CN116102706B - Preparation method of organic silicon modified flame-retardant aqueous polyurethane emulsion - Google Patents
Preparation method of organic silicon modified flame-retardant aqueous polyurethane emulsion Download PDFInfo
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- C08G18/6648—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6651—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
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Abstract
The invention belongs to the technical field of aqueous polyurethane, and discloses a preparation method of an organosilicon modified flame-retardant aqueous polyurethane emulsion, which comprises the steps of mixing hydrogen-containing silane, an olefin modified triazine compound and an isopropyl chloroplatinate solution, refluxing, adding absolute ethyl alcohol, filtering, and adding a hydroxy and carboxylic acid double-functionalized organic compound for reaction to obtain an organosilicon modified hydroxy-containing triazine compound; mixing diisocyanate and a hydroxyl-containing triazine compound for reaction, and then sequentially adding oligomeric dihydric alcohol, organic bismuth, a hydrophilic chain extender, acetone and water for self-emulsifying and dispersing to obtain an organosilicon modified hydrophilic polyurethane prepolymer; and adding a small molecular polyamine chain extender to extend the chain, and removing acetone after the system is formed into a uniform emulsion to obtain the organosilicon modified flame-retardant aqueous polyurethane emulsion. The organic silicon modified polyol synthesized by the invention can improve the water resistance, heat resistance, wear resistance and other performances of the obtained aqueous polyurethane leather product, and the triazine functional group with excellent flame retardant performance is introduced, so that the aqueous polyurethane product has flame retardance.
Description
Technical Field
The invention relates to the technical field of water-based polyurethane synthesis, in particular to a preparation method of an organosilicon modified flame-retardant water-based polyurethane emulsion.
Background
The aqueous polyurethane is a polyurethane system taking water as a dispersing agent, has the advantages of no toxicity, cleanness, excellent mechanical property, good wear resistance, solvent resistance and the like, and has been widely applied to the fields of synthetic leather, adhesives, coatings and the like. However, the traditional single water-based polyurethane material has poor high temperature resistance and water resistance, and has low oxygen index and easy combustion, thus seriously impeding the application of the material in the related fields.
The organosilicon has excellent heat resistance and water resistance, and is widely used for modifying the water-based polyurethane, so that the polyurethane has the advantages of water resistance, heat resistance, wear resistance and the like. Chinese patent CN105330813A utilizes the reaction of hydroxyl-terminated silicone oil and isocyanate to introduce organic silicone oil in situ in the molecular chain of water-based polyurethane to improve the yellowing resistance, water resistance, wear resistance and other properties of the water-based polyurethane product. However, the study did not take into account the flame retardant properties of the synthesized aqueous polyurethane. The flame retardant properties thereof still need to be achieved by the additional addition of flame retardants. And the flame retardant is added to the aqueous polyurethane emulsion, so that the characteristics of viscosity, solid content and the like of the emulsion are easily changed while the flame retardant performance of the polyurethane is obtained, thereby changing the processing characteristics of the emulsion and even affecting the final performance of the polyurethane material. In addition, the abrasion resistance of the waterborne polyurethane product of this patent is also relatively low.
Disclosure of Invention
The invention aims to: aiming at the problems existing in the prior art, the invention provides a preparation method of an organosilicon modified intrinsic flame-retardant aqueous polyurethane emulsion, which is characterized in that an organosilicon modified hydroxyl-containing triazine compound is prepared through an organic synthesis step, and then the compound is introduced onto a molecular chain of aqueous polyurethane to obtain the organosilicon modified high-performance flame-retardant aqueous polyurethane emulsion.
The technical scheme is as follows: the invention provides a preparation method of an organosilicon modified flame-retardant aqueous polyurethane emulsion, which comprises the following steps: s1, uniformly mixing hydrogen-containing silane, an olefin modified triazine compound and an isopropyl chloroplatinate solution, refluxing for 3-7 hours at 95-105 ℃, adding absolute ethyl alcohol, filtering, adding a hydroxyl and carboxylic acid difunctional organic compound, and reacting for 2-4 hours to obtain an organosilicon modified hydroxyl-containing triazine compound; s2, after mixing diisocyanate and an organosilicon modified hydroxyl-containing triazine compound for reaction, adding oligomeric dihydric alcohol, stirring at 75-85 ℃ for reaction for 0.5-2 hours, adding an organic bismuth catalyst, stirring for reaction for 0.5-1 hour, adding a hydrophilic chain extender, continuing stirring for reaction for 1-2 hours, adding acetone, continuing stirring for reaction for 0.5-1.5 hours, and then adding water for high-speed stirring for self-emulsifying dispersion to obtain an organosilicon modified hydrophilic polyurethane prepolymer; s3, adding a small molecular polyamine chain extender into the organosilicon modified hydrophilic polyurethane prepolymer, then heating to 45-55 ℃ to extend the chain for 4-8 hours, and removing acetone after the system becomes a uniform emulsion to obtain the organosilicon modified flame-retardant aqueous polyurethane emulsion.
Preferably, in S1, the molar volume ratio of the hydrosilane, the olefin-modified triazine compound, the solution of chloroplatinic acid in isopropanol, and the hydroxy and carboxylic acid difunctional organic compound is 5: 5-11: 0.4: 10-21.
Preferably, the concentration of the chloroplatinic acid isopropyl alcohol solution is 0.2mol/L.
Preferably, in S2, the molar ratio of diisocyanate, silicone modified hydroxyl-containing triazine compound and oligomeric diol is: 5: 1.2-2: 2-3.
Preferably, in S3, the small molecule polyamine chain extender is a mixture of ethylenediamine and 1,2, 3-propanetriamine (molar ratio is 1:1), and the dosage is 4-8% of the molar amount of isocyanate.
Preferably, the olefin-modified triazine compound is any one of the following: 2-vinyl-4, 6-diamino-1, 3, 5-triazine, 6- (4-vinylbenzyl-n-propyl) amino-1, 3, 5-triazine-2, 4-dithiol.
Preferably, the hydrogen-containing silane is any one of the following: 1,3, 5-hexamethyltrisiloxane, 1, 3-tetramethyldisiloxane, pentamethyldisiloxane dimethylphenylsilane, 1, 4-tetramethyl-1, 4-disilylbutane, 1, 2-tetramethyldisilane.
Preferably, the hydroxy and carboxylic acid difunctional organic compound is any one or a combination of the following: glycolic acid, 2-hydroxypropionic acid, gamma-hydroxybutyric acid, 3-hydroxyvaleric acid, 6-hydroxycaproic acid, 7-hydroxyheptanoic acid, 8-hydroxyoctanoic acid, 9-hydroxynonanoic acid, 3-hydroxynonanoic acid, 10-hydroxydecanoic acid, p-hydroxybenzoic acid.
Preferably, the diisocyanate is any one or a combination of the following: isophorone diisocyanate, hexamethylene diisocyanate, 4' -dicyclohexylmethane diisocyanate, methylcyclohexyl diisocyanate.
Preferably, the oligomeric diol is any one or a combination of the following: neopentyl glycol polyadipate diol, polyethylene glycol-propylene glycol polyadipate diol, and polyethylene glycol-1.4 butanediol polyadipate diol.
The beneficial effects are that: 1. the invention synthesizes a novel organosilicon modified hydroxyl-containing triazine compound by utilizing the hydrosilylation reaction of an olefin modified triazine compound and hydrogen-containing silane and the amidation reaction of the olefin modified triazine compound and a hydroxyl-containing carboxylic acid bifunctional organic compound, and the novel organosilicon modified hydroxyl-containing triazine compound has excellent flame retardant property, and the reaction equation is as follows:
2. The organosilicon modified waterborne polyurethane is prepared by the chain extension reaction of the organosilicon modified hydroxyl-containing triazine compound and diisocyanate, so that the organosilicon groups and the triazine flame-retardant functional groups can be dispersed on the polyurethane chain segment at molecular level, the compatibility of the organosilicon modified hydroxyl-containing triazine compound and polyurethane resin is improved, the emulsion stability is improved, the storage and the transportation are facilitated, and the flame retardance and other performances of the material can be effectively improved.
3. The superfine fiber synthetic leather prepared by adopting the aqueous polyurethane emulsion has the characteristics of no solvent residue, smoothness, softness, good flame retardant effect, excellent water resistance, heat resistance, wear resistance and the like, and has wide market prospect.
4. By utilizing the designed and synthesized organosilicon modified polyol, the performances of water resistance, heat resistance, wear resistance and the like of the obtained waterborne polyurethane leather product can be effectively improved, triazine functional groups with excellent flame retardant performance are introduced, and the obtained waterborne polyurethane product has good flame retardant performance and has adjustable solid content of 20-55 wt percent.
5. Compared with the patents mentioned in the background art, (1) the application designs and synthesizes the organosilicon modified hydroxyl-containing triazine compound according to the chemical reaction principles of hydrosilylation reaction, acid-base neutralization reaction and the like, and the introduction of the compound firstly provides flame retardant property for polyurethane chain segments; secondly, interaction forces such as pi-pi conjugation between triazine functional groups are utilized, so that the interaction forces between polyurethane chain segments are improved, the crystallization effect is increased, and the tensile strength of polyurethane is increased; finally, the triazine functional group is utilized to have certain hydrophilicity, so that the use level of the hydrophilic chain extender is reduced to a certain extent; (2) 1, 4-butanediol-2-sodium sulfonate is used as a hydrophilic chain extender, so that the use of neutralizing agents such as triethylamine and the like is avoided, one reaction step is omitted, and the production cost is saved; (3) The mixture of ethylenediamine and 1,2, 3-propanetriamine (the molar ratio is 1:1) is used as a small molecular chain extender, and the propanetriamine is used as a crosslinking point, so that the obtained aqueous polyurethane molecular chain is of a bodily form high molecular structure (three-dimensional network), and the tensile strength and the wear resistance of a polyurethane product are obviously improved.
Detailed Description
The present invention will be described in detail with reference to specific examples.
Embodiment 1:
s1, adding 5 mol dimethyl phenyl silane, 5 mol 2-vinyl-4, 6-diamino-1, 3, 5-triazine and 2 mL chloroplatinic acid isopropanol solution (0.2 mol/L) into a three-necked flask, stirring and mixing for 10min, refluxing at 100 ℃ for 5h, adding absolute ethyl alcohol 200mL, filtering, adding 10 mol glycolic acid, and reacting for 3h to obtain an organosilicon modified hydroxyl-containing triazine compound;
S2, adding 3mol poly (neopentyl glycol adipate) glycol into an organosilicon modified hydroxyl-containing triazine compound prepared from 5 mol isophorone diisocyanate and 1.2 mol S1, stirring and reacting for 1 hour, stirring and reacting at 80 ℃ for 1 hour, adding an organic bismuth catalyst, stirring and reacting for 0.5 hour, adding a hydrophilic chain extender 1,4 butanediol-2-sodium sulfonate 0.3mol, continuously stirring and reacting for 1.5 hours, adding acetone, continuously stirring and reacting for 1 hour, and then adding water, stirring at a high speed, self-emulsifying and dispersing to obtain an organosilicon modified hydrophilic polyurethane prepolymer;
s3, adding 0.2mol of ethylenediamine and 1,2, 3-propanetriamine mixture (the molar ratio is 1:1) into the organosilicon modified hydrophilic polyurethane prepolymer as a chain extender, then heating to 50 ℃ to extend the chain for 4-8 hours, and removing acetone at 50 ℃ and 0.1MPa after the system becomes a uniform emulsion to obtain the organosilicon modified flame-retardant aqueous polyurethane emulsion.
Embodiment 2:
S1, adding 5 mol of 1,3, 5-hexamethyltrisiloxane, 9.8 mol of 2-vinyl-4, 6-diamino-1, 3, 5-triazine and 2 mL of chloroplatinic acid isopropanol solution (0.2 mol/L) into a three-necked flask, stirring and mixing for 10min, refluxing at 100 ℃ for 5h, adding absolute ethyl alcohol 200 mL, filtering, adding 20.2 mol of 3-hydroxynonanoic acid, and reacting for 3h to obtain an organosilicon modified hydroxyl-containing triazine compound;
S2, adding 2.6mol of polyethylene glycol-propylene glycol adipate glycol to react for 1 hour after stirring 5 mol hexamethylene diisocyanate and 1.6mol of organosilicon modified hydroxyl-containing triazine compound prepared by S1, adding an organic bismuth catalyst to react for 1 hour after stirring, adding 0.3mol of hydrophilic chain extender 1,4 butanediol-2-sodium sulfonate to react for 1 hour after stirring, adding acetone to react for 1 hour after stirring, and then adding water to stir at a high speed for self-emulsifying dispersion to obtain an organosilicon modified hydrophilic polyurethane prepolymer;
s3, adding 0.25mol of ethylenediamine and 1,2, 3-propanetriamine mixture (the molar ratio is 1:1) into the organosilicon modified hydrophilic polyurethane prepolymer as a chain extender, then heating to 50 ℃ to extend the chain for 4-8 hours, and removing acetone at 50 ℃ and 0.1MPa after the system becomes a uniform emulsion to obtain the organosilicon modified flame-retardant aqueous polyurethane emulsion.
Embodiment 3:
S1, adding 5 mol of 1, 4-tetramethyl-1, 4-disilazane, 11 mol of 6- (4-vinylbenzyl-n-propyl) amino-1, 3, 5-triazine-2, 4-dithiol and 2 mL of chloroplatinic acid isopropanol solution (0.2 mol/L) into a three-necked flask, stirring and mixing for 10min, refluxing at 100 ℃ for 5h, adding absolute ethyl alcohol 200 mL, filtering, adding 21 mol of 3-hydroxypentanoic acid, and reacting for 3h to obtain an organosilicon modified hydroxyl-containing triazine compound;
S2, stirring and reacting the organosilicon modified hydroxyl-containing triazine compound prepared in S1 of 5mol of 4,4' -dicyclohexylmethane diisocyanate and 2mol for 1 hour, adding 2mol of polyethylene glycol-propylene glycol adipate glycol, stirring and reacting for 2 hours at 80 ℃, adding an organobismuth catalyst, stirring and reacting for 1 hour, adding 0.3mol of hydrophilic chain extender 1, 4-butanediol-2-sodium sulfonate, continuously stirring and reacting for 1.5 hours, adding acetone, continuously stirring and reacting for 1 hour, and then adding water, stirring at a high speed, self-emulsifying and dispersing to obtain an organosilicon modified hydrophilic polyurethane prepolymer;
S3, adding 0.4mol of ethylenediamine and 1,2, 3-propanetriamine mixture (the molar ratio is 1:1) into the organosilicon modified hydrophilic polyurethane prepolymer as a chain extender, then heating to 50 ℃ to extend the chain for 4-8 hours, and removing acetone at 50 ℃ and 0.1MPa after the system becomes a uniform emulsion to obtain the organosilicon modified flame-retardant aqueous polyurethane emulsion.
The flame-retardant aqueous polyurethane emulsion prepared in the above embodiments 1 to 3 has the following tensile strength, water resistance, wear resistance and flame retardance data of the adhesive film:
tensile strength: the polyurethane resin is made into a film with the thickness of about 1mm on a tetrafluoroethylene plate, and after the film is completely dried, the film is measured by a GMT-4204 microcomputer control electronic universal tester manufactured by Meite process system (China) Co., ltd according to GB 8949-2008-T;
Water resistance: the polyurethane resin is made into a film with the thickness of about 1mm on a tetrafluoroethylene plate, and the film is put into deionized water with the temperature of 25 ℃ to be soaked for 120 hours after being completely dried, and is weighed after being dried, and the total amount of the film is inspected before and after soaking.
Abrasion resistance: the polyurethane resin was formed into a film having a thickness of about 1mm on a tetrafluoroethylene plate, and after complete baking, the number of grinding turns was measured on a tab friction tester with an H22 grinding wheel.
Flame retardancy: ZR-01 oxygen index measuring instrument produced by Qingdao mountain spinning instruments Inc. is used for measuring, and the oxygen index is classified according to the value of the oxygen index, wherein the oxygen index is less than 22% and is a flammable material, the oxygen index is more than 27% and is a nonflammable material, and the oxygen index is 22% and 27% belong to the flammable materials.
The foregoing embodiments are merely illustrative of the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the present invention and to implement the same, not to limit the scope of the present invention. All equivalent changes or modifications made according to the spirit of the present invention should be included in the scope of the present invention.
Claims (9)
1. A preparation method of an organosilicon modified flame-retardant aqueous polyurethane emulsion is characterized by comprising the following steps: the method comprises the following steps:
S1, uniformly mixing hydrogen-containing silane, an olefin modified triazine compound and an isopropyl chloroplatinate solution, refluxing for 3-7 hours at 95-105 ℃, adding absolute ethyl alcohol, filtering, adding a hydroxyl and carboxylic acid difunctional organic compound, and reacting for 2-4 hours to obtain an organosilicon modified hydroxyl-containing triazine compound;
wherein the olefin-modified triazine compound is any one of the following:
2-vinyl-4, 6-diamino-1, 3, 5-triazine, 6- (4-vinylbenzyl-n-propyl) amino-1, 3, 5-triazine-2, 4-dithiol;
S2, after mixing diisocyanate and an organosilicon modified hydroxyl-containing triazine compound for reaction, adding oligomeric dihydric alcohol, stirring at 75-85 ℃ for reaction for 0.5-2 hours, adding an organic bismuth catalyst, stirring for reaction for 0.5-1 hour, adding a hydrophilic chain extender, continuing stirring for reaction for 1-2 hours, adding acetone, continuing stirring for reaction for 0.5-1.5 hours, and then adding water for high-speed stirring for self-emulsifying dispersion to obtain an organosilicon modified hydrophilic polyurethane prepolymer;
S3, adding a small molecular polyamine chain extender into the organosilicon modified hydrophilic polyurethane prepolymer, then heating to 45-55 ℃ to extend the chain for 4-8 hours, and removing acetone after the system becomes a uniform emulsion to obtain the organosilicon modified flame-retardant aqueous polyurethane emulsion.
2. The method for preparing the organosilicon modified flame retardant aqueous polyurethane emulsion according to claim 1, which is characterized in that: in S1, the molar ratio of the hydrosilane, the olefin-modified triazine compound, chloroplatinic acid, and the hydroxy and carboxylic acid difunctional organic compound is 5: 5-11: 0.4: 10-21.
3. The method for preparing the organosilicon modified flame retardant aqueous polyurethane emulsion according to claim 2, characterized in that: the concentration of the chloroplatinic acid isopropanol solution is 0.2mol/L.
4. The method for preparing the organosilicon modified flame retardant aqueous polyurethane emulsion according to claim 1, which is characterized in that: in S2, the molar ratio of diisocyanate, silicone modified hydroxyl-containing triazine compound and oligomeric diol is: 5: 1.2-2: 2-3.
5. The method for preparing the organosilicon modified flame retardant aqueous polyurethane emulsion according to claim 1, which is characterized in that: in S3, the using amount of the small molecular polyamine chain extender is 4-8% of the molar amount of isocyanate.
6. The method for producing a silicone-modified flame retardant aqueous polyurethane emulsion according to any one of claims 1 to 5, characterized in that: the hydrogen-containing silane is any one of the following:
1,3, 5-hexamethyltrisiloxane, 1, 3-tetramethyldisiloxane, pentamethyldisiloxane dimethylphenylsilane, 1, 4-tetramethyl-1, 4-disilylbutane, 1, 2-tetramethyldisilane.
7. The method for preparing a silicone-modified flame retardant aqueous polyurethane emulsion according to any one of claims 1 to 5, wherein the hydroxyl and carboxylic acid difunctional organic compound is any one or a combination of the following:
glycolic acid, 2-hydroxypropionic acid, gamma-hydroxybutyric acid, 3-hydroxyvaleric acid, 6-hydroxycaproic acid, 7-hydroxyheptanoic acid, 8-hydroxyoctanoic acid, 9-hydroxynonanoic acid, 3-hydroxynonanoic acid, 10-hydroxydecanoic acid, p-hydroxybenzoic acid.
8. The method for preparing the silicone-modified flame-retardant aqueous polyurethane emulsion according to any one of claims 1 to 5, wherein the diisocyanate is any one or a combination of the following:
isophorone diisocyanate, hexamethylene diisocyanate, 4' -dicyclohexylmethane diisocyanate, methylcyclohexyl diisocyanate.
9. The method for preparing a silicone-modified flame retardant aqueous polyurethane emulsion according to any one of claims 1 to 5, wherein the oligomeric diol is any one or a combination of the following:
neopentyl glycol polyadipate glycol, polyethylene glycol-propylene glycol polyadipate glycol, and polyethylene glycol-1, 4 butanediol polyadipate glycol.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104312407A (en) * | 2013-03-22 | 2015-01-28 | 吴小再 | Aqueous polyurethane paint preparation method |
| CN105330813A (en) * | 2015-11-03 | 2016-02-17 | 淮安凯悦科技开发有限公司 | Synthetic method for organic silicon modified waterborne polyurethane for leatherworking |
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| JP2016037457A (en) * | 2014-08-06 | 2016-03-22 | 日本ゼオン株式会社 | Triazine compound and synthesis method |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104312407A (en) * | 2013-03-22 | 2015-01-28 | 吴小再 | Aqueous polyurethane paint preparation method |
| CN105330813A (en) * | 2015-11-03 | 2016-02-17 | 淮安凯悦科技开发有限公司 | Synthetic method for organic silicon modified waterborne polyurethane for leatherworking |
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