CN104312520A - Amphoteric waterborne polyurethane shoe adhesive with high solid content and preparation method thereof - Google Patents
Amphoteric waterborne polyurethane shoe adhesive with high solid content and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of waterborne polyurethane adhesive, and discloses an amphoteric waterborne polyurethane adhesive with high solid content and a preparation method thereof. The preparation method comprises the following steps: synthesizing an amino-containing cationic hydrophilic cross-linker; adding polyester polyol into a polymerization reactor, distilling under reduced pressure to remove water, adding polyisocyanate and a catalyst, and reacting while stirring; adding the cationic hydrophilic cross-linker and a chain extender, and reacting while stirring; adding an organic solvent and a hydrophilic chain extender containing a sulfonic acid group, and continuously reacting while stirring; adding water and a silicane coupling agent to a dispersion barrel filled with the reactant, performing high-speed shear emulsification, and adding a post chain extender for reacting; and distilling under reduced pressure, and then adding a defoaming agent and a thickener to obtain the amphoteric waterborne polyurethane shoe adhesive with high solid content. The amphoteric waterborne polyurethane shoe adhesive with high solid content substantially does not have solvent residue, has excellent mechanical properties and good water and heat resistance, and can substitute the present commercial mature solvent type adhesive.
Description
Technical field
The invention belongs to Aqueous Polyurethane Adhesives technical field, both sexes aqueous polyurethane adhesives for shoes being specifically related to a kind of high solids content and preparation method thereof.
Background technology
China is that footwear boots make, consume and big export country, but is not shoemaking power, and consumption per head is also on the low side.2007 annual production more than 100 hundred million pairs, export 81.7 hundred million pairs.The overwhelming majority is rubber adhesive shoes, substantially adopts solvent-based adhesive, year glue consumption about 300,000 t (non-volatile matter quality mark < 20%).Polyurethanes sizing agent has low temperature resistant, the feature such as snappiness good, adhesive property is strong and soft durometer adjustability is good, and in shoemaking industry, usage quantity increases year by year.
Adhesive for polyurethane on domestic market is based on solvent-borne type, and by using the organic solvents such as a large amount of toluene, dimethylbenzene to obtain with solution polymerization process, but execution conditions are severe, and a large amount of solvents in product can damage human body and ecotope.Due to many reasons, China's footwear use adhesive for polyurethane (WPU) technology is made slow progress for a long time.21 century, especially in recent years, along with the cry of international energy-saving and emission-reduction grows to even greater heights, require increasingly strict to the environmental protection index of outlet footwear, in addition compatriots' environmental consciousness progressively strengthens, and country has formulated shoes-used glue compulsory standard: all have to benzene,toluene,xylene, total halohydrocarbon, free isocyanate, normal hexane and VOC etc. regulation of clearly limiting the quantity.No matter from domestic or state is external, research and develop the footwear use adhesive for polyurethane suitable with solvent borne polyurethane sizing agent performance become shoemaking industry can the important symbol of Sustainable development.Domestic Aqueous Polyurethane Adhesives exploitation is started late, and gap is comparatively large compared with foreign level, enters 21 century, R&D work starts to enliven, make substantial progress at present, what have enters the pilot scale stage, but most of aqueous polyurethane shoes-used glue still depends on import.Along with the development of society, aqueous polyurethane adhesives for shoes at home universal is the development inexorable trend of adhesives for shoes.
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 to anion-containing matrix as glass and leather have good adhesivity, insensitive to water hardness, and can use in acid condition; Cation-type water-thinned polyurethane dispersion liquid 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 CN 101698744A discloses a kind of, uses the aqueous polyurethane of the obtained high solids content of the method difficulty.Chinese patent CN 102585149B 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.
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 the preparation method of the both sexes aqueous polyurethane adhesives for shoes providing a kind of high solids content, and described preparation method is easy to produce, and preparation process is pollution-free;
Another object of the present invention is to the both sexes aqueous polyurethane adhesives for shoes of the high solids content providing above-mentioned preparation method to obtain, the both sexes aqueous polyurethane adhesives for shoes of gained high solids content can be used for the bonding of footwear material, after laminating is shaped and water Long Term Contact and not coming off, ageing-resistant and cohesive force is strong.
Object of the present invention is achieved through the following technical solutions:
A preparation method for the both sexes aqueous polyurethane adhesives for shoes of high solids content, comprises the steps:
(1) in weight fraction, the uniform dissolution in 50 parts by weight solvent by 149 weight part trolamines and 90 weight part 2 hydroxy propanoic acids, then constant temperature back flow reaction in reaction flask is joined, room temperature is cooled to after reaction terminates, filter, underpressure distillation, except desolventizing and water, obtains cationic hydrophilic linking agent;
Preferably, described solvent is acetone;
Preferably, described reaction flask is the four-hole boiling flask being equipped with electric blender, snakelike condensing reflux pipe;
Preferably, the temperature of reaction of described constant temperature back flow reaction is 40 ~ 50 DEG C, and the reaction times is 0.5 ~ 1h;
Preferably, the vacuum tightness of described underpressure distillation is-0.1MPa, and temperature is 50 ~ 55 DEG C, and the time is 2h;
As follows according to the molecular structural formula of the cationic hydrophilic linking agent of step (1) gained:
(2) with weight parts, join in polymerization reactor by 82 ~ 84 weight of polyester polyvalent alcohols, underpressure distillation dewaters, then temperature adjustment to 50 ~ 60 DEG C;
Preferably, described polyester polyol is poly-hexanodioic acid-BDO ester; Preferred, the molecular weight of described poly-hexanodioic acid-BDO ester is 2000;
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 110 ~ 120 DEG C, and the time is 2h;
(3) in step (2) described polymerization reactor, 0.04 part by weight of catalyst and 12 ~ 14 weight part polyisocyanates are added, stirring reaction;
Preferably, described catalyzer is dibutyl tin laurate;
Preferably, described polyisocyanates is tolylene diisocyanate;
Preferably, the temperature of reaction of step (3) described stirring reaction is 60 ~ 65 DEG C, and the reaction times is 2 ~ 2.5h;
(4) after step (3) stirring reaction terminates, in described polymerization reactor, add cationic hydrophilic linking agent and 0.5 ~ 0.8 weight part chainextender of step (1) gained of 0.3 ~ 0.4 weight part, stirring reaction forms performed polymer;
Preferably, described chainextender is BDO;
Preferably, the temperature of reaction of step (4) described stirring reaction is 50 ~ 60 DEG C, and the reaction times is 1.5 ~ 2h;
(5) after step (4) stirring reaction terminates, in described polymerization reactor, add 100 ~ 120 weight parts organic solvent, then add the hydrophilic chain extender of 2.6 ~ 3.0 weight parts containing sulfonic acid group, stirring reaction;
Preferably, described organic solvent is acetone;
Preferably, the described hydrophilic chain extender containing sulfonic acid group to be massfraction be 50% quadrol base ethyl sulfonic acid sodium water solution;
Preferably, the temperature of reaction of step (5) described stirring reaction is 55 ~ 60 DEG C, and the reaction times is 30min ~ 45min;
(6) reaction product after step (5) stirring reaction is transferred in dispersion bucket, 105 ~ 111 weight parts waters are added in dispersion bucket, add the silane coupling agent of 1 ~ 1.5 weight part again, high speed shear emulsification obtains emulsion, the rear chainextender of 0.5 ~ 0.8 weight part is added again in gained emulsion, low temperature stirring reaction, obtains 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 (6) 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 (6) is 40 ~ 60min, and temperature of reaction is room temperature;
(7) by the underpressure distillation of step gained emulsion, desolvation;
Preferably, the vacuum tightness of step (7) described underpressure distillation is-0.1MPa, and temperature is 45 ~ 55 DEG C, and the time is 1.5 ~ 2.5h;
(8) in the emulsion after step (7) underpressure distillation, add defoamer and thickening material, obtain the both sexes aqueous polyurethane adhesives for shoes of described high solids content;
Preferably, the addition of described defoamer is 0.4 weight part, and the addition of thickening material is 0.2 weight part;
Preferably, described defoamer is the water-based defoamer DAPRO DF1760 of extra large this special chemical of name; Described thickening material is the thickening material Thicklevelling HAS 635 of extra large river chemical science and technology.
A kind of both sexes aqueous polyurethane adhesives for shoes of high solids content is obtained according to above-mentioned preparation method.The both sexes aqueous polyurethane adhesives for shoes of described high solids content can be used for the bonding of footwear material.
The present invention has following advantage and effect relative to prior art:
(1) the cationic hydrophilic linking agent preparing use in preparation method of the present invention is formed by the trolamine and 2 hydroxy propanoic acid neutralization reaction that contain tertiary amine group, is beneficial to plant produced, not easily gel; Simultaneously, containing four hydroxyls in this cationic hydrophilic linking agent molecule, easily form network structure at polyurethane chain intersegmental part, urethane segment is arranged more fine and close, promote urethane segment mechanical property and water tolerance, solvent resistance, obtained sizing agent excellent combination property; And because having ammonium in this cationic hydrophilic cross-linker molecules structure, cation group can be introduced urethane segment, adding the water-soluble of segment.
(2) solid content of the both sexes aqueous polyurethane adhesives for shoes of high solids content of the present invention can reach 50%, belongs to high solids content sizing agent product, and solvent evaporates is fast, and time of drying is short, has good mobility and package stability simultaneously.
(3) the both sexes aqueous polyurethane adhesives for shoes of high solids content 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.
(4) the both sexes aqueous polyurethane adhesives for shoes of high solids content 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 sizing agent has excellent hydrophobic nature and adhesive power.
(5) 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.
(6) preparation method's technique of the present invention is simple, and easy and simple to handle, preparation process is pollution-free.Cationic hydrophilic linking agent can dissolve each other with polyester polyol, adds system, decrease VOC after not needing with an organic solvent to dissolve; The performed polymer solid content high viscosity that step (4) obtains 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
Cationic hydrophilic linking agent used in the embodiment of the present invention, preparation method is as follows:
With weight parts, the uniform dissolution in 50 pbw acetone by the trolamine of 149 weight parts and 90 weight part 2 hydroxy propanoic acids, then join in the four-hole boiling flask being equipped with electric blender, snakelike condensing reflux pipe, be warming up to 40 ~ 50 DEG C, constant temperature back flow reaction 0.5 ~ 1h, is cooled to room temperature, filter, again in-0.1MPa vacuum tightness, underpressure distillation 2h removes acetone and water at 50 ~ 55 DEG C, obtain cationic hydrophilic linking agent, the structural formula of gained cationic hydrophilic linking agent is as follows:
Embodiment 2
A both sexes aqueous polyurethane adhesives for shoes for high solids content, formula composition and consumption as shown in table 1, concrete preparation process is as follows:
Joined in the polymerization reactor being equipped with digital display electric blender, thermometer by the poly-hexanodioic acid-BDO ester of formula ratio, be warming up to 120 DEG C, underpressure distillation dewaters, and the insulation time of dewatering is 2h, dewaters after terminating and is cooled to 50 ~ 60 DEG C; In polymerization reactor, add catalyst dibutyltin dilaurylate, tolylene diisocyanate, be warming up to 65 DEG C, stirring reaction 2h; Then be cooled to 60 DEG C, add cationic hydrophilic linking agent described in BDO and embodiment 1, stirring reaction 1.5h; Then be cooled to 55 DEG C, add acetone, add the quadrol base ethyl sulfonic acid sodium water solution of massfraction 50% after stirring 15min, stirring reaction 45min; Reaction product in polymerization reactor is transferred in dispersion bucket, setting high-speed shear mixer rotating speed 4500rpm, 5 DEG C of deionized waters and γ aminopropyltriethoxy silane emulsification pretreatment is added in dispersion bucket, emulsification times 15min, 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, thickening material, obtain the both sexes aqueous polyurethane adhesives for shoes of described high solids content.
The both sexes aqueous polyurethane adhesives for shoes composition of raw materials of the high solids content of table 1. embodiment 2 and consumption
| Material name | Consumption/part |
| Poly-hexanodioic acid-BDO ester | 82.46 |
| Dibutyl tin laurate | 0.04 |
| Tolylene diisocyanate | 12.93 |
| Cationic hydrophilic linking agent | 0.40 |
| BDO | 0.74 |
| Acetone | 110.00 |
| 50% quadrol base ethyl sulfonic acid sodium water solution | 2.88 |
| Deionized water | 111 |
| γ aminopropyltriethoxy silane | 1.39 |
| Quadrol | 0.64 |
| Defoamer | 0.40 |
| Thickening material | 0.20 |
Embodiment 3
A both sexes aqueous polyurethane adhesives for shoes for high solids content, formula composition and consumption as shown in table 2, concrete preparation process is as follows:
Joined in the polymerization reactor being equipped with digital display electric blender, thermometer by the poly-hexanodioic acid-BDO ester of formula ratio, be warming up to 120 DEG C, underpressure distillation dewaters, and the insulation time of dewatering is 2h, dewaters after terminating and is cooled to 50 ~ 60 DEG C; In polymerization reactor, add catalyst dibutyltin dilaurylate, tolylene diisocyanate, be warming up to 65 DEG C, stirring reaction 2h; Then be cooled to 60 DEG C, add cationic hydrophilic linking agent described in BDO and embodiment 1, stirring reaction 1.5h; Then be cooled to 55 DEG C, add acetone, add the quadrol base ethyl sulfonic acid sodium water solution of massfraction 50% after stirring 15min, stirring reaction 45min; Reaction product in polymerization reactor is transferred in dispersion bucket, setting high-speed shear mixer rotating speed 4500rpm, 5 DEG C of deionized waters and γ aminopropyltriethoxy silane emulsification pretreatment is added in dispersion bucket, emulsification times 15min, 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, thickening material, obtain the both sexes aqueous polyurethane adhesives for shoes of described high solids content.
The both sexes aqueous polyurethane adhesives for shoes composition of raw materials of the high solids content of table 2. embodiment 3 and consumption
| Material name | Consumption/part |
| Poly-hexanodioic acid-BDO ester | 82.84 |
| Dibutyl tin laurate | 0.04 |
| Tolylene diisocyanate | 12.77 |
| Cationic hydrophilic linking agent | 0.38 |
| BDO | 0.72 |
| Acetone | 115.00 |
| 50% quadrol base ethyl sulfonic acid sodium water solution | 2.79 |
| Deionized water | 108 |
| γ aminopropyltriethoxy silane | 1.27 |
| Quadrol | 0.63 |
| Defoamer | 0.40 |
| Thickening material | 0.20 |
Embodiment 4
A both sexes aqueous polyurethane adhesives for shoes for high solids content, formula composition and consumption as shown in table 3, concrete preparation process is as follows:
Joined in the polymerization reactor being equipped with digital display electric blender, thermometer by the poly-hexanodioic acid-BDO ester of formula ratio, be warming up to 115 DEG C, underpressure distillation dewaters, and the insulation time of dewatering is 2h, dewaters after terminating and is cooled to 50 ~ 60 DEG C; In polymerization reactor, add catalyst dibutyltin dilaurylate, tolylene diisocyanate, be warming up to 60 DEG C, stirring reaction 2.5h; Then be cooled to 60 DEG C, add cationic hydrophilic linking agent described in BDO and embodiment 1, stirring reaction 1.5h; Then be cooled to 55 DEG C, add acetone, add the quadrol base ethyl sulfonic acid sodium water solution of massfraction 50% after stirring 15min, stirring reaction 45min; Reaction product in polymerization reactor is transferred in dispersion bucket, setting high-speed shear mixer rotating speed 4500rpm, 5 DEG C of deionized waters and γ aminopropyltriethoxy silane emulsification pretreatment is added in dispersion bucket, emulsification times 15min, 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, thickening material, obtain the both sexes aqueous polyurethane adhesives for shoes of described high solids content.
The both sexes aqueous polyurethane adhesives for shoes composition of raw materials of the high solids content of table 3. embodiment 4 and consumption
| Material name | Consumption/part |
| Poly-hexanodioic acid-BDO ester | 83.11 |
| Dibutyl tin laurate | 0.04 |
| Isophorone diisocyanate | 12.67 |
| Cationic hydrophilic linking agent | 0.37 |
| BDO | 0.70 |
| Acetone | 115.00 |
| 50% quadrol base ethyl sulfonic acid sodium water solution | 2.84 |
| Deionized water | 110 |
| γ aminopropyltriethoxy silane | 1.10 |
| Quadrol | 0.62 |
| Defoamer | 0.40 |
| Thickening material | 0.20 |
Embodiment 5
A both sexes aqueous polyurethane adhesives for shoes for high solids content, formula composition and consumption as shown in table 4, concrete preparation process is as follows:
Joined in the polymerization reactor being equipped with digital display electric blender, thermometer by the poly-hexanodioic acid-BDO ester of formula ratio, be warming up to 120 DEG C, underpressure distillation dewaters, and the insulation time of dewatering is 2h, dewaters after terminating and is cooled to 50 ~ 60 DEG C; In polymerization reactor, add catalyst dibutyltin dilaurylate, tolylene diisocyanate, be warming up to 65 DEG C, stirring reaction 2h; Then be cooled to 60 DEG C, add cationic hydrophilic linking agent described in BDO and embodiment 1, stirring reaction 1.5h; Then be cooled to 60 DEG C, add acetone, add the quadrol base ethyl sulfonic acid sodium water solution of massfraction 50% after stirring 15min, stirring reaction 30min; Reaction product in polymerization reactor is transferred in dispersion bucket, setting high-speed shear mixer rotating speed 4000rpm, 5 DEG C of deionized waters and γ aminopropyltriethoxy silane emulsification pretreatment is added in dispersion bucket, emulsification times 15min, 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, thickening material, obtain the both sexes aqueous polyurethane adhesives for shoes of described high solids content.
The both sexes aqueous polyurethane adhesives for shoes composition of raw materials of the high solids content of table 4. embodiment 5 and consumption
| Material name | Consumption/part |
| Poly-hexanodioic acid-BDO ester | 83.63 |
| Dibutyl tin laurate | 0.04 |
| Isophorone diisocyanate | 12.38 |
| Cationic hydrophilic linking agent | 0.35 |
| BDO | 0.63 |
| Acetone | 120.00 |
| 50% quadrol base ethyl sulfonic acid sodium water solution | 2.78 |
| Deionized water | 107 |
| γ aminopropyltriethoxy silane | 1.04 |
| Quadrol | 0.58 |
| Defoamer | 0.40 |
| Thickening material | 0.20 |
Embodiment 6
A both sexes aqueous polyurethane adhesives for shoes for high solids content, formula composition and consumption as shown in table 5, concrete preparation process is as follows:
Joined in the polymerization reactor being equipped with digital display electric blender, thermometer by the poly-hexanodioic acid-BDO ester of formula ratio, 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 50 ~ 60 DEG C; In polymerization reactor, add catalyst dibutyltin dilaurylate, tolylene diisocyanate, be warming up to 60 DEG C, stirring reaction 2.5h; Then be cooled to 50 DEG C, add cationic hydrophilic linking agent described in BDO and embodiment 1, stirring reaction 2h; Then be cooled to 59 DEG C, add acetone, add the quadrol base ethyl sulfonic acid sodium water solution of massfraction 50% after stirring 15min, stirring reaction 33min; Reaction product in polymerization reactor is transferred in dispersion bucket, setting high-speed shear mixer rotating speed 4500rpm, 5 DEG C of deionized waters and γ aminopropyltriethoxy silane emulsification pretreatment is added in dispersion bucket, emulsification times 15min, 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, thickening material, obtain the both sexes aqueous polyurethane adhesives for shoes of described high solids content.
The both sexes aqueous polyurethane adhesives for shoes composition of raw materials of the high solids content of table 5. embodiment 6 and consumption
| Material name | Consumption/part |
| Poly-hexanodioic acid-BDO ester | 83.32 |
| Dibutyl tin laurate | 0.04 |
| Isophorone diisocyanate | 12.55 |
| Cationic hydrophilic linking agent | 0.36 |
| BDO | 0.58 |
| Acetone | 120.00 |
| 50% quadrol base ethyl sulfonic acid sodium water solution | 2.89 |
| Deionized water | 112 |
| γ aminopropyltriethoxy silane | 1.08 |
| Quadrol | 0.66 |
| Defoamer | 0.40 |
| Thickening material | 0.20 |
Performance Detection is analyzed:
Respectively the test such as solids content, viscosity is carried out to the both sexes aqueous polyurethane adhesives for shoes of the high solids content that embodiment 2 ~ 6 obtains.The both sexes aqueous polyurethane adhesives for shoes emulsion of described high solids content is measured solid content with reference to GB1725-1979 " solids coatings assay method "; The both sexes aqueous polyurethane adhesives for shoes emulsion of described high solids content 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 the both sexes aqueous polyurethane adhesives for shoes of described high solids content at room temperature dry 24h is immersed in the water 72h, carries out the test of glue-line water-intake rate; With reference to GB/T 2792-1998 by the both sexes aqueous polyurethane adhesives for shoes of described high solids content after dry 24 hours and after dry 24 hours water soaking carry out 180 ° of peel strength tests after 7 days.The aqueous polyurethane Dispercoll series product U-54 getting Bayer Bitterfeld GmbH (Bayer) 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 both sexes aqueous polyurethane adhesives for shoes of table 6. embodiment 2-6 gained high solids content
From table 6 data, the both sexes aqueous polyurethane adhesives for shoes of the high solids content obtained by the present invention shows that stripping strength is high, 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 glue-line generally between 1.0% ~ 4.0%; The stripping strength of water soaking after 7 days does not almost obviously reduce in addition, and all will reduce by more than 10% for other aqueous adhesive general stripping strength after water soaking.In conjunction with all the other fundamental property indexs, the both sexes aqueous polyurethane adhesives for shoes excellent performance of the high solids content that the present invention obtains, can meet shoemaking industry application requiring.
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 (10)
1. a preparation method for the both sexes aqueous polyurethane adhesives for shoes of high solids content, is characterized in that comprising the steps:
(1) in weight fraction, the uniform dissolution in 50 parts by weight solvent by 149 weight part trolamines and 90 weight part 2 hydroxy propanoic acids, then constant temperature back flow reaction in reaction flask is joined, room temperature is cooled to after reaction terminates, filter, underpressure distillation, except desolventizing and water, obtains cationic hydrophilic linking agent;
(2) with weight parts, join in polymerization reactor by 82 ~ 84 weight of polyester polyvalent alcohols, underpressure distillation dewaters, then temperature adjustment to 50 ~ 60 DEG C;
(3) in step (2) described polymerization reactor, 0.04 part by weight of catalyst and 12 ~ 14 weight part polyisocyanates are added, stirring reaction;
(4) after step (3) stirring reaction terminates, in described polymerization reactor, add cationic hydrophilic linking agent and 0.5 ~ 0.8 weight part chainextender of step (1) gained of 0.3 ~ 0.4 weight part, stirring reaction forms performed polymer;
(5) after step (4) stirring reaction terminates, in described polymerization reactor, add 100 ~ 120 weight parts organic solvent, then add the hydrophilic chain extender of 2.6 ~ 3.0 weight parts containing sulfonic acid group, stirring reaction;
(6) reaction product after step (5) stirring reaction is transferred in dispersion bucket, 105 ~ 111 weight parts waters are added in dispersion bucket, add the silane coupling agent of 1 ~ 1.5 weight part again, high speed shear emulsification obtains emulsion, the rear chainextender of 0.5 ~ 0.8 weight part is added again in gained emulsion, low temperature stirring reaction, obtains emulsion;
(7) by the underpressure distillation of step gained emulsion, desolvation;
(8) in the emulsion after step (7) underpressure distillation, add defoamer and thickening material, obtain the both sexes aqueous polyurethane adhesives for shoes of described high solids content.
2. the preparation method of the both sexes aqueous polyurethane adhesives for shoes of high solids content according to claim 1, is characterized in that: step (1) described solvent is acetone; The temperature of reaction of the described constant temperature back flow reaction of step (1) is 40 ~ 50 DEG C, and the reaction times is 0.5 ~ 1h; The vacuum tightness of step (1) described underpressure distillation is-0.1MPa, and temperature is 50 ~ 55 DEG C, and the time is 2h.
3. the preparation method of the both sexes aqueous polyurethane adhesives for shoes of high solids content according to claim 1, is characterized in that: step (2) described polyester polyol is poly-hexanodioic acid-BDO ester; The vacuum tightness that step (2) described underpressure distillation dewaters is set as-0.1MPa, and temperature is 110 ~ 120 DEG C, and the time is 2h.
4. the preparation method of the both sexes aqueous polyurethane adhesives for shoes of high solids content according to claim 1, is characterized in that: step (3) described catalyzer is dibutyl tin laurate; Step (3) described polyisocyanates is tolylene diisocyanate; The temperature of reaction of step (3) described stirring reaction is 60 ~ 65 DEG C, and the reaction times is 2 ~ 2.5h.
5. the preparation method of the both sexes aqueous polyurethane adhesives for shoes of high solids content according to claim 1, is characterized in that: step (4) described chainextender is BDO; The temperature of reaction of step (4) described stirring reaction is 50 ~ 60 DEG C, and the reaction times is 1.5 ~ 2h.
6. the preparation method of the both sexes aqueous polyurethane adhesives for shoes of high solids content according to claim 1, is characterized in that: step (5) described organic solvent is acetone; The described hydrophilic chain extender containing sulfonic acid group of step (5) to be massfraction be 50% quadrol base ethyl sulfonic acid sodium water solution; The temperature of reaction of step (5) described stirring reaction is 55 ~ 60 DEG C, and the reaction times is 30min ~ 45min.
7. the preparation method of the both sexes aqueous polyurethane adhesives for shoes of high solids content according to claim 1, is characterized in that: step (6) described water to be temperature the be deionized water of 0 ~ 5 DEG C; The emulsification times of the described high speed shear emulsification of step (6) is 10 ~ 15min, and shearing rotating speed is 4000 ~ 5000rpm; Step (6) described silane coupling agent is γ aminopropyltriethoxy silane; The described rear chainextender of step (6) is quadrol; The time of the described low temperature stirring reaction of step (6) is 40 ~ 60min, and temperature of reaction is room temperature.
8. the preparation method of the both sexes aqueous polyurethane adhesives for shoes of high solids content according to claim 1, is characterized in that: the vacuum tightness of step (7) described underpressure distillation is-0.1MPa, and temperature is 45 ~ 55 DEG C, and the time is 1.5 ~ 2.5h.
9. the preparation method of the both sexes aqueous polyurethane adhesives for shoes of high solids content according to claim 1, is characterized in that: the addition of described defoamer is 0.4 weight part, and the addition of thickening material is 0.2 weight part; Described defoamer is the water-based defoamer DAPRO DF1760 of extra large this special chemical of name; Described thickening material is the thickening material Thicklevelling HAS 635 of extra large river chemical science and technology.
10. the both sexes aqueous polyurethane adhesives for shoes of high solids content that obtains of the preparation method of the both sexes aqueous polyurethane adhesives for shoes of the high solids content according to any one of claim 1 ~ 9.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105001392A (en) * | 2015-07-29 | 2015-10-28 | 光山县博正树脂有限公司 | High-heat-resistance PU adhesive for shoes |
| CN106634779A (en) * | 2016-12-28 | 2017-05-10 | 上海飞顿新材料科技有限公司 | Preparation method of adhesive for aramid fiber no-woven cloth |
| CN110093140A (en) * | 2019-05-08 | 2019-08-06 | 广东伟明涂料有限公司 | A kind of synthetic method of the silane-modified water-based polyurethane adhesive of high intensity |
| CN111072907A (en) * | 2019-12-31 | 2020-04-28 | 江苏领瑞新材料科技有限公司 | Preparation method of waterborne polyurethane for bulletproof armor plate |
| CN112961317A (en) * | 2021-02-07 | 2021-06-15 | 武汉纺织大学 | Star-shaped polyurethane thickener with anion-cation amphoteric ion core and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999023130A1 (en) * | 1997-10-31 | 1999-05-14 | H.B. Fuller Licensing & Financing, Inc. | Aqueous polyurethane dispersions formed from norbonane diisocyanate |
| CN103320084A (en) * | 2013-05-23 | 2013-09-25 | 浙江枧洋化工有限公司 | Production method of waterborne polyurethane used for artificial leather bonding resin |
| CN103421462A (en) * | 2013-08-20 | 2013-12-04 | 华南理工大学 | High-initial-adhesion waterborne polyurethane adhesive and preparation method thereof |
-
2014
- 2014-10-22 CN CN201410567024.5A patent/CN104312520B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999023130A1 (en) * | 1997-10-31 | 1999-05-14 | H.B. Fuller Licensing & Financing, Inc. | Aqueous polyurethane dispersions formed from norbonane diisocyanate |
| CN103320084A (en) * | 2013-05-23 | 2013-09-25 | 浙江枧洋化工有限公司 | Production method of waterborne polyurethane used for artificial leather bonding resin |
| CN103421462A (en) * | 2013-08-20 | 2013-12-04 | 华南理工大学 | High-initial-adhesion waterborne polyurethane adhesive and preparation method thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105001392A (en) * | 2015-07-29 | 2015-10-28 | 光山县博正树脂有限公司 | High-heat-resistance PU adhesive for shoes |
| CN106634779A (en) * | 2016-12-28 | 2017-05-10 | 上海飞顿新材料科技有限公司 | Preparation method of adhesive for aramid fiber no-woven cloth |
| CN110093140A (en) * | 2019-05-08 | 2019-08-06 | 广东伟明涂料有限公司 | A kind of synthetic method of the silane-modified water-based polyurethane adhesive of high intensity |
| CN111072907A (en) * | 2019-12-31 | 2020-04-28 | 江苏领瑞新材料科技有限公司 | Preparation method of waterborne polyurethane for bulletproof armor plate |
| CN112961317A (en) * | 2021-02-07 | 2021-06-15 | 武汉纺织大学 | Star-shaped polyurethane thickener with anion-cation amphoteric ion core and preparation method thereof |
| CN112961317B (en) * | 2021-02-07 | 2022-06-10 | 武汉纺织大学 | Star-shaped polyurethane thickener with anion-cation amphoteric ion core and preparation method thereof |
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| CN104312520B (en) | 2016-04-13 |
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