CN107629188A - A kind of preparation method of combination property high-environmental type modified aqueous polyurethane - Google Patents
A kind of preparation method of combination property high-environmental type modified aqueous polyurethane Download PDFInfo
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- CN107629188A CN107629188A CN201710802506.8A CN201710802506A CN107629188A CN 107629188 A CN107629188 A CN 107629188A CN 201710802506 A CN201710802506 A CN 201710802506A CN 107629188 A CN107629188 A CN 107629188A
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- polyurethane
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Abstract
The invention provides a kind of preparation method of combination property high-environmental type modified aqueous polyurethane, comprise the following steps：(1) polyesters performed polymer and polyalcohols performed polymer are prepared respectively；(2) it is blended, obtains composite polyurethane performed polymer；(3) composite polyurethane performed polymer is modified with polysiloxane oligomers, obtains organic silicon modified polyurethane；(4) use nertralizer in and organic silicon modified polyurethane；(5) deionized water dispersion emulsion, combination property high-environmental type modified aqueous polyurethane is obtained；(6) removal solvent is vacuumized, goes out product, it is easy that it is operated, and is easy to large-scale production.The present invention uses different performed polymers, pass through physical modification base polyurethane prepolymer for use as, organic silicon modified polyurethane copolymer is made with polysiloxanes addition polymerization, chain extending reaction again, overcomes organosiloxane and the very poor technical barrier of polyurethane compatibility, product combination property is higher.
Description
Technical field
The present invention relates to technical field of macromolecules, specifically relate to one kind and uses combination property high-environmental type modified water-soluble
The method of polyurethane.
Background technology
With the enhancing of people's environmental consciousness, material safety problem is all the more paid attention to, to packing compound adhesive, leather painting
Layer waits other daily necessitiess to propose higher and higher standard and requirement.Aqueous polyurethane (WPU) is as decentralized medium using water
Polyaminoester emulsion, in addition to solvent borne polyurethane excellent properties, also have excellent using simple, nontoxic, non-environmental-pollution etc.
Point, its product are successfully applied to the industries such as light textile, leather, timber processing, building, papermaking.But because aqueous polyurethane uses
Water is as solvent, and the surface tension of WATER AS FLOW MEDIUM is too big, heat content is high so that surface spreading is poor in its film forming procedure, drying time
Long, film forming and the compound difference of base material, mechanical property reduce；And the hydrophily base for promoting aqueous polyurethane to be stably dispersed in WATER AS FLOW MEDIUM
Group, aqueous polyurethane film forming poor water resistance and hygroscopic can be caused；High-viscosity organic phase can be led during aqueous polyurethane emulsion dispersion
The difficulties in dispersion of cause, emulsion particle diameter are big and emulsion solid content is relatively low.
Modification to aqueous polyurethane both at home and abroad, which has from molecular scale, carries out polyol molecule design modification, or by specific point
Minor structure or element introduce polyalcohol and change macromolecular main chain to improve various application performances, or carry out nanometer in micro-scale
Composite lifting mechanical property, or cost is reduced using renewable resource, or introduce particular functional group in film forming procedure and react progress
It is crosslinked to lift film forming characteristics etc..
Organosilicon has been used for the modification of polyurethane very early, because the Si-O-Si keys among its strand have it is larger
Cohesive energy and there is high temperature resistant, the excellent performance such as hydrolysis, and the chain belongs to flexible chain has that low-temperature flexibility is good, surface
The advantages that tension force is low, good biocompatibility carries out modification physically or chemically with it to base polyurethane prepolymer for use as, can improve gluing
The combination property of agent.It is that the polysiloxanes that skeleton forms is most widely used wherein with silicon oxygen bond (- SiO-Si-).Polyurethane blocks are total to
Polymers has the excellent properties of both polysiloxane and polyurethane concurrently, shows good low-temperature flexibility, dielectricity, surface richness
Collection property and excellent biocompatibility etc., the shortcomings that overcoming polysiloxanes bad mechanical property, it also compensate for polyurethane weatherability
The deficiency of difference.
It is typically due to organosiloxane to differ greatly with polyurethane segment solubility parameters, compatibility is very poor, is total to using physics
Then there is the even film layering of serious phase-separated state in mixed mode, thus mechanical property and emulsion bin stability are poor.
The content of the invention
Present invention aims at different performed polymers are used, by the method modified polyurethane prepolymer of physical blending, overcome
Single performed polymer water-fast, high temperature resistant, it is flexible poor the shortcomings that, and with the polysiloxanes with active end group with performed polymer by adding
Organic silicon modified polyurethane copolymer is made into polymerization and chain extending reaction, overcomes organosiloxane and polyurethane compatibility very poor
Technical barrier.
The present invention is that technical scheme is used by solving above-mentioned technical problem：
A kind of preparation method of combination property high-environmental type modified aqueous polyurethane, is comprised the following steps that：
(1) prepolymerization reaction：By oligomer polyol, multicomponent isocyanate, policapram, acid dihydroxy compounds and small molecule
Chain extender is in logical N2Protection under in addition reactor, control thermotonus；Specifically include,
(11) respectively by polyether polyols polyalcohol and PEPA and multicomponent isocyanate, acid dihydroxy compounds and small point
Sub- chain extender is in logical N2Protection under in addition reactor, temperature control is 75-85 DEG C, reacts 1-3 hours, and it is pre- that polyesters are made
Aggressiveness and polyalcohols performed polymer；
(2) chain extension：Continuation puts into the double hydroxymethyl propionic acids of 2,2- in a kettle, acetone carries out chain extension end capping reaction, controls temperature
60-70 DEG C, stirring, speed of agitator 280r/min, 2-3 hours are reacted, base polyurethane prepolymer for use as is made；
Specifically include：Polyesters performed polymer described in step (11) and polyalcohols performed polymer are subjected to chain extension in a kettle respectively
Reaction, then it is blended and composite polyurethane performed polymer is made.
(3) organic-silicon-modified performed polymer：Base polyurethane prepolymer for use as described in step (2) is added in solvent, protected in N2
7%~10% polysiloxane oligomers of lower addition, temperature is adjusted after heating to 70~90 DEG C, adds chain extender, insulation reaction, system
Obtain organic silicon modified polyurethane performed polymer；.
(4) neutralization reaction：Nertralizer is added in the organic silicon modified polyurethane performed polymer described in step (3) to be neutralized,
Obtain organic silicon modified polyurethane pre-polymerization precursor emulsion；
Specifically, cool less than 30 DEG C, add nertralizer and neutralized；Described nertralizer is 5% triethylamine.
(5) moisture dissipates：It is 0~20 DEG C to adjust temperature, and deionized water is instilled into the organic-silicon-modified poly- ammonia described in step (4)
Being emulsified in ester pre-polymerization precursor emulsion, then add chain extender, strong agitation, rotating speed control is 127min, chain extension 8-15min,
React and vacuumized removal solvent, obtained combination property high-environmental type modified aqueous polyurethane.
Above-mentioned small molecule chain extender is BDO and ethylenediamine；
Above-mentioned multicomponent isocyanate includes：IPDI, toluene 2,4- diisocyanate；
Above-mentioned oligomer polyol includes：Polytetrahydrofuran diol；
Above-mentioned polysiloxane oligomers are dimethyl silicone polymers；
Above-mentioned dimethyl silicone polymer is the one or two of the polysiloxanes after part methyl is substituted；
Above-mentioned solvent is dioxane and tetrahydrofuran mixed liquor, N, N '-dimethyl formamide and dimethyl sulfoxide mixed liquor times
It is a kind of.
The beneficial effect of invention
Combination property high-environmental type modified aqueous polyurethane combination property of the present invention is high.The present invention is using polyalcohol synthesis not of the same race
Different performed polymers, then by the method modified polyurethane prepolymer of physical blending, single performed polymer is overcome in water-fast, resistance to height
The shortcomings that temperature, poor flexibility, obtain the high Waterborne Polyurethane Prepolymer of combination property.
Combination property high-environmental type modified aqueous polyurethane of the present invention has a wide range of application, and its weather resistance is good, mechanical performance
Well, so as to solving the technological difficulties of current aqueous polyurethane product application.
The preparation method technique of combination property high-environmental type modified aqueous polyurethane of the present invention is simple, and condition is easily controllable,
Easily accomplish scale production.
With reference to embodiment, the present invention is further described.
Embodiment
Embodiment 1
A kind of preparation method of combination property high-environmental type modified aqueous polyurethane is present embodiments provided, specifically including following
Step：
1st, performed polymer is prepared
(1) performed polymer A is prepared：It is equipped with 5 in the three-necked flask of thermometer, reflux condensing tube, agitator, by polyadipate fourth two
Alcohol ester (after molecular weight M=21 row vacuum dehydrations, adds 4.5 grams of BDO, 49.2 grams of IPDI, gathered
12 grams of acetamide, 0.15 gram of catalyst dibutyltin dilaurylate, reacted 3 hours at 80 DEG C, measure NCO content is less than 5.2%
When, cool to 60 DEG C, add 9.6 grams of dihydromethyl propionic acid, 50 grams of acetone, reacted 3 hours in 70 DEG C, obtain during to fixed NCO
To performed polymer A.
(2) performed polymer B：It is equipped with 5 in the three-necked flask of thermometer, reflux condensing tube, agitator, by PPG
PPG (after molecular weight M=21 row vacuum dehydrations, adds 4.5 grams of BDO, 49.2 grams of IPDI, catalysis
0.15 gram of agent dibutyl tin laurate, reacted 3 hours at 80 DEG C, when measure NCO content is less than 5.2%, cool 60 DEG C, add
9.6 grams of dihydromethyl propionic acid, 50 grams of acetone react 3 hours in 70 DEG C, obtain performed polymer B during to fixed NCO.
2nd, composite polyurethane performed polymer is prepared
5 equipped with thermometer, reflux condensing tube, agitator three-necked flask in add A70 grams of performed polymer, B30 grams of performed polymer plus
Enter 5.6 grams of polysiloxane oligomers (PDMS), 10 grams of acetone reacts 3 hours in 70 DEG C.
3rd, neutralize
Cool to 30 DEG C and add 3.5 grams of progress neutralization reactions of triethylamine, obtain emulsion.
4th, moisture dissipates
Emulsion is cooled in less than 20 DEG C, 114 grams of deionized water is added under high speed deployment conditions and is emulsified, then adds second
1.4 grams of diamines and the mixed liquor of 5.6 grams of deionized water carry out chain extending reaction, obtain crude product.
5th, solvent is removed
Crude product vacuum is sloughed into acetone and obtains 40% (wt) organic silicon modified polyurethane resin.
Embodiment 2
1st, performed polymer is prepared
(1) performed polymer A is prepared：It is equipped with 5 in the three-necked flask of thermometer, reflux condensing tube, agitator, by polyadipate fourth two
Alcohol ester (after molecular weight M=21 row vacuum dehydrations, adds 4.5 grams of BDO, 38.6 grams of toluene di-isocyanate(TDI), poly- acetyl
12 grams of amine, 0.14 gram of catalyst dibutyltin dilaurylate, reacted 3 hours at 80 DEG C, when measure NCO content is less than 6.9%, drop
60 DEG C of temperature, 9.4 grams of dihydromethyl propionic acid is added, 50 grams of acetone reacts 3 hours in 70 DEG C, obtains performed polymer during to fixed NCO
A。
(2) performed polymer B is prepared：It is equipped with 5 in the three-necked flask of thermometer, reflux condensing tube, agitator, by polyether polyols
Alcohol PPG (after molecular weight M=21 row vacuum dehydrations, adds 4.5 grams of BDO, 38.6 grams of toluene di-isocyanate(TDI), catalyst
0.15 gram of dibutyl tin laurate, reacted 3 hours at 80 DEG C, when measure NCO content is less than 6.9%, cool 60 DEG C, add two
9.4 grams of hydroxymethyl propionic acid, 50 grams of acetone, reacted 3 hours in 70 DEG C, to fixed NCO, obtain performed polymer B.
2nd, composite polyurethane performed polymer is prepared
5 equipped with thermometer, reflux condensing tube, agitator three-necked flask in add A70 grams of performed polymer, B30 grams of performed polymer plus
Enter 5.3 grams of polysiloxane oligomers (PDMS), 10 grams of acetone reacts 3 hours in 70 DEG C.
3rd, neutralize
Cool and 3.7 grams of progress neutralization reactions of triethylamine are added in 30 DEG C.
4th, moisture dissipates
Cooling is less than less than 20 DEG C, and 115 grams of deionized water is added under high speed deployment conditions and is emulsified, then adds ethylenediamine
1.4 grams and the mixed liquor progress chain extending reaction of 5.6 grams of deionized water.
5th, solvent is removed
Vacuum sloughs acetone and obtains 40% (wt) organic silicon modified polyurethane resin.
Embodiment 3
The present embodiment is substantially the same manner as Example 1, and its difference is：The step of " 1, prepare performed polymer " in " (2) prepare performed polymer
The middle polytetrahydrofuran diols of B " (PTMG) substitute PPG.
The present invention is not limited to above-described embodiment, every all equivalent embodiments that can realize the object of the invention,
Within protection scope of the present invention.
Claims (8)
1. a kind of preparation method of combination property high-environmental type modified aqueous polyurethane, it is characterised in that walked including following technique
Suddenly：
(1) prepolymerization reaction：By oligomer polyol, multicomponent isocyanate, policapram, acid dihydroxy compounds and small molecule
Chain extender is added in reactor under logical N2 protection, controls temperature；
(2) chain extension：Continuation puts into the double hydroxymethyl propionic acids of 2,2- in a kettle, acetone carries out chain extension end capping reaction, and poly- ammonia is made
Ester performed polymer；
(3) organic-silicon-modified performed polymer：Base polyurethane prepolymer for use as described in step (2) is added in solvent, added under N2 protections
Enter 7%~10% polysiloxane oligomers and chain extender, insulation reaction, organic silicon modified polyurethane performed polymer is made；
(4) neutralization reaction：Nertralizer is added in the organic silicon modified polyurethane performed polymer described in step (3) to be neutralized, and must be had
Machine silicon modified polyurethane pre-polymerization precursor emulsion；
(5) moisture dissipates：Deionized water is instilled in the organic silicon modified polyurethane pre-polymerization precursor emulsion described in step (4) and carries out breast
Change, then add chain extender, strong agitation, chain extension, reacted and vacuumized solvent, obtain combination property high-environmental type modified water
Property polyurethane.
2. the preparation method of combination property high-environmental type modified aqueous polyurethane according to claim 1, it is characterised in that
The step (1) also includes：
(11) respectively by polyether polyols polyalcohol and PEPA and multicomponent isocyanate, acid dihydroxy compounds and small point
Sub- chain extender is in logical N2Protection under in addition reactor, temperature control is 75-85 DEG C, reacts 1-3 hours, and it is pre- that polyesters are made
Aggressiveness and polyalcohols performed polymer；
The step (2) also includes：
(22) the polyesters performed polymer described in step (11) and polyalcohols performed polymer are subjected to chain extending reaction in a kettle respectively,
Then it is blended and composite polyurethane performed polymer is made.
3. the preparation method of combination property high-environmental type modified aqueous polyurethane according to claim 1, it is characterised in that
The step (2) includes：60-70 DEG C of temperature is controlled, stirring, speed of agitator 280r/min, reacts 2-3 hours.
4. the preparation method of combination property high-environmental type modified aqueous polyurethane according to claim 1, it is characterised in that
The step (3) also includes：Add 7%~10% polysiloxane oligomers under N2 protections, adjusted after heating temperature to 70~
90 DEG C, add chain extender.
5. the preparation method of combination property high-environmental type modified aqueous polyurethane according to claim 1, it is characterised in that
The step (4) also includes：Less than 30 DEG C of cooling, add nertralizer and neutralized；Described nertralizer is 5% triethylamine.
6. the preparation method of combination property high-environmental type modified aqueous polyurethane according to claim 1, it is characterised in that
The step (5) includes：It is 0~20 DEG C to adjust temperature, and deionized water is instilled into the organic silicon modified polyurethane described in step (4)
Emulsified in pre-polymerization precursor emulsion, then add chain extender, strong agitation, rotating speed control is 1200~1700r/min, chain extension 8-
15min, obtain combination property high-environmental type modified aqueous polyurethane.
7. the preparation method of combination property high-environmental type modified aqueous polyurethane according to claim 1, it is characterised in that
Step (1) described small molecule chain extender is BDO and ethylenediamine；The multicomponent isocyanate includes：Isophorone two is different
Cyanate, toluene 2,4- diisocyanate；The oligomer polyol includes：Polytetrahydrofuran diol.
8. the preparation method of combination property high-environmental type modified aqueous polyurethane according to claim 1, it is characterised in that
Step (3) described polysiloxane oligomers are dimethyl silicone polymers；The dimethyl silicone polymer is substituted for part methyl
The one or two of polysiloxanes afterwards；The solvent is dioxane and tetrahydrofuran mixed liquor, N, N '-dimethyl formamide
It is any with dimethyl sulfoxide mixed liquor.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107973894A (en) * | 2017-12-07 | 2018-05-01 | 遂宁市明川零贰零科技有限公司 | A kind of preparation method of comprehensive performance high-environmental type modified aqueous polyurethane |
| CN108178822A (en) * | 2017-12-29 | 2018-06-19 | 何俊 | A kind of preparation method of environment-friendly modified aqueous polyurethane |
| CN109553747A (en) * | 2018-12-05 | 2019-04-02 | 长春工业大学 | A kind of preparation method of the biodegradable aqueous polyurethane of large arch dam |
| CN109734875A (en) * | 2018-12-24 | 2019-05-10 | 上海东大化学有限公司 | A kind of aminosilane coupling agent modifying aqueous polyurethane and preparation method thereof |
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| CN102093530A (en) * | 2010-12-21 | 2011-06-15 | 东莞市宏达聚氨酯有限公司 | Preparation method of organosilicon-modified aqueous polyurethane |
| CN102134387A (en) * | 2010-12-27 | 2011-07-27 | 邬元娟 | Method for reactive-organosilicon-modified aqueous polyurethane |
| CN102746818A (en) * | 2012-07-26 | 2012-10-24 | 南京工业大学 | Waterborne polyurethane material and preparation method thereof |
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Patent Citations (3)
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| CN102093530A (en) * | 2010-12-21 | 2011-06-15 | 东莞市宏达聚氨酯有限公司 | Preparation method of organosilicon-modified aqueous polyurethane |
| CN102134387A (en) * | 2010-12-27 | 2011-07-27 | 邬元娟 | Method for reactive-organosilicon-modified aqueous polyurethane |
| CN102746818A (en) * | 2012-07-26 | 2012-10-24 | 南京工业大学 | Waterborne polyurethane material and preparation method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107973894A (en) * | 2017-12-07 | 2018-05-01 | 遂宁市明川零贰零科技有限公司 | A kind of preparation method of comprehensive performance high-environmental type modified aqueous polyurethane |
| CN108178822A (en) * | 2017-12-29 | 2018-06-19 | 何俊 | A kind of preparation method of environment-friendly modified aqueous polyurethane |
| CN109553747A (en) * | 2018-12-05 | 2019-04-02 | 长春工业大学 | A kind of preparation method of the biodegradable aqueous polyurethane of large arch dam |
| CN109553747B (en) * | 2018-12-05 | 2021-06-08 | 长春工业大学 | Preparation method of high-solid content biodegradable waterborne polyurethane |
| CN109734875A (en) * | 2018-12-24 | 2019-05-10 | 上海东大化学有限公司 | A kind of aminosilane coupling agent modifying aqueous polyurethane and preparation method thereof |
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Application publication date: 20180126 |