h is answered, obtains Waterborne Polyurethane Prepolymer a3；
D) the Waterborne Polyurethane Prepolymer a obtained to step c)3Middle addition acetone, sodium hydroxide is added under high speed shear,
5 times of water-reducible 2- amino-ethyls disulphide of addition after water high speed dispersion and emulsion 5min, stirring are added after stirring 1min
20min, then desolvation under vacuo, produces the high-strength aqueous polyurethane of the low mould of selfreparing；
Macromolecule dihydric alcohol I：PolyTHF dihydric alcohol：4,4'- dicyclohexyl methyl hydride diisocyanates：2- methyl isophthalic acids,
Ammediol：Dimethylolpropionic acid：Tin dilaurate normal-butyl tin：Ethylenediamine base sodium sulfonate：Sodium hydroxide：The sulphur of 2- amino-ethyls two
The mass ratio of compound is 25：55：80：9：8：0.18：5：6：7；
Acetone and 4,4'- dicyclohexyl methyl hydride diisocyanates in acetone, step d) in butanone, step c) in step b)
Mass ratio is 3：1.2：1.5：1.
Embodiment 3
A) it is 3000 macromolecule dihydric alcohol I by relative molecular weight, relative molecular weight is 3000 PolyTHF dihydric alcohol
3h is reacted in 100 DEG C with 4,4`- methyl diphenylene diisocyanates, obtains polyurethane prepolymer a1；Macromolecule dihydric alcohol I is two
Phenyl disulfide and adipic acid are esterified obtained polyester diol；
B) the polyurethane prepolymer a obtained to step a)1Middle addition neopentyl glycol, dihydromethyl propionic acid, acetone, isooctyl acid
Bismuth, zinc methide, 5h is reacted in 70 DEG C, obtains Waterborne Polyurethane Prepolymer a2；
C) the Waterborne Polyurethane Prepolymer a obtained to step b)2Middle addition butanone and ethylenediamine base sodium sulfonate, it is anti-in 60 DEG C
1h is answered, obtains Waterborne Polyurethane Prepolymer a3；
D) the Waterborne Polyurethane Prepolymer a obtained to step c)3Middle addition butanone, potassium hydroxide is added under high speed shear,
4 times of water-reducible 2- amino-ethyls disulphide of addition after water high speed dispersion and emulsion 4min, stirring are added after stirring 3min
30min, then desolvation under vacuo, produces the high-strength aqueous polyurethane of the low mould of selfreparing；
Macromolecule dihydric alcohol I：PolyTHF dihydric alcohol：4,4`- methyl diphenylene diisocyanates：Neopentyl glycol：Two
Hydroxymethylbutyrate：Isooctyl acid bismuth：Zinc methide：Ethylenediamine base sodium sulfonate：Potassium hydroxide：The quality of 2- amino-ethyl disulphide
Than for 30：45：100：8：6：0.08：0.08：4：5：6；
In step b) in acetone, step c) in butanone, step d) butanone and 4,4`- methyl diphenylene diisocyanates matter
Amount is than being 2.5：1：1：1.
Embodiment 4
A) it is 4000 macromolecule dihydric alcohol I by relative molecular weight, relative molecular weight is 2000 PolyTHF dihydric alcohol
3h is reacted in 90 DEG C with IPDI, obtains polyurethane prepolymer a1；Macromolecule dihydric alcohol I is 2- ethoxys two
Sulfide and adipic acid are esterified obtained polyester diol；
B) the polyurethane prepolymer a obtained to step a)1Middle addition TMPD, dimethylolpropionic acid, butanone, two
Zinc ethyl, 6h is reacted in 80 DEG C, obtains Waterborne Polyurethane Prepolymer a2；
C) the Waterborne Polyurethane Prepolymer a obtained to step b)2Middle addition butanone and ethylenediamine base sodium sulfonate, it is anti-in 50 DEG C
0.8h is answered, obtains Waterborne Polyurethane Prepolymer a3；
D) the Waterborne Polyurethane Prepolymer a obtained to step c)3Middle addition butanone, triethylamine is added under high speed shear, is stirred
4 times of water-reducible 2- amino-ethyls disulphide of addition after water high speed dispersion and emulsion 4min are added after mixing 4min, stir 30min,
Then desolvation under vacuo, produces the high-strength aqueous polyurethane of the low mould of selfreparing；
Macromolecule dihydric alcohol I：PolyTHF dihydric alcohol：IPDI：TMPD：Dihydroxy first
Base butyric acid：Diethyl zinc：Ethylenediamine base sodium sulfonate：Triethylamine：The mass ratio of 2- amino-ethyl disulphide is 40：52：150：
4:5：0.12：2：1：3；
The mass ratio of butanone and IPDI is in butanone, step d) in butanone, step c) in step b)
2.3：0.9：0.60：1.
Embodiment 5
A) it is 3000 macromolecule dihydric alcohol I by relative molecular weight, relative molecular weight is 3000 PolyTHF dihydric alcohol
3h is reacted in 100 DEG C with toluene di-isocyanate(TDI), obtains polyurethane prepolymer a1；Macromolecule dihydric alcohol I is Diphenyl disulfide
Thing and adipic acid are esterified obtained polyester diol；
B) the polyurethane prepolymer a obtained to step a)1Middle addition 2- methyl-1,3-propanediols, dihydromethyl propionic acid, third
Ketone, bismuth neodecanoate, 5h is reacted in 70 DEG C, obtains Waterborne Polyurethane Prepolymer a2；
C) the Waterborne Polyurethane Prepolymer a obtained to step b)2Middle addition acetone and ethylenediamine base sodium sulfonate, it is anti-in 50 DEG C
0.8h is answered, obtains Waterborne Polyurethane Prepolymer a3；
D) the Waterborne Polyurethane Prepolymer a obtained to step c)3Middle addition acetone, triethylamine is added under high speed shear, is stirred
4 times of water-reducible 2- amino-ethyls disulphide of addition after water high speed dispersion and emulsion 3min are added after mixing 3min, stir 30min,
Then desolvation under vacuo, produces the high-strength aqueous polyurethane of the low mould of selfreparing；
Macromolecule dihydric alcohol I：PolyTHF dihydric alcohol：Toluene di-isocyanate(TDI)：2- methyl-1,3-propanediols：Dihydroxy
Methylbutanoic acid：Bismuth neodecanoate：Ethylenediamine base sodium sulfonate：Triethylamine：The mass ratio of 2- amino-ethyl disulphide is 40：48：
200：2：3：0.1：1：0.5：1.5；
The mass ratio of acetone and toluene di-isocyanate(TDI) is 2.7 in acetone, step d) in acetone, step c) in step b)：
1.1：2：1.
Embodiment 6
A) it is 3000 macromolecule dihydric alcohol I by relative molecular weight, relative molecular weight is 3000 PolyTHF dihydric alcohol
4h is reacted in 90 DEG C with 4,4`- methyl diphenylene diisocyanates, obtains polyurethane prepolymer a1；Macromolecule dihydric alcohol I is two
Phenyl disulfide and adipic acid are esterified obtained polyester diol；
B) the polyurethane prepolymer a obtained to step a)1Middle addition TMPD, dihydromethyl propionic acid, acetone, the moon
Gui Jiao acid bismuths, 6h is reacted in 80 DEG C, obtains Waterborne Polyurethane Prepolymer a2；
C) the Waterborne Polyurethane Prepolymer a obtained to step b)2Middle addition acetone and ethylenediamine base sodium sulfonate, it is anti-in 60 DEG C
1h is answered, obtains Waterborne Polyurethane Prepolymer a3；
D) the Waterborne Polyurethane Prepolymer a obtained to step c)3Middle addition acetone, triethylamine is added under high speed shear, is stirred
4 times of water-reducible 2- amino-ethyls disulphide of addition after water high speed dispersion and emulsion 2min are added after mixing 5min, stir 40min,
Then desolvation under vacuo, produces the high-strength aqueous polyurethane of the low mould of selfreparing；
Macromolecule dihydric alcohol I：PolyTHF dihydric alcohol：4,4`- methyl diphenylene diisocyanates：Trimethyl penta 2
Alcohol：Dihydromethyl propionic acid：Yue Gui Jiao acid bismuths：Ethylenediamine base sodium sulfonate：Triethylamine：The mass ratio of 2- amino-ethyl disulphide is
30：40：125：6：6.5：0.15：3.5：4：5；
The mass ratio of acetone and toluene di-isocyanate(TDI) is 2.5 in acetone, step d) in acetone, step c) in step b)：
1.0：1.7：1.
The cut channel for measuring the high-strength aqueous polyurethane of the low mould of selfreparing made from embodiment 1~6 repairs situation hardness, stretching by force
Degree and modulus, the results are shown in Table 1.
Wherein, cut channel repairs situation：With blade on the high-strength aqueous polyurethane of the low mould of selfreparing made from embodiment 1~6
Standardized cut channel, is placed in room temperature environment, repairs situation with observation by light microscope cut channel immediately.
The test result of the embodiment 1~6 of table 1
Low high-strength aqueous polyurethane of mould of a kind of selfreparing provided by the invention and preparation method thereof has been carried out in detail above
Introduction, specific case used herein is set forth to the principle and embodiment of the present invention, and above example is said
It is bright to be only intended to help the method and its core concept for understanding the present invention, it is noted that for the ordinary skill of the art
For personnel, under the premise without departing from the principles of the invention, some improvement and modification, these improvement can also be carried out to the present invention
Also fallen into modification in the protection domain of the claims in the present invention.
Claims (10)
1. the preparation method of the low high-strength aqueous polyurethane of mould of a kind of selfreparing, it is characterised in that comprise the following steps：
A) macromolecule dihydric alcohol I, macromolecular polyol II and diisocyanate are reacted into 2~4h in 90~100 DEG C, obtains poly- ammonia
Ester prepolymer a1；The macromolecule dihydric alcohol I is the polyester diol that disulphide and adipic acid are esterified to obtain；
B) the polyurethane prepolymer a obtained to step a)1Middle addition small molecule chain extender, hydrophilic chain extender I, solvent, catalyst,
4~7h is reacted in 60~80 DEG C, obtains Waterborne Polyurethane Prepolymer a2；
C) the Waterborne Polyurethane Prepolymer a obtained to step b)2Middle addition solvent and hydrophilic chain extender II, in 50~60 DEG C of reactions
0.5~1h, obtain Waterborne Polyurethane Prepolymer a3；
D) the Waterborne Polyurethane Prepolymer a obtained to step c)3Middle addition solvent, adds salt forming agent under high speed shear, and stirring 1~
3~5 times of water-reducible rear chain extenders are added after 2~5min of water high speed dispersion and emulsion is added after 5min, stir 20~40min, so
Desolvation under vacuo afterwards, produces aqueous polyurethane；The rear chain extender is 2- amino-ethyl disulphide.
2. preparation method as claimed in claim 1, it is characterised in that the macromolecular polyol II is PolyTHF binary
Alcohol.
3. preparation method as claimed in claim 1, it is characterised in that the diisocyanate is toluene di-isocyanate(TDI), different
Isophorone diisocyanate, 4,4`- methyl diphenylene diisocyanates or 4,4'- dicyclohexyl methyl hydride diisocyanates.
4. preparation method as claimed in claim 1, it is characterised in that the small molecule chain extender is 1,2-PD, 2- first
Base -1,3- propane diols, neopentyl glycol or TMPD.
5. preparation method as claimed in claim 1, it is characterised in that the hydrophilic chain extender I is dihydromethyl propionic acid or two
Hydroxymethylbutyrate.
6. preparation method as claimed in claim 1, it is characterised in that the hydrophilic chain extender II is ethylenediamine base sodium sulfonate.
7. preparation method as claimed in claim 1, it is characterised in that the catalyst is being selected from stannous octoate, tin dilaurate just
One or more in butyl tin, organic Bi salt catalysts, organic Zn salt catalysts.
8. preparation method as claimed in claim 1, it is characterised in that the salt forming agent is triethylamine, N, N dimethyl ethanol
Amine, sodium hydroxide or potassium hydroxide.
9. preparation method as claimed in claim 1, it is characterised in that in step b), step c) and step d), the solvent is equal
Independently selected from acetone or butanone.
10. the low high-strength aqueous polyurethane of mould of a kind of selfreparing, it is characterised in that reviewed one's lessons by oneself using described in any one of claim 1~9
The preparation method of the multiple low high-strength aqueous polyurethane of mould is made.
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| CN108503782A (en) * | 2018-03-22 | 2018-09-07 | 中国科学院化学研究所 | A kind of all-transparent high intensity selfreparing polyurethane elastomer, preparation method and application |
| CN108559052A (en) * | 2018-04-19 | 2018-09-21 | 清华大学 | Crosslinking polyurea elastomer with self-healing properties and preparation method thereof |
| CN109100918A (en) * | 2018-07-25 | 2018-12-28 | 深圳市华星光电技术有限公司 | A kind of photosensitive polymer combination and its preparation method and application |
| CN109836550A (en) * | 2019-01-23 | 2019-06-04 | 湖南邦弗特新材料技术有限公司 | A kind of polyurethane resin and preparation method thereof of aqueous self-repair function |
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