CN104292414A - Organosilicone-modified amphiprotic water-based polyurethane emulsion and preparation method thereof - Google Patents
Organosilicone-modified amphiprotic water-based polyurethane emulsion and preparation method thereof Download PDFInfo
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- C08G18/752—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
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- C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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Abstract
The invention belongs to the technical field of a waterborne polyurethane emulsion and discloses an organosilicone-modified amphiprotic water-based polyurethane emulsion and a preparation method thereof. The preparation method comprises the following steps: firstly, adding polyesterdiol (containing a sulfonic acid group) and polyether polyol to a polymerization reactor, heating and carrying out reduced pressure distillation to remove water; adding polyisocyanate and a catalyst, carrying out stirred reaction; cooling, adding a solvent, a chain extender and a crosslinking containing a tertiary amine structure to further react; cooling and adding a neutralizer for neutralization to obtain an amine salt; adding water and a silane coupling agent to a reactant; carrying out high-speed shear emulsifying, adding a post chain extender and carrying out post chain extension reaction, and then carrying out reduced pressure distillation on the reactant to remove the solvent; and adding adjuvants such as a defoaming agent and a flatting agent, so as to obtain the organosilicone-modified amphiprotic water-based polyurethane emulsion. The organosilicone-modified amphiprotic water-based polyurethane emulsion disclosed by the invention is free of organic solvent residues basically, and is high in solid content, excellent in mechanical property and good in water resistance and heat resistance.
Description
Technical field
The invention belongs to aqueous polyurethane emulsion technical field, be specifically related to a kind of organic-silicon-modified both sexes aqueous polyurethane emulsion and preparation method thereof.
Background technology
Urethane (PU) is the multifunctional polymer of amido-containing acid ester structure (-NHCOO-), it has high-adhesive-strength and stripping strength, the aspect advantages such as excellent shock-resistant, low temperature resistant, oil resistant and wear resistance, are widely used in the fields such as coating, sizing agent, hide finishes, ink.And aqueous polyurethane take water as the binary colloidal system of dispersion medium, compared with solvent borne polyurethane, has the advantages such as nontoxic, nonflammable, free from environmental pollution.In recent years, along with improving and the enhancing of people's environmental consciousness and the concern to own health of legislations of environmental protection, the development of aqueous polyurethane is facilitated.
Aqueous polyurethane is divided into polyether-type, polyester type, polycarbonate waterborne polyurethane according to the difference of soft section of raw material.The low price of polyether type aqueous urethane, elasticity, hydrolytic resistance, lower temperature resistance are excellent, film good hand touch, but mechanical property is poor; The low price of polyester type aqueous polyurethane, wear resisting property, excellent in mechanical performance, but hydrolytic resistance is poor, film is soft not; Polycarbonate waterborne polyurethane excellent combination property, but expensive, and use range is limited.
Aqueous polyurethane is divided into anionic, non-ionic type, cationic according to the electrically charged polarity difference of hydrophilic radical.Cationic contained hydrophilic radical is positively charged ion, can be divided into amine salt type and quaternary according to structure.Amine salt type aqueous polyurethane is in its building-up process, introduces tertiary amine group, adds hydrochloric acid or organic acid as in formic acid, acetic acid etc. and form amine salt when disperseing in water.4 hydrogen atoms of quaternary aqueous polyurethane wetting ability ammonium salt are all replaced by organic group and are formed, and normally tertiary amine and alkylating reagent carry out reacting obtained.Cation-type water-thinned polyurethane dispersion liquid is to anion-containing matrix as glass and leather have good adhesivity, and insensitive to water hardness, and can use in acid condition, emulsion has germ resistance simultaneously.
At present, anion-type water-thinned polyurethane research is the most extensive, and this kind of urethane mainly adopts sulfonate type or carboxylic acid type hydrophilic monomer to provide hydrophilic radical.The aqueous polyurethane emulsion viscosity of independent employing carboxylic acid type hydrophilic monomer synthesis is comparatively large, and solid content is difficult to improve (about 35%); The aqueous polyurethane emulsion adopting sulfonate type hydrophilic monomer to prepare has large arch dam, feature that degree of crystallinity is high.
Although aqueous polyurethane have do not fire, smell is little, free from environmental pollution, energy-conservation, operate the advantages such as easy to process, but also there is water tolerance, strong not and hardness and application performance require shortcomings such as not being suitable for mutually with the sticking power of base material, have impact on applying of it largely.The water tolerance that modification improves aqueous polyurethane can be carried out by introducing silane coupling agent, and due to silane coupling agent be small molecules, the problem of poor compatibility is there is not with its modification, siloxane structure is introduced in urethane segment, improved the degree of crosslinking of system after emulsification by the hydrolysis-condensation reaction of alkoxyl group, can avoid because linking agent adds too much, is cross-linked the emulsification difficulty excessively caused.
Be cross-linked the important method of the performance such as adhesive power, mechanical property, hardness being raising aqueous polyurethane.Introduce crosslinked method to mainly contain: (1) adopts the polyethers of polyfunctionality or polyester polyol or polyisocyanates in the feed; (2) there is amino urethane epoxy chloropropane process and can obtain heat cured aqueous polyurethane dispersing liquid; (3) blocked isocyanate dispersion liquid, or be mixed to form stable dispersion liquid with other aqueous polyurethane dispersing liquid, film forming post-heating then-NCO group regeneration, the radical reaction containing reactive hydrogen with urethane, forms crosslinked glued membrane; (4) the small molecules linking agent of polyfunctionality is adopted, as: TriMethylolPropane(TMP), polyethylene polyamine, trolamine etc.
Cross-linking monomer in domestic urethane synthesis mainly adopts TriMethylolPropane(TMP), and as CN-102516920, CN-102827571, but TriMethylolPropane(TMP) reactive group is active the same, and speed of response is difficult to control, easy gel, is unfavorable for producing.US Patent No.-6017998 discloses the preparation method of the aqueous polyurethane emulsion that one is hydrophilic chain extender with dimethylol propionic acid (DMPA), uses the aqueous polyurethane of the obtained large arch dam of the method difficulty.It take methyldiethanolamine as the preparation method of a kind of cation-type water-thinned polyurethane/organic montmorillonoid composite resin of cationic hydrophilic monomer that Chinese patent CN101698744A discloses a kind of, uses the aqueous polyurethane of the obtained high solids content of the method difficulty.Chinese patent CN102585149B discloses a kind of with the preparation method of the aqueous polyurethane by adding both sexes hydrophilic chain extender and/or non-hydrophilic chainextender, Chinese patent CN102585149B discloses a kind of with the preparation method of the aqueous polyurethane by adding both sexes hydrophilic chain extender and/or non-hydrophilic chainextender, uses the method that a large amount of organic solvent being difficult to remove will be used as dimethyl formamide, dimethyl sulfoxide (DMSO) and the aqueous polyurethane of difficult obtained water-tolerant.The synthetic method of the large arch dam polyester type aqueous polyurethane emulsion that Chinese patent CN103570915A and CN103360563A announces, obtained aqueous polyurethane glued membrane is comparatively hard, and feel is not good enough, and elasticity is poor.
Summary of the invention
In order to overcome the shortcoming of prior art with not enough, primary and foremost purpose of the present invention is to provide a kind of preparation method being easy to the aqueous polyurethane emulsion of the polyether polyester mixed type of the organic-silicon-modified high solids content produced;
Another object of the present invention is to the organic-silicon-modified both sexes aqueous polyurethane emulsion providing above-mentioned preparation method to obtain, the solid content of described organic-silicon-modified both sexes aqueous polyurethane emulsion, the water tolerance of glued membrane, thermotolerance, mechanical property all increase, and may be used for the fields such as coating, hide finishes, pressure sensitive adhesive.
Object of the present invention is achieved through the following technical solutions:
A preparation method for organic-silicon-modified both sexes aqueous polyurethane emulsion, comprises the steps:
(1) with weight parts, join in polymerization reactor by the polyester diol containing sulfonic acid group of 52 ~ 60 weight part polyether glycols and 12 ~ 15 weight parts, underpressure distillation dewaters, then temperature adjustment to 60 ~ 70 DEG C;
Preferably, described polyether glycol is polyoxypropyleneglycol; Preferred, the molecular weight of described polyoxypropyleneglycol is 1000;
Preferably, the described polyester diol containing sulfonic acid group is the terminal hydroxy group sulfonate type polyester diol BY3306 of Beijing one hundred source Chemical Co., Ltd.;
Preferably, described polymerization reactor is the polymerization reactor being equipped with digital display electric blender, thermometer;
Preferably, the vacuum tightness that described underpressure distillation dewaters is set as-0.1MPa, and temperature is 100 ~ 110 DEG C, and the time is 2h;
(2) in step (1) described polymerization reactor, 0.04 part by weight of catalyst and 25 ~ 30 weight part polyisocyanates are added, stirring reaction;
Preferably, described catalyzer is dibutyl tin laurate;
Preferably, described polyisocyanates is isophorone diisocyanate;
Preferably, the temperature of reaction of step (2) described stirring reaction is 80 ~ 85 DEG C, and the reaction times is 3 ~ 3.5h;
(3) after step (2) stirring reaction terminates, in described polymerization reactor, add 60 ~ 80 parts by weight solvent, then add the linking agent of 1 ~ 2 weight part containing tertiary amine structure, then add 1 ~ 1.6 weight part chainextender, stirring reaction;
Preferably, described solvent is acetone;
Preferably, the described linking agent containing tertiary amine structure is trolamine;
Preferably, described chainextender is BDO;
Preferably, the temperature of reaction of step (3) described stirring reaction is 55 ~ 60 DEG C, and the reaction times is 3 ~ 4h;
(4) after step (3) stirring reaction terminates, in described polymerization reactor, the neutralizing agent of 0.6 ~ 1 weight part is added, stirring reaction;
Preferably, described neutralizing agent is Glacial acetic acid;
Preferably, the temperature of reaction of step (4) described stirring reaction is 40 ~ 50 DEG C, and the reaction times is 0.5 ~ 1h;
(5) reaction product after step (4) stirring reaction is transferred in dispersion bucket, 106 ~ 112 weight parts waters are added in dispersion bucket, add the silane coupling agent of 1 ~ 2 weight part again, high speed shear emulsification obtains emulsion, the rear chainextender of 0.4 ~ 0.8 weight part is added again, low temperature stirring reaction in gained emulsion;
Preferably, described water to be temperature the be deionized water of 0 ~ 5 DEG C
Preferably, described silane coupling agent is γ aminopropyltriethoxy silane;
Preferably, the emulsification times of the described high speed shear emulsification of step (5) is 10 ~ 15min, and shearing rotating speed is 4000 ~ 5000rpm;
Preferably, described rear chainextender is quadrol; Rear chainextender is before joining emulsion, and first dilute with water, can make rear chain extending reaction gentle, the emulsion shelf-stable prepared;
Preferably, the time of the described low temperature stirring reaction of step (5) is 40 ~ 60min, and temperature of reaction is room temperature;
(6) by the emulsion underpressure distillation after step (5) low temperature stirring reaction, desolvation;
Preferably, the vacuum tightness of step (6) described underpressure distillation is-0.1MPa, and temperature is 45 ~ 55 DEG C, and the time is 1.5 ~ 2.5h;
(7) in the emulsion after step (6) underpressure distillation, add defoamer and flow agent, obtain described organic-silicon-modified both sexes aqueous polyurethane emulsion;
Preferably, the addition of described defoamer is 0.4 weight part, and the addition of flow agent is 0.2 weight part;
Preferably, described defoamer is the water-based defoamer DAPRO DF1760 of extra large this special chemical of name; Described flow agent is the water-based flow agent DC-57 of Dow Corning Corporation.
A kind of organic-silicon-modified both sexes aqueous polyurethane emulsion is obtained according to above-mentioned preparation method; Described organic-silicon-modified both sexes aqueous polyurethane emulsion can be used for the preparation field of elastomerics, hide finishes, coating or pressure sensitive adhesive.
The present invention has following advantage and effect relative to prior art:
(1) preparation method of the present invention is by employing aliphatic polyisocyante, makes gained aqueous polyurethane non yellowing, and obtained by performance and aromatic polyisocyanate, Property of Waterborne Polyurethane is suitable.
(2) preparation method of the present invention can to make in aqueous polyurethane segment soft section simultaneously containing sulfonic acid group, polyester polyol, polyether glycol, solves the difficult problem that consistency is bad.
(3) preparation method of the present invention uses the polyester type dibasic alcohol containing sulfonic acid group, and crystallinity is high, more easily forms hydrogen bond, and promote urethane segment mechanical property, the advantage that the elongation at break in conjunction with polyether Glycols is large, obtained mechanics performance of latex film is excellent; Use the polyester diol of small-molecular-weight, the molecular weight distribution of the finished product can be made to broaden, the first viscous force of obtained product is excellent.
(4) preparation method of the present invention uses low temperature deionized water to carry out shearing dispersion, chain extension after simultaneously carrying out after formation emulsion, and rear chain extending reaction is gentle, and obtained emulsion median size is little, and good emulsion stability, period of storage is long.
(5) solid content of organic-silicon-modified both sexes aqueous polyurethane emulsion of the present invention can reach 50%, belongs to high-solid content water-based polyurethane product, and solvent evaporates is fast, and time of drying is short, has good mobility and package stability simultaneously.
(6) preparation method of the present invention introduces the linking agent trolamine containing tertiary amine structure of three-functionality-degree, can form network structure, improve the mechanical property of urethane segment in urethane segment; By becoming amine salt with trolamine in Glacial acetic acid, making urethane segment introduce cation group, adding the performance such as water-soluble of urethane segment.
(7) organic-silicon-modified both sexes aqueous polyurethane emulsion of the present invention combines cationic and advantage that is anion-type water-thinned polyurethane, after emulsion film forming, intermolecular reactive force is stronger, force of cohesion is stronger, and the both sexes aqueous polyurethane product of preparation has excellent mechanical property, cohesive strength and good water tolerance.
(8) organic-silicon-modified both sexes aqueous polyurethane emulsion of the present invention is by silane coupler modified, between urethane segment and between urethane and base material, form the firmly 3 D cross-linked structure of interpenetrating(polymer)networks, obtained emulsion has excellent hydrophobic nature and adhesive power.
(9) preparation method's technique of the present invention is simple, and easy and simple to handle, preparation process is pollution-free.Use the polyester diol containing sulfonic acid group, because this polyester diol is terminal hydroxy group, speed of response is more easy to control, is beneficial to plant produced, not easily gel; And because sulfonic acid group is on soft section, prepolymerization reaction is gentle, does not need a large amount of solvent, decreases VOC; Step (2) gained reactant is the performed polymer containing sulfonic acid group, and its solid content is high, viscosity is low, only needs to add a small amount of organic solvent and reduces viscosity, and use solvent to recycle in production process, no solvent residue, environmental friendliness.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1
A kind of organic-silicon-modified both sexes aqueous polyurethane emulsion, formula composition and consumption as shown in table 1, concrete preparation process is as follows:
By the polyoxypropyleneglycol of formula ratio, to join containing the polyester diol of sulfonic acid group be equipped with digital display electric blender, thermometer polymerization reactor in, be warming up to 110 DEG C, underpressure distillation dewaters, and the insulation time of dewatering is 2h, dewaters after terminating and is cooled to 60 ~ 70 DEG C; In above-mentioned polymerization reactor, add catalyst dibutyltin dilaurylate, isophorone diisocyanate, be warming up to 85 DEG C, stirring reaction 3h; Then be cooled to 60 DEG C, add acetone, after stirring 10min, add trolamine and BDO, stirring reaction 3h; Then be cooled to 50 DEG C, add Glacial acetic acid, stirring reaction 0.5h; Reaction product in above-mentioned polymerization reactor is transferred in dispersion bucket, setting high-speed shear mixer rotating speed 4500rpm, adds 5 DEG C of deionized water emulsification pretreatments, emulsification times 15min in dispersion bucket, in gained emulsion, add quadrol, continue to stir chain extension 40min; Gained emulsion is warming up to 55 DEG C, underpressure distillation desolvation; In emulsion, add defoamer, flow agent, obtain described organic-silicon-modified both sexes aqueous polyurethane emulsion.
The organic-silicon-modified both sexes aqueous polyurethane emulsion composition of raw materials of table 1. embodiment 1 and consumption
| Material name | Consumption/part |
| Polyoxypropyleneglycol | 57.76 |
| Containing the polyester diol of sulfonic acid group | 12.91 |
| Dibutyl tin laurate | 0.04 |
| Isophorone diisocyanate | 27.83 |
| Trolamine | 1.59 |
| BDO | 1.31 |
| Acetone | 65.00 |
| Glacial acetic acid | 0.64 |
| Deionized water | 107 |
| γ aminopropyltriethoxy silane | 1.104 |
| Quadrol | 0.56 |
| Defoamer | 0.40 |
| Flow agent | 0.20 |
Embodiment 2
A kind of organic-silicon-modified both sexes aqueous polyurethane emulsion, formula composition and consumption as shown in table 2, concrete preparation process is as follows:
By the polyoxypropyleneglycol of formula ratio, to join containing the polyester diol of sulfonic acid group be equipped with digital display electric blender, thermometer polymerization reactor in, be warming up to 110 DEG C, underpressure distillation dewaters, and the insulation time of dewatering is 2h, dewaters after terminating and is cooled to 60 ~ 70 DEG C; In above-mentioned polymerization reactor, add catalyst dibutyltin dilaurylate, isophorone diisocyanate, be warming up to 85 DEG C, stirring reaction 3h; Then be cooled to 60 DEG C, add acetone, after stirring 10min, add trolamine and BDO, stirring reaction 3h; Then be cooled to 45 DEG C, add Glacial acetic acid, stirring reaction 0.75h; Reaction product in above-mentioned polymerization reactor is transferred in dispersion bucket, setting high-speed shear mixer rotating speed 4000rpm, adds 5 DEG C of deionized water emulsification pretreatments, emulsification times 10min in dispersion bucket, in gained emulsion, add quadrol, continue to stir chain extension 40min; Gained emulsion is warming up to 50 DEG C, underpressure distillation desolvation; In emulsion, add defoamer, flow agent, obtain described organic-silicon-modified both sexes aqueous polyurethane emulsion.
The organic-silicon-modified both sexes aqueous polyurethane emulsion composition of raw materials of table 2. embodiment 2 and consumption
| Material name | Consumption/part |
| Polyoxypropyleneglycol | 53.43 |
| Containing the polyester diol of sulfonic acid group | 12.59 |
| Dibutyl tin laurate | 0.04 |
| Isophorone diisocyanate | 28.85 |
| Trolamine | 1.81 |
| BDO | 1.49 |
| Acetone | 75.00 |
| Glacial acetic acid | 0.73 |
| Deionized water | 109 |
| γ aminopropyltriethoxy silane | 1.18 |
| Quadrol | 0.64 |
| Defoamer | 0.40 |
| Flow agent | 0.20 |
Embodiment 3
A kind of organic-silicon-modified both sexes aqueous polyurethane emulsion, formula composition and consumption as shown in table 3, concrete preparation process is as follows:
By the polyoxypropyleneglycol of formula ratio, to join containing the polyester diol of sulfonic acid group be equipped with digital display electric blender, thermometer polymerization reactor in, be warming up to 110 DEG C, underpressure distillation dewaters, and the insulation time of dewatering is 2h, dewaters after terminating and is cooled to 60 ~ 70 DEG C; In above-mentioned polymerization reactor, add catalyst dibutyltin dilaurylate, isophorone diisocyanate, be warming up to 80 DEG C, stirring reaction 3.5h; Then be cooled to 55 DEG C, add acetone, after stirring 10min, add trolamine and BDO, stirring reaction 4h; Then be cooled to 50 DEG C, add Glacial acetic acid, stirring reaction 0.5h; Reaction product in above-mentioned polymerization reactor is transferred in dispersion bucket, setting high-speed shear mixer rotating speed 4500rpm, adds 5 DEG C of deionized water emulsification pretreatments, emulsification times 15min in dispersion bucket, in gained emulsion, add quadrol, continue to stir chain extension 40min; Gained emulsion is warming up to 55 DEG C, underpressure distillation desolvation; In emulsion, add defoamer, flow agent, obtain described organic-silicon-modified both sexes aqueous polyurethane emulsion.
The organic-silicon-modified both sexes aqueous polyurethane emulsion composition of raw materials of table 3. embodiment 3 and consumption
| Material name | Consumption/part |
| Polyoxypropyleneglycol | 56.08 |
| Containing the polyester diol of sulfonic acid group | 13.21 |
| Dibutyl tin laurate | 0.04 |
| Isophorone diisocyanate | 26.71 |
| Trolamine | 1.35 |
| BDO | 1.08 |
| Acetone | 70.00 |
| Glacial acetic acid | 0.55 |
| Deionized water | 109 |
| γ aminopropyltriethoxy silane | 1.06 |
| Quadrol | 0.48 |
| Defoamer | 0.40 |
| Flow agent | 0.20 |
Embodiment 4
A kind of organic-silicon-modified both sexes aqueous polyurethane emulsion, formula composition and consumption as shown in table 4, concrete preparation process is as follows:
By the polyoxypropyleneglycol of formula ratio, to join containing the polyester diol of sulfonic acid group be equipped with digital display electric blender, thermometer polymerization reactor in, be warming up to 110 DEG C, underpressure distillation dewaters, and the insulation time of dewatering is 2h, dewaters after terminating and is cooled to 60 ~ 70 DEG C; In above-mentioned polymerization reactor, add catalyst dibutyltin dilaurylate, isophorone diisocyanate, be warming up to 85 DEG C, stirring reaction 3h; Then be cooled to 60 DEG C, add acetone, after stirring 10min, add trolamine and BDO, stirring reaction 3h; Then be cooled to 50 DEG C, add Glacial acetic acid, stirring reaction 0.5h; Reaction product in above-mentioned polymerization reactor is transferred in dispersion bucket, setting high-speed shear mixer rotating speed 4500rpm, adds 5 DEG C of deionized water emulsification pretreatments, emulsification times 15min in dispersion bucket, in gained emulsion, add quadrol, continue to stir chain extension 40min; Gained emulsion is warming up to 55 DEG C, underpressure distillation desolvation; In emulsion, add defoamer, flow agent, obtain described organic-silicon-modified both sexes aqueous polyurethane emulsion.
The organic-silicon-modified both sexes aqueous polyurethane emulsion composition of raw materials of table 4. embodiment 4 and consumption
| Material name | Consumption/part |
| Polyoxypropyleneglycol | 53.99 |
| Containing the polyester diol of sulfonic acid group | 12.73 |
| Dibutyl tin laurate | 0.04 |
| Isophorone diisocyanate | 28.29 |
| Trolamine | 1.70 |
| BDO | 1.36 |
| Acetone | 70.00 |
| Glacial acetic acid | 0.68 |
| Deionized water | 112 |
| γ aminopropyltriethoxy silane | 1.33 |
| Quadrol | 0.60 |
| Defoamer | 0.40 |
| Flow agent | 0.20 |
Embodiment 5
A kind of organic-silicon-modified both sexes aqueous polyurethane emulsion, formula composition and consumption as shown in table 5, concrete preparation process is as follows:
By the polyoxypropyleneglycol of formula ratio, to join containing the polyester diol of sulfonic acid group be equipped with digital display electric blender, thermometer polymerization reactor in, be warming up to 110 DEG C, underpressure distillation dewaters, and the insulation time of dewatering is 2h, dewaters after terminating and is cooled to 60 ~ 70 DEG C; In above-mentioned polymerization reactor, add catalyst dibutyltin dilaurylate, isophorone diisocyanate, be warming up to 85 DEG C, stirring reaction 3h; Then be cooled to 60 DEG C, add acetone, after stirring 10min, add trolamine and BDO, stirring reaction 3h; Then be cooled to 50 DEG C, add Glacial acetic acid, stirring reaction 0.5h; Reaction product in above-mentioned polymerization reactor is transferred in dispersion bucket, setting high-speed shear mixer rotating speed 4500rpm, adds 5 DEG C of deionized water emulsification pretreatments, emulsification times 15min in dispersion bucket, in gained emulsion, add quadrol, continue to stir chain extension 40min; Gained emulsion is warming up to 55 DEG C, underpressure distillation desolvation; In emulsion, add defoamer, flow agent, obtain described organic-silicon-modified both sexes aqueous polyurethane emulsion.
The organic-silicon-modified both sexes aqueous polyurethane emulsion composition of raw materials of table 5. embodiment 5 and consumption
| Material name | Consumption/part |
| Polyoxypropyleneglycol | 55.23 |
| Containing the polyester diol of sulfonic acid group | 13.02 |
| Dibutyl tin laurate | 0.04 |
| Isophorone diisocyanate | 27.36 |
| Trolamine | 1.49 |
| BDO | 1.19 |
| Acetone | 60.00 |
| Glacial acetic acid | 0.60 |
| Deionized water | 110 |
| γ aminopropyltriethoxy silane | 1.17 |
| Quadrol | 0.53 |
| Defoamer | 0.40 |
| Flow agent | 0.20 |
Performance Detection is analyzed:
Respectively the test such as solids content, viscosity is carried out to the organic-silicon-modified both sexes aqueous polyurethane emulsion that embodiment 1 ~ 5 obtains.Described organic-silicon-modified both sexes aqueous polyurethane emulsion is measured solid content with reference to GB1725-1979 " solids coatings assay method "; Described organic-silicon-modified both sexes aqueous polyurethane emulsion is at room temperature used Shanghai City Jing Hui plant and instrument company limited NDJ-8S type digital display viscometer determining viscosity; The glued membrane obtained after described organic-silicon-modified both sexes aqueous polyurethane emulsion film at room temperature dry 24h is immersed in the water 72h, carries out the test of glue-line water-intake rate; Instron company 3367 of Britain type universal testing machine is used by described organic-silicon-modified both sexes aqueous polyurethane emulsion film to carry out tensile strength and elongation at break test at normal temperatures.The aqueous polyurethane product D8 getting Italy (Cesalpinia Chemicals) company carries out the test of identical items, as a control group.
Above test event result data is as shown in table 6:
The performance measurement result of the organic-silicon-modified both sexes aqueous polyurethane emulsion of table 6. embodiment 1-5 gained
From table 6 data, organic-silicon-modified both sexes aqueous polyurethane emulsion solids content obtained by the present invention is high, show that outward appearance is good, mechanical property good, water-tolerant and the excellent properties of environmental protection, the glue-line water-intake rate of product of the present invention is less than 1.0%, and on market the water-intake rate of aqueous polyurethane generally between 1% ~ 4%.In conjunction with all the other fundamental property indexs, the organic-silicon-modified both sexes aqueous polyurethane emulsion excellent performance that the present invention obtains, can meet coating, synthetic leather, the requirement of sizing agent industrial application.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (9)
1. a preparation method for organic-silicon-modified both sexes aqueous polyurethane emulsion, is characterized in that comprising the steps:
(1) with weight parts, join in polymerization reactor by the polyester diol that 52 ~ 60 weight part polyether glycols and 12 ~ 15 weight parts contain sulfonic acid group, underpressure distillation dewaters, then temperature adjustment to 60 ~ 70 DEG C;
(2) in step (1) described polymerization reactor, 0.04 part by weight of catalyst and 25 ~ 30 weight part polyisocyanates are added, stirring reaction;
(3) after step (2) stirring reaction terminates, in described polymerization reactor, add 60 ~ 80 parts by weight solvent, then add the linking agent containing tertiary amine structure of 1 ~ 2 weight part, then add 1 ~ 1.6 weight part chainextender, stirring reaction;
(4) after step (3) stirring reaction terminates, in described polymerization reactor, the neutralizing agent of 0.6 ~ 1 weight part is added, stirring reaction;
(5) reaction product after step (4) stirring reaction is transferred in dispersion bucket, 106 ~ 112 weight parts waters are added in dispersion bucket, add the silane coupling agent of 1 ~ 2 weight part again, high speed shear emulsification obtains emulsion, the rear chainextender of 0.4 ~ 0.8 weight part is added again, low temperature stirring reaction in gained emulsion;
(6) by the emulsion underpressure distillation after step (5) low temperature stirring reaction, desolvation;
(7) in the emulsion after step (6) underpressure distillation, add defoamer and thickening material, obtain described organic-silicon-modified both sexes aqueous polyurethane emulsion.
2. the preparation method of organic-silicon-modified both sexes aqueous polyurethane emulsion according to claim 1, is characterized in that: step (1) described polyether glycol is polyoxypropyleneglycol; The vacuum tightness of step (1) described underpressure distillation is-0.1MPa, and temperature is 100 ~ 110 DEG C, and the time is 2h.
3. the preparation method of organic-silicon-modified both sexes aqueous polyurethane emulsion according to claim 1, is characterized in that: step (2) described catalyzer is dibutyl tin laurate; Step (2) described polyisocyanates is isophorone diisocyanate; The temperature of reaction of step (2) described stirring reaction is 80 ~ 85 DEG C, and the reaction times is 3 ~ 3.5h.
4. the preparation method of organic-silicon-modified both sexes aqueous polyurethane emulsion according to claim 1, is characterized in that: step (3) described solvent is acetone; Step (3) described chainextender is BDO; The described linking agent containing tertiary amine structure of step (3) is trolamine; The temperature of reaction of step (3) described stirring reaction is 55 ~ 60 DEG C, and the reaction times is 3 ~ 4h.
5. the preparation method of organic-silicon-modified both sexes aqueous polyurethane emulsion according to claim 1, is characterized in that: step (4) described neutralizing agent is Glacial acetic acid; The temperature of reaction of step (4) described stirring reaction is 40 ~ 50 DEG C, and the reaction times is 0.5h ~ 1h.
6. the preparation method of organic-silicon-modified both sexes aqueous polyurethane emulsion according to claim 1, is characterized in that: step (5) described water to be temperature the be deionized water of 0 ~ 5 DEG C; Step (5) described silane coupling agent is γ aminopropyltriethoxy silane; The described rear chainextender of step (5) is quadrol; The emulsification times of the described high speed shear emulsification of step (5) is 10 ~ 15min, and shearing rotating speed is 4000 ~ 5000rpm; The time of the described low temperature stirring reaction of step (5) is 40 ~ 60min, and temperature of reaction is room temperature.
7. the preparation method of organic-silicon-modified both sexes aqueous polyurethane emulsion according to claim 1, is characterized in that: the vacuum tightness of step (6) described underpressure distillation is-0.1MPa, and temperature is 45 ~ 55 DEG C, and the time is 1.5 ~ 2.5h.
8. the preparation method of organic-silicon-modified both sexes aqueous polyurethane emulsion according to claim 1, is characterized in that: the addition of described defoamer is 0.4 weight part, and the addition of flow agent is 0.2 weight part; Described defoamer is the water-based defoamer DAPRO DF1760 of extra large this special chemical of name; Described flow agent is the water-based flow agent DC-57 of Dow Corning Corporation.
9. the organic-silicon-modified both sexes aqueous polyurethane emulsion that obtains of the preparation method of the organic-silicon-modified both sexes aqueous polyurethane emulsion according to any one of claim 1 ~ 8.
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| CN115613388B (en) * | 2022-09-30 | 2023-07-21 | 重庆美力斯新材料科技股份有限公司 | Coating agent for napped fiber paper of paper diaper and preparation method thereof |
| CN117820956A (en) * | 2024-03-05 | 2024-04-05 | 上海豫宏建设集团有限公司 | Water-based waterproof paint and preparation method thereof |
| CN117820956B (en) * | 2024-03-05 | 2024-05-17 | 上海豫宏建设集团有限公司 | Water-based waterproof paint and preparation method thereof |
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