CN108178822A - A kind of preparation method of environment-friendly modified aqueous polyurethane - Google Patents
A kind of preparation method of environment-friendly modified aqueous polyurethane Download PDFInfo
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- 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
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Abstract
The present invention provides a kind of preparation methods of environment-friendly modified aqueous polyurethane, include 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) in neutralizer and organic silicon modified polyurethane；(5) deionized water dispersion emulsion obtains comprehensive performance high-environmental type modified aqueous polyurethane；(6) removal solvent is vacuumized, goes out product, operation is easy, 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 comprehensive performance is higher.
Description
Technical field
The present invention relates to technical field of macromolecules, specifically relate to a kind of preparation side of environment-friendly modified aqueous polyurethane
Method.
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, product are successfully applied to the industries such as light textile, leather, timber processing, building, papermaking.But since aqueous polyurethane uses
Water is as solvent, and the surface tension of medium water 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 that aqueous polyurethane is promoted to be stably dispersed in medium water
Group can cause aqueous polyurethane film forming poor water resistance and hygroscopic；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.
Have to the modification of aqueous polyurethane both at home and abroad from molecular scale and carry 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 reduces cost using renewable resource or introduces particular functional group's reaction progress in film forming procedure
It is crosslinked to promote film forming characteristics etc..
Organosilicon has been used for the modification of polyurethane very early, because the Si-O-Si keys in its strand are with larger
Cohesive energy and with the excellent performance such as high temperature resistant, hydrolysis, and the chain belongs to flexible chain, has that low-temperature flexibility is good, surface
The advantages that tension is low, good biocompatibility carries out base polyurethane prepolymer for use as with it modification physically or chemically, can improve gluing
The comprehensive performance of agent.It is wherein most widely used for the polysiloxanes that skeleton forms with silicon oxygen bond (- SiO-Si-).Polyurethane blocks are total to
Polymers has both the excellent properties of both polysiloxane and polyurethane, shows good low-temperature flexibility, dielectricity, surface richness
Collection property and excellent biocompatibility etc., also compensate for polyurethane weatherability at the shortcomings that overcoming polysiloxanes bad mechanical property
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
Mixed mode is then there are the even film layering of serious phase-separated state, and thus mechanical property and lotion bin stability are poor.
Invention content
The object of the invention provides a kind of preparation method of environment-friendly modified aqueous polyurethane, is using different pre-polymerizations
Body by the method modified polyurethane prepolymer of physical blending, overcomes single performed polymer water-fast, and high temperature resistant, flexible difference lack
Point, and organic-silicon-modified poly- ammonia is made by addition polymerization and chain extending reaction with the polysiloxanes with active end group and performed polymer
Ester copolymer overcomes organosiloxane and the very poor technical barrier of polyurethane compatibility.
The used to solve above-mentioned technical problem technical solution of the present invention is：
A kind of preparation method of environment-friendly modified aqueous polyurethane, comprises the following steps that：
(1) prepolymerization reaction：By oligomer polyol, multicomponent isocyanate, policapram, acid dihydroxy compounds and small molecule
Chain extender is added under the protection of logical N2 in reaction kettle, controls thermotonus；It specifically includes,
(11) respectively by polyether polyols polyalcohol and polyester polyol and multicomponent isocyanate, acid dihydroxy compounds and small point
Sub- chain extender is added under the protection of logical N2 in reaction kettle, and temperature control is 75-85 DEG C, is reacted 1-3 hours, and it is pre- that polyesters are made
Aggressiveness and polyalcohols performed polymer；
(2) chain extension：Continuation puts into the bis- 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 reacts 2-3 hours, and base polyurethane prepolymer for use as is made；
It specifically includes：Polyesters performed polymer described in step (11) and polyalcohols performed polymer are subjected to chain extension in a kettle respectively
Then reaction 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, is protected in N2
7%~10% polysiloxane oligomers of lower addition adjust temperature to 70~90 DEG C, add in chain extender, insulation reaction, system after heating
Obtain organic silicon modified polyurethane performed polymer；.
(4) neutralization reaction：Neutralizer 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 down 30 DEG C and neutralized hereinafter, adding in neutralizer；The neutralizer is 5% triethylamine.
(5) moisture dissipates：It is 0~20 DEG C to adjust temperature, and deionized water is instilled the organic-silicon-modified poly- ammonia described in step (4)
It is emulsified in ester pre-polymerization precursor emulsion, then adds in chain extender, strong to stir, rotating speed control is 127min, chain extension 8-15min,
It has reacted and has vacuumized removal solvent, obtained comprehensive performance high-environmental type modified aqueous polyurethane.
Above-mentioned small molecule chain extender is 1,4-butanediol and ethylenediamine；
Above-mentioned multicomponent isocyanate includes：Isophorone diisocyanate, 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 times of dioxane and tetrahydrofuran mixed liquor, N, N '-dimethyl formamide and dimethyl sulfoxide mixed liquor
It is a kind of.
Advantageous effect of the invention
（1）Comprehensive performance high-environmental type modified aqueous polyurethane comprehensive performance of the present invention is high.The present invention uses polyalcohol not of the same race
Synthesize different performed polymers, then by the method modified polyurethane prepolymer of physical blending, overcome single performed polymer it is water-fast,
The shortcomings that high temperature resistant, flexible difference, obtain the high Waterborne Polyurethane Prepolymer of comprehensive performance.
（2）Comprehensive performance high-environmental type modified aqueous polyurethane of the present invention has a wide range of application, and weather resistance is good, mechanicalness
Can be good, so as to solve the technological difficulties of current aqueous polyurethane product application.
（3）A kind of preparation method of environment-friendly modified aqueous polyurethane of the present invention is simple for process, and condition is easily controllable, easily
It accomplishes scale production.
Specific embodiment
The embodiment of the present invention is described in detail below, the embodiment method described in following exemplary embodiment
Do not represent all embodiments consistent with the disclosure.On the contrary, they be only with as being described in detail in the appended claims
, the example of the consistent device and method of some aspects of the disclosure.
Embodiment 1
A kind of preparation method of environment-friendly modified aqueous polyurethane is present embodiments provided, is specifically included the following steps：
1st, performed polymer is prepared
(1) performed polymer A is prepared：Equipped with thermometer, reflux condensing tube, blender three-necked flask in, by polyadipate fourth two
Alcohol ester (after molecular weight M=21 row vacuum dehydrations, adds in 4.5 grams of 1,4-butanediol, 49.2 grams of isophorone diisocyanate, gathers
12 grams of acetamide, 0.15 gram of catalyst dibutyltin dilaurylate react 3 hours at 80 DEG C, measure NCO content and are less than 5.2%
When, it cools to 60 DEG C, adds in 9.6 grams of dihydromethyl propionic acid, 50 grams of acetone reacts 3 hours in 70 DEG C, and to fixed NCO when obtains
To performed polymer A.
(2) performed polymer B：Equipped with thermometer, reflux condensing tube, blender three-necked flask in, by polyether polyol PPG
(after molecular weight M=21 row vacuum dehydrations, add in 4.5 grams of 1,4-butanediol, 49.2 grams of isophorone diisocyanate, catalyst
0.15 gram of dibutyl tin laurate reacts 3 hours at 80 DEG C, when measuring NCO content less than 5.2%, cools down 60 DEG C, adds in two
9.6 grams of hydroxymethyl propionic acid, 50 grams of acetone react 3 hours in 70 DEG C, and to fixed NCO when obtains performed polymer B.
2nd, composite polyurethane performed polymer is prepared
Equipped with thermometer, reflux condensing tube, blender three-necked flask in add in A70 grams of performed polymer, the addition of B30 grams of performed polymer
5.6 grams of polysiloxane oligomers (PDMS), 10 grams of acetone react 3 hours in 70 DEG C.
3rd, it neutralizes
It cools to 30 DEG C and adds in 3.5 grams of progress neutralization reactions of triethylamine, obtain lotion.
4th, moisture dissipates
Lotion is cooled down in 20 DEG C and is emulsified hereinafter, adding in 114 grams of deionized water in high speed dispersion, then adds in 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 the organic silicon modified polyurethane resin of 40% (wt).
Embodiment 2
1st, performed polymer is prepared
(1) performed polymer A is prepared：It is equipped in the three-necked flask of thermometer, reflux condensing tube, blender 5, by polyadipate fourth two
Alcohol ester (after molecular weight M=21 row vacuum dehydrations, adds in 4.5 grams of 1,4-butanediol, 38.6 grams of toluene di-isocyanate(TDI), poly- acetyl
12 grams of amine, 0.14 gram of catalyst dibutyltin dilaurylate react 3 hours at 80 DEG C, when measuring NCO content less than 6.9%, drop
60 DEG C of temperature adds in 9.4 grams of dihydromethyl propionic acid, and 50 grams of acetone reacts 3 hours in 70 DEG C, and to fixed NCO when obtains performed polymer
A。
(2) performed polymer B is prepared：It is equipped in the three-necked flask of thermometer, reflux condensing tube, blender 5, by polyether polyols
Alcohol PPG (after molecular weight M=21 row vacuum dehydrations, adds in 4.5 grams of 1,4-butanediol, 38.6 grams of toluene di-isocyanate(TDI), catalyst
0.15 gram of dibutyl tin laurate reacts 3 hours at 80 DEG C, when measuring NCO content less than 6.9%, cools down 60 DEG C, adds in two
9.4 grams of hydroxymethyl propionic acid, 50 grams of acetone react 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, blender three-necked flask in add in 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, it neutralizes
Cool down and 3.7 grams of progress neutralization reactions of triethylamine are added in 30 DEG C.
4th, moisture dissipates
Cooling is less than 20 DEG C and is emulsified hereinafter, adding in 115 grams of deionized water in high speed dispersion, then adds in 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 the organic silicon modified polyurethane resin of 40% (wt).
Embodiment 3
The present embodiment is substantially the same manner as Example 1, difference lies in：The step of " 1, prepare performed polymer " in " (2) prepare performed polymer
The middle polytetrahydrofuran diols of B " (PTMG) replace polyether polyol.
It is understood that the above description of the embodiments is intended to facilitate those skilled in the art and using this hair
It is bright.Person skilled in the art obviously easily can make various modifications, and described herein to these embodiments
General Principle is applied in other embodiment without having to go through creative labor.Therefore, the present invention is not limited to implementations here
Example, those skilled in the art's announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be
Within protection scope of the present invention.
Claims (8)
1. a kind of preparation method of environment-friendly modified aqueous polyurethane, which is characterized in that comprise the following steps that：
(1) prepolymerization reaction：By oligomer polyol, multicomponent isocyanate, policapram, acid dihydroxy compounds and small molecule
Chain extender is added under the protection of logical N2 in reaction kettle, controls temperature；
(2) chain extension：Continuation puts into the bis- 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, is added under N2 protections
Enter 7%~10% polysiloxane oligomers and chain extender, organic silicon modified polyurethane performed polymer is made in insulation reaction；
(4) neutralization reaction：Neutralizer 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 in chain extender, strong to stir, chain extension has reacted and vacuumized solvent, obtains comprehensive performance high-environmental type modified water
Property polyurethane.
2. a kind of preparation method of environment-friendly modified aqueous polyurethane according to claim 1, which is characterized in that
The step (1) further includes：
(11) respectively by polyether polyols polyalcohol and polyester polyol and multicomponent isocyanate, acid dihydroxy compounds and small point
Sub- chain extender is added under the protection of logical N2 in reaction kettle, and temperature control is 75-85 DEG C, is reacted 1-3 hours, and it is pre- that polyesters are made
Aggressiveness and polyalcohols performed polymer；
The step (2) further 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.
A kind of 3. preparation method of environment-friendly modified aqueous polyurethane according to claim 1, which is characterized in that the step
Suddenly (2) include：60-70 DEG C of temperature, stirring are controlled, speed of agitator 280r/min reacts 2-3 hours.
A kind of 4. preparation method of environment-friendly modified aqueous polyurethane according to claim 1, which is characterized in that the step
Suddenly (3) further include：7%~10% polysiloxane oligomers are added under N2 protections, temperature is adjusted after heating to 70~90 DEG C, is added
Enter chain extender.
A kind of 5. preparation method of environment-friendly modified aqueous polyurethane according to claim 1, which is characterized in that the step
Suddenly (4) further include：30 DEG C of cooling is neutralized hereinafter, adding in neutralizer；The neutralizer is 5% triethylamine.
A kind of 6. preparation method of environment-friendly modified aqueous polyurethane according to claim 1, which is characterized in that the step
Suddenly (5) include：It is 0~20 DEG C to adjust temperature, and deionized water is instilled the organic silicon modified polyurethane performed polymer described in step (4)
It is emulsified in lotion, then adds in chain extender, strong to stir, rotating speed control is 1200~1700r/min, chain extension 8-15min,
Obtain comprehensive performance high-environmental type modified aqueous polyurethane.
A kind of 7. preparation method of environment-friendly modified aqueous polyurethane according to claim 1, which is characterized in that step
(1) small molecule chain extender is 1,4-butanediol and ethylenediamine；The multicomponent isocyanate includes：Isophorone diisocyanate
Ester, toluene 2,4- diisocyanate；The oligomer polyol includes：Polytetrahydrofuran diol.
A kind of 8. preparation method of environment-friendly modified aqueous polyurethane according to claim 1, which is characterized in that step
(3) polysiloxane oligomers are dimethyl silicone polymers；After the dimethyl silicone polymer is substituted for part methyl
The one or two of polysiloxanes；The solvent be dioxane and tetrahydrofuran mixed liquor, N, N '-dimethyl formamide and two
First sulfoxide mixed liquor it is any.
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| 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 |
| CN114570321A (en) * | 2022-05-09 | 2022-06-03 | 昱垠科技有限公司 | Polyurethane prepolymer production equipment and production method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107629188A (en) * | 2017-09-07 | 2018-01-26 | 绵阳凤面科技有限公司 | A kind of preparation method of combination property high-environmental type modified aqueous polyurethane |
| 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 |
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| CN107629188A (en) * | 2017-09-07 | 2018-01-26 | 绵阳凤面科技有限公司 | A kind of preparation method of combination property high-environmental type modified aqueous polyurethane |
| 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 |
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| 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 |
| CN114570321A (en) * | 2022-05-09 | 2022-06-03 | 昱垠科技有限公司 | Polyurethane prepolymer production equipment and production method thereof |
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Application publication date: 20180619 |