CN102134387B - Method for reactive-organosilicon-modified aqueous polyurethane - Google Patents
Method for reactive-organosilicon-modified aqueous polyurethane Download PDFInfo
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- CN102134387B CN102134387B CN 201010606940 CN201010606940A CN102134387B CN 102134387 B CN102134387 B CN 102134387B CN 201010606940 CN201010606940 CN 201010606940 CN 201010606940 A CN201010606940 A CN 201010606940A CN 102134387 B CN102134387 B CN 102134387B
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Abstract
The invention discloses a method for preparing reactive-organosilicon-modified aqueous polyurethane, which comprises: firstly, reacting double-hydroxyalkyl-terminated polysiloxane of which the lateral group has a ketone carbonyl with polyisocyanate, and introducing reactive organosilicon into the structure of the polyurethane; secondly, dispersing a reactive-organosilicon-modified polyurethane prepolymer in water by using acetone method and by self-emulsification; and finally, after the dispersion is finished, dissolving diacylhydrazine according to a molar ratio of the ketone carbonyl to the diacylhydrazine of 2:1 on the basis of the molar content of the ketone carbonyl in the reaction system, and stirring uniformly to obtain the reactive-organosilicon-modified polyurethane dispersion. The synthesized polyurethane dispersion can be stored stably, and in a drying film forming process, a crosslinked structure is formed by reacting the ketone carbonyl with the diacylhydrazine in the polyurethane dispersion at room temperature. Compared with the conventional aqueous polyisocyanate, the reactive-organosilicon-modified polyurethane can greatly improve the physical and chemical performance of coatings.
Description
Technical field
The present invention relates to a kind of preparation method of response type organic silicon modified aqueous polyurethane, a kind of specifically preparation method that can carry out organic-silicon-modified and cross-linking modified aqueous polyurethane dispersion simultaneously.
Background technology
Because environmentally friendly, aqueous polyurethane has obtained significant progress in the finishing agent field since coming out, but has also run into a difficult problem that restricts its application.Because the synthetic aqueous polyurethane mostly is the line style dispersion product greatly, add the existence of hydrophilic radical in the molecule segment, make the poor water resistance that aqueous polyurethane is filmed.Research data shows, organic-silicon-modifiedly can improve the water tolerance that aqueous polyurethane is filmed.Though the organosilicon segment is incorporated into goes in the polyurethane molecular significantly to improve the water tolerance of filming, the shortcoming of organosilicon self bad mechanical property has also influenced the physical and mechanical properties of filming.In order to overcome the organic-silicon-modified shortcoming of bringing, improve the physical and mechanical properties of filming, most effectual way makes the dispersion mould material obtain three-dimensional crosslinking structure exactly.
Owing to disperse the membrane formation mechanism restriction, the unique method that obtains this three-dimensional crosslinking structure is exactly that the back is crosslinked, and promptly the polymkeric substance of dispersion is uncrosslinked line style or branched structure, causes crosslinking reaction behind the dispersion drying and forming-film and forms crosslinking structure.At present, cross-linking system is exactly a ketone hydrazine cross-linking system behind unique successful aqueous polyurethane.By in the aqueous polyurethane structure, introducing the ketone carbonyl, in drying process, along with the volatilization of volatilizable organic amine neutralizing agent, ketone carbonyl and hydrazides react form crosslinked.
Summary of the invention
In order to improve the water resistance that aqueous polyurethane is filmed, overcome the shortcoming of bringing after organic-silicon-modified simultaneously, the invention provides a kind of preparation method of response type organic silicon modified aqueous polyurethane, a kind of specifically preparation method that can carry out organic-silicon-modified and cross-linking modified aqueous polyurethane dispersion simultaneously.
Technical characterictic of the present invention is: with response type organosilicon, polyisocyanates, polymer polyatomic alcohol, hydrophilic chain extender, general chainextender, organic amine neutralizing agent, dispersion chainextender is raw material, by prepolymerization reaction, salt-forming reaction and dispersion chain extending reaction, obtain the organic silicon modified polyurethane dispersion; According to the amount of substance of ketone carbonyl in the reaction system, by ketone carbonyl and bishydrazide mol ratio 2: 1 bishydrazide is dissolved in, obtain the response type organic silicon modified polyurethane aqueous dispersoid after stirring.
The response type organosilicon has following structural formula:
R wherein
1Be hydroxyl alkyl, have following structure:
A
1)CH
2CH
2CH
2OH A
2)CH
2CH
2CH
2CH
2OH A
3)CH
2CH
2CH
2CH
2CH
2OH
A
4)CH
2CH
2CH
2CH
2CH
2CH
2OH A
5)CH
2CH
2CH
2OCH
2CH(OH)CH
2OCH
3
A
6)CH
2CH
2CH
2OCH
2CH(OH)CH
2N(CH
3)
2 A
7)CH
2CH
2CH
2OCH
2CH(OH)CH
2N(CH
2CH
3)
2
A
8)CH
2CH
2CH
2OCH
2CH(OH)CH
2N(CH
2CH
2CH
3)
2
A
10)CH
2CH
2CH
2OCH
2CH(OH)CH
2N(CH
2CH
2CH
2CH
3)
2 
R wherein
2Be the ketone carbonyl, have following structure:
Wherein, n represents the integer of 1-14, and m represents the integer of 1-36.
Polyisocyanates is any one in tolylene diisocyanate, '-diphenylmethane diisocyanate, polymethylene polyphenyl vulcabond, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, dicyclohexyl methyl hydride isocyanic ester, trimethyl hexamethylene diisocyanate and the hydrogenated tolylene diisocyanate.
Polymer polyatomic alcohol is any one in the pure and mild polycarbonate polyol of polyether glycol, polyester polyols, wherein: (1) employed polyether glycol is any one in polytetrahydrofuran polyvalent alcohol, polyoxyethylene polyvalent alcohol, the polyoxytrimethylene polyvalent alcohol, or tetrahydrofuran (THF), ethylene oxide, propylene oxide are a kind of in both polyol arbitrarily, or tetrahydrofuran (THF), ethylene oxide, propylene oxide three polyol; (2) employed polyester polyol is any one in poly-hexanodioic acid hexylene glycol ester, poly adipate succinic acid ester, polyethylene glycol adipate, polyneopentyl glycol adipate, the poly-phthalic acid hexylene glycol ester, or the polyester polyol that forms by diprotic acid and dibasic alcohol condensation, or the polyester polyol that forms by lactone ring opening polymerization, for example: the polycaprolactone dibasic alcohol; (3) employed polycarbonate polyol is the oligopolymer that contains two or more terminal hydroxy group carbonate-containing structures, is to be obtained by transesterify by carbonic diester and dibasic alcohol.
Hydrophilic chain extender is any one in dimethylol propionic acid, dimethylolpropionic acid and the N-sulfonic acid ethylethylenediamine.
General chainextender is any one in ethylene glycol, propylene glycol, butyleneglycol, Diethylene Glycol, triethylene glycol, quadrol, propylene diamine, butanediamine and the hexanediamine.
The organic amine neutralizing agent is any one in triethylamine and the ammoniacal liquor.
The dispersion chainextender is any one in diethylenetriamine, diethanolamine, trolamine, serinol and the glycerol.
Bishydrazide is any one in adipic dihydrazide, sebacic dihydrazide, ethylene acid hydrazide, succinic acid hydrazide ii, propanedioic acid two hydrazides and carbonic acid two hydrazides.
The amount of the synthetic required various raw materials of above-mentioned response type organic silicon modified polyurethane aqueous dispersoid is by response type organosilicon content (response type organosilicon quality accounts for the per-cent of total solids quality), polymer polyatomic alcohol content (the polymer polyatomic alcohol quality accounts for the per-cent of total solids quality), hydrophilic radical carboxylic acid group content (the hydrophilic radical quality accounts for the per-cent of total solids quality), solid content (the total solids quality accounts for the per-cent of product), isocyanato content decides in mol ratio of isocyanate group and hydroxyl (amino is equal to hydroxyl) and the prepolymer.Wherein, the mol ratio of the hydroxyl summation in the raw material polyisocyanates in isocyanate group and raw material reaction type organosilicon, polymer polyatomic alcohol, hydrophilic chain extender and the general chainextender is: 1.5: 1～1: 1, the mol ratio of hydrophilic chain extender and organic amine neutralizing agent is: 1: 1, range of solid content is: 20%～40%, response type organosilicon content range is: 3%～11%, the polymer polyatomic alcohol content range is: 46%～54%, hydrophilic radical carboxylic acid group content range is: 1%～4%, and isocyanato content theoretical value is 0.1%-5% in the prepolymer; When described dispersion chainextender and prepolymerization reaction finish in the prepolymer mol ratio of isocyanato be 0.33～0.4.Described total solids quality is the total mass of response type organosilicon, polyisocyanates, polymer polyatomic alcohol, hydrophilic chain extender, general chainextender and organic amine neutralizing agent.
Illustrate as follows with regard to above-mentioned reinforced method of calculation, every production 1kg response type organic silicon modified polyurethane aqueous dispersoid, wherein the mol ratio of isocyanate group and hydroxyl is: 1.3: 1, solid content was: 20%, polyisocyanates is that tolylene diisocyanate, response type organosilicon content are (with R
1=A
1, R
2=B
4, m=2, n=3, M
n=1000 for example) be 5%, hydrophilic radical carboxylic acid group content is: 2%, polymer polyatomic alcohol content is polyether glycol (M
n=2000), general chainextender is that ethylene glycol, organic amine neutralizing agent are that triethylamine, dispersion chainextender are that diethylenetriamine, bishydrazide are adipic dihydrazide, the amount of required various raw materials sees the following form.
Table 1 is produced the raw material scale of 1kg response type organic silicon modified polyurethane aqueous dispersoid
The principal reaction of synthetic method of the present invention is as follows:
Prepolymerization reaction: add polyisocyanates and response type organosilicon in the reaction vessel, be warming up to 50～80 ℃ of afterreaction 30～60min; Add polymer polyatomic alcohol then, continue reaction 30～60min under the same temperature; Hydrophilic chain extender is joined in the reaction system, behind reaction 30～60min under 50～80 ℃; Add general chainextender then and analyze isocyanato content in the prepolymer with standard Di-n-Butyl Amine back titration method behind reaction 40～60min down for 50～80 ℃, when isocyanato content reaches theoretical value, termination reaction, obtain main chain and contain ether, urethano and polysiloxane segment, the polynary block prepolymer of side chain ketocarbonyl-containing.Wherein, isocyanato content theoretical value in the prepolymer=(the total amount of substance of polyisocyanates amount of substance-oxy-compound (raw material reaction type organosilicon, polymer polyatomic alcohol, hydrophilic chain extender and general chainextender)) * 2* isocyanato molecular weight/total solids quality.
Salt-forming reaction: prepolymer is reduced to room temperature, adds acetone and reduce viscosity, stir under the room temperature, obtain homogeneous phase solution until the prepolymer dissolving, add in the organic amine neutralizing agent again and molecular chain in the carboxylic acid group.
Disperse chain extending reaction: the base polyurethane prepolymer for use as brute force is scattered in the deionized water that disperses chainextender makes its emulsification chain extension.The emulsification chain extension is removed acetone in 50 ℃ after finishing.
Add bishydrazide: according to the amount of substance of ketocarbonyl-containing in the reaction system, dissolve in adipic dihydrazide at 2: 1 by the mol ratio of ketone carbonyl and bishydrazide, stirring obtains the response type organic silicon modified polyurethane aqueous dispersoid.
Reaction principle of the present invention is: at first, select for use end capped polysiloxane of two hydroxyl alkyls and the polyisocyanates that side group contains the ketone carbonyl to react, hydroxypropyl and isocyanato reaction by organosilicon main chain two ends are incorporated into the organosilicon segment on the aqueous polyurethane molecule segment, thereby obtain organic-silicon-modified aqueous polyurethane; Then, adopt the acetone method base polyurethane prepolymer for use as that response type is organic-silicon-modified to be distributed in the water by self-emulsifying.After disperse finishing,, bishydrazide is dissolved in, obtain the response type organic silicon modified polyurethane aqueous dispersoid after stirring by ketone carbonyl and bishydrazide mol ratio 2: 1 according to the amount of substance of ketocarbonyl-containing in the reaction system.
Beneficial effect of the present invention is:
1, hydroxyl alkyl organosilicon and linking agent are designed into a molecule and get on, thereby it is single-component modified that the two-pack modification is become, and reduced the reinforced number of times in the building-up process, shortened the reaction times, improved production efficiency;
2, hydroxypropyl and the isocyanato reaction by organosilicon main chain two ends is incorporated into the organosilicon segment on the aqueous polyurethane molecule segment, thereby obtains organic-silicon-modified aqueous polyurethane, improves the water tolerance of filming after the aqueous polyurethane film forming; In film process, utilize ketone carbonyl and hydrazides generation crosslinking reaction on the organosilicon main chain side group, thereby improve molecular weight of polymer, the physical and mechanical properties that aqueous polyurethane is filmed behind the improvement introducing organosilicon.
Description of drawings
Fig. 1 is the infrared spectrogram of the response type organic silicon modified polyurethane aqueous dispersoid of the embodiment of the invention 1 preparation.
Embodiment
Below in conjunction with embodiment technical scheme of the present invention is further specified.
Embodiment 1 (solid content=20%, response type organosilicon content=5%, COOH%=2%, NCO/OH=1.3: 1)
Prepolymerization reaction
In the there-necked flask that agitator and thermometer are housed, add the response type organosilicon A of 6.01g tolylene diisocyanate and 1.00g
1B
4(wherein: R
1=A
1, R
2=B4, m=2, n=3, M
n=1000), be warming up to 70 ℃ of afterreaction 30min; Add 10.20g polyether Glycols (M then
n=2000), continue reaction 30min under the same temperature.The 119g dimethylol propionic acid is joined in the reaction system, behind reaction 30min under 70 ℃, add 0.71g ethylene glycol then and analyze isocyanato content in the prepolymer with standard Di-n-Butyl Amine back titration method behind the reaction 40min down for 70 ℃, when isocyanato content reaches theoretical value 3.4%, termination reaction, obtain main chain and contain ether, urethano and polysiloxane segment, the polynary block prepolymer of side chain ketocarbonyl-containing and carboxyl.
Salt-forming reaction
Prepolymer is reduced to room temperature, adds 30g acetone viscosity reduction, stir under the room temperature, obtain homogeneous phase solution until the prepolymer dissolving, add in the 0.90g triethylamine again and molecular chain in the carboxylic acid group.
Disperse chain extending reaction
The base polyurethane prepolymer for use as brute force is scattered in makes its emulsification chain extension in the 80mL deionized water that contains the 0.56g diethylenetriamine.The emulsification chain extension is removed acetone in 50 ℃ after finishing.
Add bishydrazide
According to the amount of substance of ketocarbonyl-containing in the reaction system, dissolve in adipic dihydrazide 0.261 gram at 2: 1 by the mol ratio of ketone carbonyl and bishydrazide, stirring and obtaining solid content is 20% response type organic silicon modified polyurethane aqueous dispersoid.
With infrared spectra this water dispersion is characterized, obtain infrared spectrum as shown in drawings.3300cm
-1The symmetrical stretching vibration absorption peak of the ammonia ester bond N-H of place key, 1728cm
-1The vibration absorption peak of the ammonia ester bond C=O of place, 2870-2970cm
-1The CH of place
2And CH
3Vibration absorption peak and 1103cm
-1The absorption peak of the C-O-C of place, these characteristic peaks show that urethane is successfully synthesized.1017cm among the figure
-1The vibration absorption peak of the Si-O of place key, 805cm
-1The Si-CH of place
3The vibration absorption peak of key shows that organosilicon successfully is connected in the polyurethane molecular.To sum up analyze, the response type organic silicon modified polyurethane aqueous dispersoid is successfully preparation.The response type organic silicon modified polyurethane aqueous dispersoid is prepared film forming, every performance index of film are tested, and compare with pure polyurethane film, correlation parameter sees the following form.By data in the table as can be seen, add adipic dihydrazide and crosslinked response type organic silicon modified polyurethane film takes place, its mechanical property all increases than the mechanical property that does not add adipic dihydrazide or pure polyurethane film; The suction of this adventitia and suction toluene rate have also obtained corresponding improvement.
The performance that table 2 response type organic silicon modified polyurethane aqueous dispersoid of the present invention prepares film forming and pure polyurethane film compares
* crosslinked response type organic silicon modified polyurethane film takes place after adding adipic dihydrazide
* does not add the response type organic silicon modified polyurethane film of adipic dihydrazide
Embodiment 2 (solid content=20%, response type organosilicon content %=7%, COOH%=1%, NCO/OH=1.04: 1)
Prepolymerization reaction
In the there-necked flask that agitator and thermometer are housed, add the response type organosilicon A of 6.22g isophorone diisocyanate and 1.40g
1B
4(wherein: R
1=A
1, R
2=B
4, m=6, n=4, M
n=1500), be warming up to 70 ℃ of afterreaction 30min; Add 10.34g polyether Glycols (M then
n=2000), continue reaction 30min under the same temperature.The 0.59g dimethylol propionic acid is joined in the reaction system, behind reaction 30min under 70 ℃, analyze isocyanato content in the prepolymer with standard Di-n-Butyl Amine back titration method after adding 70 ℃ of following 40min of 1.01g glycol reaction, when isocyanato content reaches theoretical value 0.46%, termination reaction, obtain main chain and contain ether, urethano and polysiloxane segment, the polynary block prepolymer of side chain ketocarbonyl-containing and carboxyl.
Salt-forming reaction
Prepolymer is reduced to room temperature, adds 30g acetone viscosity reduction, stir under the room temperature, obtain homogeneous phase solution until the prepolymer dissolving, add in the 0.44g triethylamine again and molecular chain in the carboxylic acid group.
Disperse chain extending reaction
The base polyurethane prepolymer for use as brute force is scattered in makes its emulsification chain extension in the 80mL deionized water that contains the 0.076g diethylenetriamine.The emulsification chain extension is removed acetone in 50 ℃ after finishing.
Add bishydrazide
According to the amount of substance of ketocarbonyl-containing in the reaction system, dissolve in sebacic dihydrazide 0.43 gram at 2: 1 by the mol ratio of ketone carbonyl and bishydrazide, stirring and obtaining solid content is 20% response type organic silicon modified polyurethane aqueous dispersoid.
Embodiment 3 (solid content=25%, response type organosilicon content %=4%, COOH%=3%, NCO/OH=1.06: 1)
In the there-necked flask that agitator and thermometer are housed, add the response type organosilicon A of 5.88g hexamethylene diisocyanate and 1.00g
5B
3(wherein: R
1=A
5, R
2=B
3, m=10, n=10, M
n=2500), be warming up to 60 ℃ of afterreaction 45min; Add 13.25g polyester diol (M then
n=3000), continue reaction 40min under the same temperature.The 2.47g dimethylolpropionic acid is joined in the reaction system, behind reaction 60min under 50 ℃, add 0.72g ethylene glycol and analyze isocyanato content in the prepolymer with standard Di-n-Butyl Amine back titration method behind the reaction 40min down for 50 ℃, when isocyanato content reaches theoretical value 0.6%, termination reaction, obtain main chain and contain ether, urethano and polysiloxane segment, the polynary block prepolymer of side chain ketocarbonyl-containing and carboxyl.
Salt-forming reaction
Prepolymer is reduced to room temperature, adds 30g acetone viscosity reduction, stir under the room temperature, obtain homogeneous phase solution until the prepolymer dissolving, add in the 1.68g triethylamine again and molecular chain in the carboxylic acid group.
Disperse chain extending reaction
The base polyurethane prepolymer for use as brute force is scattered in makes its emulsification chain extension in the 75mL deionized water that contains the 0.12g diethylenetriamine.The emulsification chain extension is removed acetone in 50 ℃ after finishing.
Add bishydrazide
According to the amount of substance of ketocarbonyl-containing in the reaction system, dissolve in adipic dihydrazide 0.35 gram at 2: 1 by the mol ratio of ketone carbonyl and bishydrazide, stirring and obtaining solid content is 25% response type organic silicon modified polyurethane aqueous dispersoid.
Embodiment 4 (solid content=30%, response type organosilicon content %=8.4%, COOH%=2%, NCO/OH=1.33:1)
In the there-necked flask that agitator and thermometer are housed, add the response type organosilicon A of 12.18g tolylene diisocyanate and 2.50g
5B
3(wherein: R
1=A
5, R
2=B
3, m=10, n=10, M
n=2500), be warming up to 80 ℃ of afterreaction 30min; Add 9.00g polyester diol (M then
n=3000), continue reaction 30min under the same temperature.The 1.79g dimethylol propionic acid is joined in the reaction system, behind reaction 45min under 80 ℃, add the 3.18g butyleneglycol and analyze isocyanato content in the prepolymer with standard Di-n-Butyl Amine back titration method behind the reaction 40min down for 80 ℃, when isocyanato content reaches theoretical value 4.8%, termination reaction, obtain main chain and contain ether, urethano and polysiloxane segment, the polynary block prepolymer of side chain ketocarbonyl-containing and carboxyl.
Salt-forming reaction
Prepolymer is reduced to room temperature, adds 30g acetone viscosity reduction, stir under the room temperature, obtain homogeneous phase solution until the prepolymer dissolving, add in the 1.35g triethylamine again and molecular chain in the carboxylic acid group.
Disperse chain extending reaction
The base polyurethane prepolymer for use as brute force is scattered in makes its emulsification chain extension in the 70mL deionized water that contains the 1.25g diethylenetriamine.The emulsification chain extension is removed acetone in 50 ℃ after finishing.
Add bishydrazide
According to the amount of substance of ketocarbonyl-containing in the reaction system, dissolve in adipic dihydrazide 0.87 gram at 2: 1 by the mol ratio of ketone carbonyl and bishydrazide, stirring and obtaining solid content is 30% response type organic silicon modified polyurethane aqueous dispersoid.
Embodiment 5
Tolylene diisocyanate among the embodiment 1 is changed to isophorone diisocyanate, and the response type organosilicon is changed to A
4B
4Polyether Glycols is changed to PCDL, and dimethylol propionic acid is changed to N-sulfonic acid ethylethylenediamine, and other reaction conditionss obtain being different from the response type organic silicon modified polyurethane aqueous dispersoid of embodiment 1 as described in example 1 above.
Embodiment 6
Tolylene diisocyanate among the embodiment 1 is changed to hexamethylene diisocyanate, and the response type organosilicon is changed to A
3B
3Polyether Glycols is changed to PCDL, dimethylol propionic acid is changed to dimethylolpropionic acid, ethylene glycol is changed to propylene glycol, diethylenetriamine is changed to diethanolamine, adipic dihydrazide is changed to succinic acid hydrazide ii, and other reaction conditionss obtain being different from the response type organic silicon modified polyurethane aqueous dispersoid of embodiment 1 as described in example 1 above.
Claims (6)
1. the preparation method of a response type organic silicon modified aqueous polyurethane, it is characterized in that, with response type organosilicon, polyisocyanates, polymer polyatomic alcohol, hydrophilic chain extender, general chainextender, organic amine neutralizing agent, dispersion chainextender is raw material, by prepolymerization reaction, salt-forming reaction and dispersion chain extending reaction, obtain the organic silicon modified polyurethane dispersion; According to the amount of substance of ketone carbonyl in the reaction system, bishydrazide is dissolved in then, obtain product after stirring by ketone carbonyl and bishydrazide mol ratio 2:1;
Described prepolymerization reaction is: add polyisocyanates and response type organosilicon in the reaction vessel, be warming up to 50～80 ℃ of afterreaction 30～60min; Add polymer polyatomic alcohol then, continue reaction 30～60min under the same temperature; Hydrophilic chain extender is joined in the reaction system, behind reaction 30～60min under 50～80 ℃; Add general chainextender then and react isocyanato content in 40～60min post analysis prepolymer down for 50～80 ℃, when isocyanato content reaches theoretical value, termination reaction obtains main chain and contains ether, urethano and polysiloxane segment, the polynary block prepolymer of side chain ketocarbonyl-containing; Wherein, isocyanato content in the prepolymer=(the total amount of substance of polyisocyanates amount of substance-oxy-compound) * 2* isocyanato molecular weight/total solids quality;
Described salt-forming reaction is: prepolymer is reduced to room temperature, adds acetone and reduce viscosity, stir under the room temperature, obtain homogeneous phase solution until the prepolymer dissolving, add in the organic amine neutralizing agent again and molecular chain in the carboxylic acid group;
Described dispersion chain extending reaction is: above-mentioned product brute force is scattered in the deionized water that disperses chainextender makes its emulsification chain extension; The emulsification chain extension is removed acetone in 50 ℃ after finishing;
Wherein, isocyanate group and raw material reaction type organosilicon in the described raw material polyisocyanates, polymer polyatomic alcohol, the mol ratio of the hydroxyl summation in hydrophilic chain extender and the general chainextender is: 1.5:1～1:1, the mol ratio of described hydrophilic chain extender and organic amine neutralizing agent is: 1:1, the range of solid content of described product is: 20%～40%, described response type organosilicon content range is: 3%～11%, described polymer polyatomic alcohol content range is: 46%～54%, described hydrophilic radical carboxylic acid group content range is: 1%～4%, and isocyanato content theoretical value is 0.1%-5% in the described prepolymer; When described dispersion chainextender and prepolymerization reaction finish in the prepolymer mol ratio of isocyanato be 0.33～0.4; The quality that described response type organosilicon, polymer polyatomic alcohol and hydrophilic radical carboxylic acid group's content is respectively response type organosilicon, polymer polyatomic alcohol and hydrophilic radical carboxylic acid group accounts for the per-cent of total solids quality; Described total solids quality is the total mass of response type organosilicon, polyisocyanates, polymer polyatomic alcohol, hydrophilic chain extender, general chainextender and organic amine neutralizing agent; The organosilyl structural formula of described response type is:
R wherein
1Be in the following structure any one:
A
1)CH
2CH
2CH
2OH A
2)CH
2CH
2CH
2CH
2OH A
3)CH
2CH
2CH
2CH
2CH
2OH
A
4)CH
2CH
2CH
2CH
2CH
2CH
2OH A
5)CH
2CH
2CH
2OCH
2CH(OH)CH
2OCH
3
R
2Be in the following structure any one:
N represents the integer of 1-14, and m represents the integer of 1-36;
Described hydrophilic chain extender is any one of dimethylol propionic acid and dimethylolpropionic acid; Described general chainextender is any one in ethylene glycol, propylene glycol, butyleneglycol, Diethylene Glycol, triethylene glycol, quadrol, propylene diamine, butanediamine and the hexanediamine; Described dispersion chainextender is any one in diethylenetriamine, diethanolamine, trolamine, serinol and the glycerol.
2. the preparation method of response type organic silicon modified aqueous polyurethane according to claim 1 is characterized in that: described polyisocyanates is any one in tolylene diisocyanate, '-diphenylmethane diisocyanate, polymethylene polyphenyl vulcabond, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, dicyclohexyl methyl hydride isocyanic ester, trimethyl hexamethylene diisocyanate and the hydrogenated tolylene diisocyanate.
3. the preparation method of response type organic silicon modified aqueous polyurethane according to claim 1 is characterized in that: described polymer polyatomic alcohol is any one in the pure and mild polycarbonate polyol of polyether glycol, polyester polyols.
4. the preparation method of a kind of response type organic silicon modified aqueous polyurethane according to claim 3 is characterized in that:
Described polyether glycol is any one in polytetrahydrofuran polyvalent alcohol, polyoxyethylene polyvalent alcohol, the polyoxytrimethylene polyvalent alcohol, or tetrahydrofuran (THF), ethylene oxide, propylene oxide are a kind of in both polyol arbitrarily, or tetrahydrofuran (THF), ethylene oxide, propylene oxide three polyol;
Described polyester polyol is the polyester polyol that is formed by diprotic acid and dibasic alcohol condensation, or the polyester polyol that is formed by lactone ring opening polymerization;
Described polycarbonate polyol is the oligopolymer that contains two or more terminal hydroxy group carbonate-containing structures, is to be obtained by transesterify by carbonic diester and dibasic alcohol.
5. the preparation method of response type organic silicon modified aqueous polyurethane according to claim 1 is characterized in that: described organic amine neutralizing agent is any one in triethylamine and the ammoniacal liquor.
6. the preparation method of response type organic silicon modified aqueous polyurethane according to claim 1 is characterized in that: described bishydrazide is any one in adipic dihydrazide, sebacic dihydrazide, ethylene acid hydrazide, succinic acid hydrazide ii, propanedioic acid two hydrazides and carbonic acid two hydrazides.
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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 |
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| CN108840987B (en) * | 2018-06-28 | 2022-02-15 | 优美特（北京）环境材料科技股份公司 | Organosilicon polyol modified waterborne polyurethane emulsion and preparation method thereof |
| CN109180899A (en) * | 2018-07-20 | 2019-01-11 | 张家港市东方高新聚氨酯有限公司 | aqueous polyurethane and preparation method thereof |
| CN111073579B (en) * | 2018-10-22 | 2022-07-12 | 万华化学集团股份有限公司 | High-initial-viscosity polyurethane adhesive for artificial board and preparation method and application thereof |
| CN112500774A (en) * | 2019-09-16 | 2021-03-16 | 天津大学 | Mixed type solvent-free silicon-containing waterborne polyurethane coating and preparation method thereof |
| CN112796110B (en) * | 2020-12-31 | 2023-01-06 | 四川省纺织科学研究院 | Ketone-hydrazine cross-linking type water-based fluorine-free fabric waterproof finishing agent and preparation method and application thereof |
| CN115873256B (en) * | 2023-02-16 | 2024-02-13 | 四川大学 | Crosslinked polydimethylsiloxane elastomer material and preparation method thereof |
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| CN101885844A (en) * | 2010-07-08 | 2010-11-17 | 邬元娟 | Method for synthesizing ketocarbonyl-containing bis-hydroxypropyl terminated polysiloxane |
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