CN109503799A - A kind of waterborne polyurethane resin and preparation method thereof - Google Patents
A kind of waterborne polyurethane resin and preparation method thereof Download PDFInfo
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- CN109503799A CN109503799A CN201811281991.XA CN201811281991A CN109503799A CN 109503799 A CN109503799 A CN 109503799A CN 201811281991 A CN201811281991 A CN 201811281991A CN 109503799 A CN109503799 A CN 109503799A
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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
- C08G18/65—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
- C08G18/08—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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3225—Polyamines
- C08G18/3228—Polyamines acyclic
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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
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
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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
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
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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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
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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
- C08G18/28—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
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
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- Chemical Kinetics & Catalysis (AREA)
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- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The present invention provides a kind of waterborne polyurethane resin and preparation method thereof, waterborne polyurethane resin in the preparation, by percentage to the quality, including following material component: macromolecule dihydric alcohol 8~14%；Single terminal dihydroxy polyethylene glycol 1~1.5%；Diisocyanate 4~6%；Hydrophilic chain extender 0.1~0.5%；Small molecule chain extender 0.3~0.6%；Organic bismuth catalyst 0.05~0.1%；Salt forming agent 0.05~0.4%；Crosslinking agent 0.3~0.5%；Rear chain extender aqueous solution 2~10%；Mixture of ice and water 40~55%；Acetone 25~30%.Anionic and nonionic type of the invention is from delustring waterborne polyurethane resin, stability is high, avoids the risk that the flatting silica occurred in the prior art is precipitated, apply has excellent dumb light, blackness and sense of touch on leather, and resistance to 220 DEG C of high temperature embossing, improve the performance of leather.
Description
Technical field
The present invention relates to aqueous high molecular technical field, in particular to a kind of waterborne polyurethane resin and preparation method thereof.
Background technique
Waterborne polyurethane resin is a kind of environment-friendly type macromolecule material being concerned in recent years, using water as decentralized medium,
Have the characteristics that environmental-friendly, easy processing, non-ignitable, intensity is high, in coating, adhesive, fabric coating and finishing agent, leather finish
It is used widely in the fields such as agent.
With the raising of people's aesthetic standards, dumb light coating is increasingly taken seriously, and extinction type PUD coating does leather surface
Inorganic agent, so that leather surface has superior appearance and sense of touch.Aqueous poly- when traditional aqueous polyurethane antiglossing pigment
Flatting silica is added in urethane to reach extinction effect, but flatting silica main component is silica, with waterborne polyurethane resin
Lamination easily occurs during storage for poor compatibility, in addition, due to flatting silica have with waterborne polyurethane resin refractive index it is larger
The phenomenon that it is poor to be easy to appear into membrane permeability after covering with paint, lacquer, colour wash, etc. for difference, surface " hair mist ", at the same will lead to delustred coating scratch resistance and
Resistance to complications performance decline.
In recent years, one-component is gradually taken seriously from the exploitation of delustring waterborne polyurethane resin.Patent CN 103740250A
A kind of preparation method from extinction type leather waterborne polyurethane coating agent is disclosed, is gathered by the aqueous of two kinds of partial sizes that will be synthesized
Obtained from delustring waterborne polyurethane coating agent after the mixing thickening of urethane resin, finishing agent can stablize storage 6 months or more, gloss compared with
Height, blackness are inadequate.Patent CN 105330812A discloses a kind of low gloss aqueous polyurethane with skin sense effect and its preparation
Method, patent are hydrophilic chain extender using sulfonation polyethylene glycol, prepare partial size in the waterborne polyurethane resin of 100~1000nm,
Waterborne polyurethane coating agent is prepared in this approach haves the shortcomings that water resistance difference, gloss are slightly higher.CN 103936959A discloses one kind
The aqueous preparation method from delustring atomization resin, is prepared using mode of the internal emulsification in conjunction with additional emulsifier, uses this method
It can get high atomisation coating, but additional emulsifier easily has precipitation.
Summary of the invention
In view of the foregoing deficiencies of prior art, the purpose of the present invention is to provide a kind of waterborne polyurethane resin and its
Preparation method, to solve the above technical problems.
In order to achieve the above objects and other related objects, the present invention provides a kind of waterborne polyurethane resin, with quality percentage
Than meter, including following material component:
Preferably, the molecular weight of the macromolecule dihydric alcohol is 1000~3000, and the macromolecule dihydric alcohol is poly- tetrahydro
Furans ether glycol (PTMEG), polycaprolactone (PCL), one or more of mixtures in polycarbonate (PCD).
Preferably, single terminal dihydroxy polyethylene glycol is Perstorp Ymer N210.
Preferably, the diisocyanate is isophorone diisocyanate, hydrogenation methylenebis phenyl isocyanate, six Asias
One or more of mixtures in methyl diisocyanate.
Preferably, the hydrophilic chain extender is dihydromethyl propionic acid.
Preferably, the small molecule chain extender is cyclohexanedimethanol, 1,4-butanediol, methyl propanediol, trihydroxy methyl third
One or more of mixtures in alkane, pentaerythrite.
Preferably, the crosslinking agent is that lotus opens up and receives resting form isocyanate crosslinking.
Preferably, the rear chain extender is ethylenediamine, isophorone diamine, any one in polyether diamine, after described
Chain extension aqueous solution is 5~10 times of aqueous solutions of rear chain extender.
The present invention also provides a kind of anionic and nonionic types from the preparation method of delustring waterborne polyurethane resin, including following step
It is rapid:
S1, performed polymer is prepared；
The emulsification of S2, performed polymer obtain pre-polymerization precursor emulsion；
S3, precipitation is carried out to pre-polymerization precursor emulsion, obtains anionic and nonionic type from delustring waterborne polyurethane resin.
Preferably, the process of performed polymer is prepared are as follows: by 8~14% macromolecule dihydric alcohol and 0~1.5% single-ended double hydroxyls
Base polyethylene glycol puts into reaction kettle, is heated with stirring to 100~110 DEG C, and vacuum dehydration is to macromolecule dihydric alcohol under the conditions of -0.1MPa
For middle water content 0.03% hereinafter, being cooled to 40 DEG C, the diisocyanate of investment 4~6%, stirring is warming up to 80~90 DEG C, protects
Temperature reaction 2~3 hours, is cooled to 50 DEG C, puts into 0.1~0.5% hydrophilic chain extender, 0.3~0.6% small molecule chain extender
Acetone with 3.64%, stirs and is warming up to 80 DEG C of reactions 3~4 hours, is cooled to 50 DEG C, the organo-bismuth of investment 0.05~0.1%
Catalyst and 1.82% acetone, stirring are warming up to 70~75 DEG C and react 2~3 hours, be then cooled to 10~20 DEG C, be added 0.05
~0.4% salt forming agent and 24.29% acetone, stir 30min, obtain performed polymer；The emulsion process of performed polymer are as follows: by pre-polymerization
Body is transferred in emulsifier, and 0.3~0.5% crosslinking agent is added, and 300r/min stirs 30min, adjusts 1000~1400r/min
At the uniform velocity 40~55% mixture of ice and water is added in performed polymer under high-speed stirred, performed polymer continues to stir 5min after opening, so
Revolving speed is adjusted to 400r/min afterwards, 2~10% rear chain extender aqueous solution is added, continues stirring 3~5 hours, obtains pre-polymerization
Precursor emulsion；The desolvation process of pre-polymerization precursor emulsion are as follows: pre-polymerization precursor emulsion is warming up to 40~45 DEG C, cream is sloughed under the conditions of -0.09MPa
Acetone in liquid obtains anionic and nonionic type from delustring waterborne polyurethane resin.
For the anionic and nonionic type that the present invention is prepared using the above method from delustring waterborne polyurethane resin, stability is high, keeps away
The risk for having exempted from the flatting silica occurred in the prior art precipitation, apply has excellent dumb light, blackness and sense of touch on leather,
And resistance to 220 DEG C of high temperature embossing, improve the performance of leather.
Specific embodiment
Illustrate embodiments of the present invention below by way of specific specific example, those skilled in the art can be by this specification
Other advantages and efficacy of the present invention can be easily understood for disclosed content.The present invention can also pass through in addition different specific realities
The mode of applying is embodied or practiced, the various details in this specification can also based on different viewpoints and application, without departing from
Various modifications or alterations are carried out under spirit of the invention.It should be noted that in the absence of conflict, following embodiment and implementation
Feature in example can be combined with each other.
The present invention provides a kind of present invention to provide a kind of anionic and nonionic type from delustring waterborne polyurethane resin, with quality hundred
Divide than meter, including following material component:
Wherein, the molecular weight of macromolecule dihydric alcohol is 1000~3000, and the macromolecule dihydric alcohol is polytetrahydrofuran ether
Glycol (PTMEG), polycaprolactone (PCL), one or more of mixtures in polycarbonate (PCD).
Single terminal dihydroxy polyethylene glycol is Perstorp Ymer N210.
Diisocyanate is isophorone diisocyanate, hydrogenation methylenebis phenyl isocyanate, two isocyanide of hexa-methylene
One or more of mixtures in acid esters.
Hydrophilic chain extender is dihydromethyl propionic acid.
Small molecule chain extender is cyclohexanedimethanol, 1,4-butanediol, methyl propanediol, trimethylolpropane, pentaerythrite
Middle one or more mixture.
Crosslinking agent is that lotus opens up and receives resting form isocyanate crosslinking.
Rear chain extender is ethylenediamine, isophorone diamine, any one in polyether diamine, and rear chain extension aqueous solution expands after being
5~10 times of aqueous solutions of chain agent.
Embodiment 1
The present invention provides a kind of anionic and nonionic types for preparing from the method for delustring waterborne polyurethane resin, and steps are as follows:
The preparation of S1, performed polymer: single terminal dihydroxy polyethylene glycol of 12.14% macromolecule dihydric alcohol and 1.21% is thrown
Enter reaction kettle, be heated with stirring to 100~110 DEG C, vacuum dehydration water content into macromolecule dihydric alcohol exists under the conditions of -0.1MPa
0.03% hereinafter, be cooled to 40 DEG C, puts into 5.2% diisocyanate, and stirring is warming up to 90 DEG C, and insulation reaction 3 hours, cooling
To 50 DEG C, put into 0.15% hydrophilic chain extender, 0.56% small molecule chain extender and 3.64% acetone, stirring be warming up to 80
DEG C reaction 3 hours, 50 DEG C are cooled to, puts into 0.1% organic bismuth catalyst and 1.82% acetone, stirring is warming up to 75 DEG C of reactions
3 hours, 20 DEG C are then cooled to, 0.11% salt forming agent and 24.29% acetone is added, stirs 30min, obtains performed polymer；
S2, performed polymer is emulsified, emulsion process are as follows: performed polymer is transferred in emulsifier, 0.3% friendship is added
Join agent, 300r/min stirs 30min, adjusts and pre-polymerization at the uniform velocity is added in 48% mixture of ice and water under 1400r/min high-speed stirred
In body, performed polymer continues to stir 5min after opening, and then adjusts revolving speed to 400r/min, 2.45% rear chain extender water is added
Solution continues stirring 5 hours, obtains pre-polymerization precursor emulsion；
S3, precipitation, desolvation process are as follows: pre-polymerization precursor emulsion is warming up to 41 DEG C, -0.09MPa are carried out to pre-polymerization precursor emulsion
Under the conditions of slough acetone in lotion, obtain anionic and nonionic type from delustring waterborne polyurethane resin.
Embodiment 2
The present invention provides a kind of anionic and nonionic types for preparing from the method for delustring waterborne polyurethane resin, and steps are as follows:
The preparation of S1, performed polymer: single terminal dihydroxy polyethylene glycol of 12.14% macromolecule dihydric alcohol and 1.11% is thrown
Enter reaction kettle, be heated with stirring to 100~110 DEG C, vacuum dehydration water content into macromolecule dihydric alcohol exists under the conditions of -0.1MPa
0.03% hereinafter, be cooled to 40 DEG C, puts into 5.2% diisocyanate, and stirring is warming up to 90 DEG C, and insulation reaction 3 hours, cooling
To 50 DEG C, put into 0.2% hydrophilic chain extender, 0.6% small molecule chain extender and 3.64% acetone, stirring be warming up to 80 DEG C
Reaction 4 hours, is cooled to 50 DEG C, puts into 0.1% organic bismuth catalyst and 1.82% acetone, and stirring is warming up to 70 DEG C of reactions 3
Hour, 10 DEG C are then cooled to, 0.16% salt forming agent and 24.29% acetone is added, stirs 30min, obtains performed polymer；
S2, performed polymer is emulsified, emulsion process are as follows: performed polymer is transferred in emulsifier, 0.5% friendship is added
Join agent, 300r/min stirs 30min, adjusts and at the uniform velocity 45.24% mixture of ice and water is added in advance under 1400r/min high-speed stirred
In aggressiveness, performed polymer continues to stir 5min after opening, and then adjusts revolving speed to 400r/min, 5% rear chain extender water is added
Solution continues stirring 4 hours, obtains pre-polymerization precursor emulsion；
S3, precipitation, desolvation process are as follows: pre-polymerization precursor emulsion is warming up to 45 DEG C, -0.09MPa are carried out to pre-polymerization precursor emulsion
Under the conditions of slough acetone in lotion, obtain anionic and nonionic type from delustring waterborne polyurethane resin.
Embodiment 3
The present invention provides a kind of anionic and nonionic types for preparing from the method for delustring waterborne polyurethane resin, and steps are as follows:
The preparation of S1, performed polymer: single terminal dihydroxy polyethylene glycol of 10% macromolecule dihydric alcohol and 1% is put into reaction
Kettle is heated with stirring to 100~110 DEG C, under the conditions of -0.1MPa vacuum dehydration into macromolecule dihydric alcohol water content 0.03% with
Under, 40 DEG C are cooled to, 4.2% diisocyanate is put into, stirring is warming up to 80 DEG C, insulation reaction 2 hours, is cooled to 50 DEG C,
Put into 0.2% hydrophilic chain extender, 0.6% small molecule chain extender and 3.64% acetone, it is 3 small that stirring is warming up to 80 DEG C of reactions
When, 50 DEG C are cooled to, 0.05% organic bismuth catalyst and 1.82% acetone are put into, stirring is warming up to 75 DEG C of reactions 2 hours, so
After be cooled to 20 DEG C, be added 0.38% salt forming agent and 24.29% acetone, stir 30min, obtain performed polymer；
S2, performed polymer is emulsified, emulsion process are as follows: performed polymer is transferred in emulsifier, is added 0.32%
Crosslinking agent, 300r/min stir 30min, adjust and at the uniform velocity 50% mixture of ice and water is added in advance under 1400r/min high-speed stirred
In aggressiveness, performed polymer continues to stir 5min after opening, and then adjusts revolving speed to 400r/min, 3.5% rear chain extender is added
Aqueous solution continues stirring 3~5 hours, obtains pre-polymerization precursor emulsion；
S3, precipitation, desolvation process are carried out to pre-polymerization precursor emulsion are as follows: pre-polymerization precursor emulsion is warming up to 40~45 DEG C ,-
The acetone in lotion is sloughed under the conditions of 0.09MPa, obtains anionic and nonionic type from delustring waterborne polyurethane resin.
Embodiment 4
The present invention provides a kind of anionic and nonionic types for preparing from the method for delustring waterborne polyurethane resin, and steps are as follows:
The preparation of S1, performed polymer: single terminal dihydroxy polyethylene glycol of 13.6% macromolecule dihydric alcohol and 1% is put into anti-
Answer kettle, be heated with stirring to 100~110 DEG C, under the conditions of -0.1MPa vacuum dehydration into macromolecule dihydric alcohol water content 0.03%
Hereinafter, being cooled to 40 DEG C, 4.2% diisocyanate is put into, stirring is warming up to 80 DEG C, insulation reaction 2 hours, is cooled to 50
DEG C, put into 0.2% hydrophilic chain extender, 0.3% small molecule chain extender and 3.64% acetone, stirring be warming up to 80 DEG C of reactions
3 hours, 50 DEG C are cooled to, puts into 0.06% organic bismuth catalyst and 1.82% acetone, it is small that stirring is warming up to 75 DEG C of reactions 2
When, 20 DEG C are then cooled to, 0.1% salt forming agent and 24.29% acetone is added, stirs 30min, obtains performed polymer；
S2, performed polymer is emulsified, emulsion process are as follows: performed polymer is transferred in emulsifier, is added 0.32%
Crosslinking agent, 300r/min stir 30min, adjust and at the uniform velocity 45% mixture of ice and water is added in advance under 1400r/min high-speed stirred
In aggressiveness, performed polymer continues to stir 5min after opening, and then adjusts revolving speed to 400r/min, 5.47% rear chain extender is added
Aqueous solution continues stirring 3~5 hours, obtains pre-polymerization precursor emulsion；
S3, precipitation, desolvation process are carried out to pre-polymerization precursor emulsion are as follows: pre-polymerization precursor emulsion is warming up to 40~45 DEG C ,-
The acetone in lotion is sloughed under the conditions of 0.09MPa, obtains anionic and nonionic type from delustring waterborne polyurethane resin.
Above description is only the preferred embodiment of the application and the explanation to institute's application technology principle, those skilled in the art
Member is it should be appreciated that invention scope involved in the application, however it is not limited to technology made of the specific combination of above-mentioned technical characteristic
Scheme, while should also cover in the case where not departing from the inventive concept, it is carried out by above-mentioned technical characteristic or its equivalent feature
Any combination and the other technical solutions formed, such as features described above have similar function with (but being not limited to) disclosed herein
Can technical characteristic replaced mutually and the technical solution that is formed.
Except for the technical features described in the specification, remaining technical characteristic is the known technology of those skilled in the art, is prominent
Innovative characteristics of the invention out, details are not described herein for remaining technical characteristic.
Claims (10)
1. a kind of waterborne polyurethane resin, which is characterized in that by percentage to the quality, including following material component:
2. waterborne polyurethane resin according to claim 1, it is characterised in that: the molecular weight of the macromolecule dihydric alcohol is
1000~3000, the macromolecule dihydric alcohol is polytetrahydrofuran ether glycol (PTMEG), polycaprolactone (PCL), polycarbonate
(PCD) one or more of mixtures in.
3. waterborne polyurethane resin according to claim 1, it is characterised in that: the list terminal dihydroxy polyethylene glycol is single
Terminal dihydroxy polyethylene glycol.
4. waterborne polyurethane resin according to claim 1, it is characterised in that: the diisocyanate is isophorone two
Isocyanates, hydrogenation methylenebis phenyl isocyanate, one or more of mixtures in hexamethylene diisocyanate.
5. waterborne polyurethane resin according to claim 1, it is characterised in that: the hydrophilic chain extender is dihydroxymethyl
Propionic acid.
6. waterborne polyurethane resin according to claim 1, it is characterised in that: the small molecule chain extender is hexamethylene diformazan
Alcohol, 1,4-butanediol, methyl propanediol, trimethylolpropane, one or more of mixtures in pentaerythrite.
7. waterborne polyurethane resin according to claim 1, it is characterised in that: the crosslinking agent is that lotus opens up that receive resting form different
Isocyanate cross-linking agent.
8. waterborne polyurethane resin according to claim 1, it is characterised in that: the rear chain extender is ethylenediamine, different Buddhist
Any one in your ketone diamines, polyether diamine, it is described after chain extension aqueous solution be 5~10 times of aqueous solutions of rear chain extender.
9. a kind of preparation method of waterborne polyurethane resin as described in any one of claims 1 to 8, which is characterized in that including
Following steps:
S1, performed polymer is prepared；
The emulsification of S2, performed polymer obtain pre-polymerization precursor emulsion；
S3, precipitation is carried out to pre-polymerization precursor emulsion, obtains anionic and nonionic type from delustring waterborne polyurethane resin.
10. the preparation method of waterborne polyurethane resin according to claim 9, which is characterized in that
Prepare the process of performed polymer are as follows: by 8~14% macromolecule dihydric alcohol and 0~1.5% single terminal dihydroxy polyethylene glycol
Reaction kettle is put into, is heated with stirring to 100~110 DEG C, vacuum dehydration water content into macromolecule dihydric alcohol exists under the conditions of -0.1MPa
0.03% hereinafter, be cooled to 40 DEG C, the diisocyanate of investment 4~6%, stirring is warming up to 80~90 DEG C, insulation reaction 2~3
Hour, it is cooled to 50 DEG C, investment 0.1~0.5% hydrophilic chain extender, 0.3~0.6% small molecule chain extender and 3.64%
Acetone, stirring are warming up to 80 DEG C and react 3~4 hours, are cooled to 50 DEG C, the organic bismuth catalyst of investment 0.05~0.1% and
1.82% acetone, stirring are warming up to 70~75 DEG C and react 2~3 hours, be then cooled to 10~20 DEG C, be added 0.05~0.4%
Salt forming agent and 24.29% acetone, stir 30min, obtain performed polymer；
The emulsion process of performed polymer are as follows: performed polymer is transferred in emulsifier, 0.3~0.5% crosslinking agent, 300r/min is added
30min is stirred, adjusts and performed polymer at the uniform velocity is added in 40~55% mixture of ice and water under 1000~1400r/min high-speed stirred
In, performed polymer continues to stir 5min after opening, and then adjusts revolving speed to 400r/min, 2~10% rear chain extender water is added
Solution continues stirring 3~5 hours, obtains pre-polymerization precursor emulsion；
The desolvation process of pre-polymerization precursor emulsion are as follows: pre-polymerization precursor emulsion is warming up to 40~45 DEG C, lotion is sloughed under the conditions of -0.09MPa
In acetone, obtain anionic and nonionic type from delustring waterborne polyurethane resin.
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| CN112900107A (en) * | 2021-01-15 | 2021-06-04 | 江苏华缘高科股份有限公司 | Waterborne polyurethane/organic silicon composite mirror leather and preparation method thereof |
| CN112961318A (en) * | 2021-02-07 | 2021-06-15 | 武汉纺织大学 | Polyurethane thickener compound with mixed side long-chain alkyl and preparation method thereof |
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Application publication date: 20190322 |