CN102617822B - Preparation method of pyridine sulfonic acid type water-based polyurethane emulsion - Google Patents
Preparation method of pyridine sulfonic acid type water-based polyurethane emulsion Download PDFInfo
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- CN102617822B CN102617822B CN2012100774751A CN201210077475A CN102617822B CN 102617822 B CN102617822 B CN 102617822B CN 2012100774751 A CN2012100774751 A CN 2012100774751A CN 201210077475 A CN201210077475 A CN 201210077475A CN 102617822 B CN102617822 B CN 102617822B
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Abstract
The invention relates to a preparation method of a pyridine sulfonic acid type water-based polyurethane emulsion, which comprises the following steps: (1) carrying out prepolymerization reaction on polyester polyol, organic diisocyanate and dihydroxymethylpropionic acid in the presence of a catalyst; (2) dissolving in acetone, and neutralizing by adding a salifying reagent; (3) adding a pyridine sulfonic acid diamine hydrophilic chain extender to carry out chain extension reaction, thereby obtaining a polymer of which the terminal group contains an NCO group; (4) adding deionized water, stirring at high speed to be dispersed into an emulsion, and adding low-molecular weight polyamine to carry out secondary chain extension reaction; and (5) distilling under reduced pressure to remove the acetone, thereby obtaining the pyridine sulfonic acid type water-based polyurethane emulsion. Since the diamine containing pyridine sulfonic acid structure is used as the hydrophilic chain extender, the prepared polyurethane emulsion has the advantages of high adhesive strength and yellowing resistance.
Description
Technical field
The invention belongs to the fine polymer field, relate to a kind of preparation method of pyridine-sulfonic acid type aqueous polyurethane emulsion.
Background technology
Aqueous polyurethane is as a kind of environmentally friendly macromolecular material, have solvent-free, odorless, pollution-free, do not fire, with the easy blending of other emulsions, be conducive to the characteristics such as modification, be widely used in wherein at tackiness agent and paint field, being most widely used in the products such as tackiness agent, coating, paper coating, hide finishes, fiber or fabric-treating agent.
US Patent No. 3036998, US3756992 had once reported the preparation method of aqueous polyurethane emulsion, but the aqueous polyurethane emulsion solid content of the method preparation is lower.Because the low-solid content tackiness agent exists moisture evaporation speed slow, gluing often, the problems such as storage and transportation, therefore limited its application.US Patent No. 4870129 has been reported a kind of method that adopts the sulfonate type hydrophilic chain extender to prepare water-based polyurethane adhesive.The polyisocyanates and the hydrophilic chain extender that adopt in this patent are aliphatics, and therefore, the aqueous polyurethane crystal property for preparing, tack and anti-physics shrinkage there is no method and meet the requirement of aqueous adhesive.2007 Zhongshan University's master thesis " preparation of footwear use polyurethane adhesive " (Qin Chang rolling) reported that employing sulfonic acid type aromatic ring diamines prepares aqueous polyurethane as hydrophilic chain extender, crystal property and tack improve, but owing to containing benzene ring structure in the hydrophilic chain extender that uses, so not anti-xanthochromia.
Summary of the invention
The purpose of this invention is to provide a kind of good film-forming property, crystal property is good, and cohesive strength is high, the preparation method of the pyridine-sulfonic acid type aqueous polyurethane emulsion of anti-xanthochromia, high solids content.
The preparation method of this pyridine-sulfonic acid type aqueous polyurethane emulsion comprises the following steps:
(1) polyester polyol is carried out vacuum hydro-extraction and process, then with organic diisocyanate, dimethylol propionic acid, carry out prepolymerization reaction under catalyzer exists, the reaction times is 2～5 hours, and temperature of reaction is 75～85 ℃;
(2) gained prepolymer of upper step is cooled to below 50 ℃, then use acetone solution, then add the salt-forming reagent neutralization, the time of neutralization is 10～30 minutes;
(3) add pyridine-sulfonic acid sodium diamines hydrophilic chain extender to carry out chain extending reaction in upper step gained material, obtain the polymkeric substance that end group contains the NCO group, the temperature of reaction is 10～60 ℃, and the reaction times is 0.5～1h, and described pyridine-sulfonic acid sodium diamines hydrophilic chain extender is expressed by the following formula:
N=2,3 or 4 in formula;
Above-mentioned pyridine-sulfonic acid sodium diamines by
With H
2N (CH
2)
nNH
2After reaction again with NaHSO
3Reaction makes, n=2,3 or 4 in formula.
(4) add the deionized water high-speed stirring to be dispersed into emulsion in the polymkeric substance of upper step gained, then add low-molecular-weight polyamine to carry out the secondary chain extension reaction, the reaction times is 0.5～1h;
(5) decompression steams acetone, namely makes pyridine-sulfonic acid type aqueous polyurethane emulsion.
The preparation method of pyridine-sulfonic acid type aqueous polyurethane emulsion of the present invention is owing to having used the diamines that contains the pyridine-sulfonic acid structure as hydrophilic chain extender, it had both contained regular pyridine ring structure, can improve crystal property and initial adhesion intensity, and possesses anti-physics shrinkage preferably, pyridine ring is the electron deficiency system on organic chemistry simultaneously, it is difficult for oxidized and makes color burn, has the performance of anti-xanthochromia, thereby makes the high and anti-xanthochromia of the polyurethane dispersions cohesive strength that makes.
Embodiment
The preparation method of this pyridine-sulfonic acid type aqueous polyurethane emulsion comprises the following steps:
(1) polyester polyol is carried out vacuum hydro-extraction and process, then with organic diisocyanate, dimethylol propionic acid (DMPA), carry out prepolymerization reaction under catalyzer exists, the reaction times is 2～5 hours, is preferably 4h; 70～100 ℃ of temperature of reaction, be preferably 75～85 ℃;
(2) gained prepolymer of upper step is cooled to below 50 ℃, then use acetone solution, then add the salt-forming reagent neutralization, the time of neutralization is 10～30 minutes;
(3) add pyridine-sulfonic acid sodium diamines hydrophilic chain extender to carry out chain extending reaction in upper step gained material, obtain end group and contain the polymkeric substance of NCO group, the temperature of reaction is 10～60 ℃, and the reaction times is 0.5～1h.Described pyridine-sulfonic acid sodium diamines hydrophilic chain extender is expressed by the following formula:
N=2,3 or 4 in formula;
(4) add the deionized water high-speed stirring to be dispersed into emulsion in the polymkeric substance of upper step gained, then add low-molecular-weight polyamine to carry out the secondary chain extension reaction, the reaction times is 0.5～1h;
(5) decompression steams acetone, namely makes the pyridine-sulfonic acid type aqueous polyurethane emulsion of high solids content.
In the preparation method of this pyridine-sulfonic acid type aqueous polyurethane emulsion, in the prepolymerization reaction in (1) step, the molar ratio of organic diisocyanate and polyester polyol can be 1.2～2.0, and the quality of the dimethylol propionic acid that adds is 0.3～2% of prepolymer total mass; Described catalyzer is dibutyl tin laurate (DBTDL) or stannous octoate, and add-on is 0.01～0.1% of prepolymer total mass, is preferably 0.01～0.03%; In (2) step the acetone quality that adds be contained solid in emulsion quality 40～120%, be preferably 50～100%; The salt-forming reagent that adds, for can generate with carboxyl the reagent of salt or ionic group, common are triethylamine, ammoniacal liquor, potassium hydroxide, sodium hydroxide, is preferably triethylamine; Degree of neutralization is 70～100%; In (3) step, the quality of the pyridine-sulfonic acid sodium diamines hydrophilic chain extender that adds is that the 1～5%, the (4) step of the quality of contained solid in emulsion to add the quality of water be 40～60% of total aqueous polyurethane emulsion quality; The low-molecular-weight polyamine that adds is quadrol, and the quadrol amount that adds is: the amido in quadrol: the isocyano in aqueous polyurethane emulsion=1: 0.6～1.8(mol ratio).
In the preparation method of this pyridine-sulfonic acid type aqueous polyurethane emulsion, organic diisocyanate in the prepolymerization reaction in (1) step can be isophorone diisocyanate (IPDI) or 1, the mixture of one or more of hexamethylene-diisocyanate (HDI), Methylcyclohexyl diisocyanate (HTDI), be preferably a kind of in isophorone diisocyanate (IPDI) and hexamethylene diisocyanate (HDI) or two kinds; Described polyester polyol is polyester glycol, the pure and mild polycarbonate diol of polylactone two, and preferred polyester glycol or polylactone glycol, molecular weight are 500～5000, and preferred molecular weight is 1000～3000.
in the preparation method of this pyridine-sulfonic acid type aqueous polyurethane emulsion, polyester glycol described in the prepolymerization reaction in (1) step can be one or both di-carboxylic acid (succsinic acid, tartrate, pentanedioic acid, hexanodioic acid, toxilic acid, SA, 1, the di-carboxylic acid such as 4-cyclohexyl dicarboxylic acid) with a kind of or two kinds of low molecular weight polyols (ethylene glycol, propylene glycol, 1, the 2-butyleneglycol, 1, the 3-butyleneglycol, 1, the 4-butyleneglycol, neopentyl glycol, 1, the 6-hexylene glycol, 1, the 8-ethohexadiol, 1, the 9-nonanediol, the low molecular weight polyols such as Diethylene Glycol) make by method of condensing.The polylactone glycol can replace the cyclic ester monomer ring-opening polymerizations such as 6-caprolactone, δ-valerolactone by 6-caprolactone, alkyl and make, preferably poly-hexanodioic acid-BDO ester (PBA) and poly-epsilon-caprolactone (PCL).
In the preparation method of this pyridine-sulfonic acid type aqueous polyurethane emulsion, (3) step described in pyridine-sulfonic acid sodium diamines can by
With H
2N (CH
2)
nNH
2After reaction again with NaHSO
3Reaction makes, n=2,3 or 4 in formula.
Concrete preparation method is as follows:
(1) 2-[6-(2-aminoethylamino) picolyl] preparation method of ethylsulfonic acid sodium:
(2) 2-[6-(2-amino propyl amino) picolyl] preparation method of ethylsulfonic acid sodium:
(3) 2-[6-(2-aminobutyl amino) picolyl] preparation method of ethylsulfonic acid sodium:
The preparation method of this pyridine-sulfonic acid type aqueous polyurethane emulsion adopts pyridine-sulfonic acid sodium diamines as the synthetic aqueous polyurethane emulsion of hydrophilic chain extender, crystal property and the anti-yellowing property of aqueous polyurethane emulsion have greatly been improved, synthesis technique is simple, synthetic aqueous polyurethane emulsion solid content is between 40～60%, and particle diameter is 70～200nm.
Below with specific embodiment, technical scheme of the present invention is further described, but protection scope of the present invention is not limited to this:
Embodiment 1:
In the reactor with agitator, thermometer, water cooler, the PBA(number-average molecular weight that adds 200g is 2000), in 100～120 ℃ of fusings, vacuum hydro-extraction 1h, sampling is surveyed moisture content and is started cooling less than 0.1% the time; When temperature drops to 80 ℃, add 13.3g IPDI, 19.5g HDI, 1.1g DMPA and 0.05g DBTDL catalyzer to carry out prepolymerization reaction, stirring reaction approximately obtains prepolymer after 4h.Above-mentioned prepolymer is cooled to 50 ℃, adds 170g acetone solution prepolymer, then add 0.7g triethylamine neutralization, in and the time be 15min; Adding 4.2g2-[6-(2-aminoethylamino) picolyl] ethylsulfonic acid sodium carries out chain extending reaction, and reaction times 0.5h, obtain end group and contain the polymkeric substance of NCO group; Add the 210g deionized water in above-mentioned polymkeric substance, high-speed stirring is dispersed into emulsion, then adds the 1.5g quadrol to carry out secondary chain extension, reaction times 0.5h; Finally, acetone is extracted in decompression out, namely makes the high solid content aqueous polyurethane emulsion (WPU-1) that contains pyridine-sulfonic acid diamines hydrophilic chain extender.
The solid content of WPU-1 is 51.5%, appearance milky white band blue light, and median size is 176nm.
Embodiment 2:
In the reactor with agitator, thermometer, water cooler, adding 200g PBA(number-average molecular weight is 2000), in 100～120 ℃ of fusings, vacuum hydro-extraction 1h, sampling is surveyed moisture content and is started cooling less than 0.1% the time; When temperature drops to 80 ℃, add 38.1g IPDI, 3.1g DMPA and 0.05g DBTDL catalyzer to carry out prepolymerization reaction, stirring reaction approximately obtains prepolymer after 4h.Above-mentioned prepolymer is cooled to 50 ℃, adds 210g acetone solution prepolymer, then add 2.1g triethylamine neutralization, in and the time be 15min; Adding 3.5g2-[6-(2-amino propyl amino) picolyl] ethylsulfonic acid sodium carries out chain extending reaction, and reaction times 0.5h, obtain end group and contain the polymkeric substance of NCO group; Add the 225g deionized water in above-mentioned polymkeric substance, high-speed stirring is dispersed into emulsion, then adds the 1.5g quadrol to carry out secondary chain extension, reaction times 0.5h; Finally, acetone is extracted in decompression out, namely makes the high solid content aqueous polyurethane emulsion (WPU-2) that contains pyridine-sulfonic acid diamines hydrophilic chain extender.
The solid content of WPU-2 is 51.9%, appearance milky white band blue light, and median size is 154nm.
Embodiment 3:
In the reactor with agitator, thermometer, water cooler, adding 250g PCL(number-average molecular weight is 2000), in 100～120 ℃ of fusings, vacuum hydro-extraction 1h, sampling is surveyed moisture content and is started cooling less than 0.1% the time; When temperature drops to 80 ℃, add 46.9g HDI, 3.9g DMPA and 0.06g DBTDL catalyzer to carry out prepolymerization reaction, stirring reaction approximately obtains prepolymer after 4h.Above-mentioned prepolymer is cooled to 50 ℃, adds 265g acetone solution prepolymer, then add 2.4g triethylamine neutralization, in and the time be 15min; Adding 3g2-[6-(2-aminobutyl amino) picolyl] ethylsulfonic acid sodium carries out chain extending reaction, and reaction times 0.5h, obtain end group and contain the polymkeric substance of NCO group; Add the 290g deionized water in above-mentioned polymkeric substance, high-speed stirring is dispersed into emulsion, then adds the 2.3g quadrol to carry out secondary chain extension, reaction times 0.5h; Finally, acetone is extracted in decompression out, namely makes the high solid content aqueous polyurethane emulsion (WPU-3) that contains pyridine-sulfonic acid diamines hydrophilic chain extender.
The solid content of WPU-3 is 48.9%, appearance milky white band blue light, and median size is 110nm.
Embodiment 4:
In the reactor with agitator, thermometer, water cooler, the PBA(number-average molecular weight that adds 268g is 3000), the PBA(number-average molecular weight of 124g is 1000), in 100～120 ℃ of fusings, vacuum hydro-extraction 1h, sampling is surveyed moisture content and is started cooling less than 0.1% the time; When temperature drops to 80 ℃, add 50.1g IPDI, 16.2g HDI, 2.2g DMPA and 0.11gDBTDL catalyzer to carry out prepolymerization reaction, stirring reaction approximately obtains prepolymer after 4h.Above-mentioned prepolymer is cooled to 50 ℃, adds 260g acetone solution prepolymer, then add 1.6g triethylamine neutralization, in and the time be 15min; Adding 9.8g2-[6-(2-aminoethylamino) picolyl] ethylsulfonic acid sodium carries out chain extending reaction, and reaction times 0.5h, obtain end group and contain the polymkeric substance of NCO group; Add the 440g deionized water in above-mentioned polymkeric substance, high-speed stirring is dispersed into emulsion, then adds the 2.1g quadrol to carry out secondary chain extension, reaction times 0.5h; Finally, acetone is extracted in decompression out, namely makes the high solid content aqueous polyurethane emulsion (WPU-4) that contains pyridine-sulfonic acid diamines hydrophilic chain extender.
The solid content of WPU-4 is 50.1%, appearance milky white band blue light, and median size is 178nm.
Embodiment 5:
In the reactor with agitator, thermometer, water cooler, the PBA(number-average molecular weight that adds 176g is 2000), the PCL(number-average molecular weight of 64g is 2000), in 100～120 ℃ of fusings, vacuum hydro-extraction 1h, sampling is surveyed moisture content and is started cooling less than 0.1% the time; When temperature drops to 80 ℃, add 10.8g IPDI, 32.7g HDI, 4.3g DMPA and 0.08g DBTDL catalyzer to carry out prepolymerization reaction, stirring reaction approximately obtains prepolymer after 4h.Above-mentioned prepolymer is cooled to 50 ℃, adds 260g acetone solution prepolymer, then add 2.8g triethylamine neutralization, in and the time be 15min; Adding 3.1g2-[6-(2-aminoethylamino) picolyl] ethylsulfonic acid sodium carries out chain extending reaction, and reaction times 0.5h, obtain end group and contain the polymkeric substance of NCO group; Add the 280g deionized water in above-mentioned polymkeric substance, high-speed stirring is dispersed into emulsion, then adds the 1.9g quadrol to carry out secondary chain extension, reaction times 0.5h; Finally, acetone is extracted in decompression out, namely makes the high solid content aqueous polyurethane emulsion (WPU-5) that contains pyridine-sulfonic acid diamines hydrophilic chain extender.
The solid content of WPU-5 is 49.8%, appearance milky white band blue light, and median size is 122nm.
Embodiment 6:
In the reactor with agitator, thermometer, water cooler, the PBA(number-average molecular weight that adds 120g is 3000), the PCL(number-average molecular weight of 202g is 2000), in 100～120 ℃ of fusings, vacuum hydro-extraction 1h, sampling is surveyed moisture content and is started cooling less than 0.1% the time; When temperature drops to 80 ℃, add 27.8g IPDI, 21.1g HDI, 1.9g DMPA and 0.1g DBTDL catalyzer to carry out prepolymerization reaction, stirring reaction approximately obtains prepolymer after 4h.Above-mentioned prepolymer is cooled to 50 ℃, adds 360g acetone solution prepolymer, then add 1.4g triethylamine neutralization, in and the time be 15min; Adding 7.5g2-[6-(2-amino propyl amino) picolyl] ethylsulfonic acid sodium carries out chain extending reaction, and reaction times 0.5h, obtain end group and contain the polymkeric substance of NCO group; Add the 360g deionized water in above-mentioned polymkeric substance, high-speed stirring is dispersed into emulsion, then adds the 2.1g quadrol to carry out secondary chain extension, reaction times 0.5h; Finally, acetone is extracted in decompression out, namely makes the high solid content aqueous polyurethane emulsion (WPU-6) that contains pyridine-sulfonic acid diamines hydrophilic chain extender.
The solid content of WPU-6 is 50.2%, appearance milky white band blue light, and median size is 110nm.
Above-mentioned 6 embodiment gained polyaminoester emulsions are carried out the T-peel strength test, and the mensuration of T-stripping strength is carried out with reference to GB/T27912-1995, and its draw speed is 100mm/min, and base material is PVC.Test-results is as shown in the table:
Claims (4)
1. the preparation method of a pyridine-sulfonic acid type aqueous polyurethane emulsion is characterized in that it comprises the following steps:
(1) polyester polyol is carried out vacuum hydro-extraction and process, then with organic diisocyanate, dimethylol propionic acid, carry out prepolymerization reaction under catalyzer exists, the reaction times is 2～5 hours, and temperature of reaction is 75～85 ℃;
(2) gained prepolymer of upper step is cooled to below 50 ℃, then use acetone solution, then add the salt-forming reagent neutralization, the time of neutralization is 10～30 minutes;
(3) add pyridine-sulfonic acid sodium diamines hydrophilic chain extender to carry out chain extending reaction in upper step gained material, obtain the polymkeric substance that end group contains the NCO group, the temperature of reaction is 10～60 ℃, and the reaction times is 0.5～1h, and described pyridine-sulfonic acid sodium diamines hydrophilic chain extender is expressed by the following formula:
N=2,3 or 4 in formula;
Above-mentioned pyridine-sulfonic acid sodium diamines by
With H
2N (CH
2)
nNH
2After reaction again with NaHSO
3Reaction makes, n=2,3 or 4 in formula.
(4) add the deionized water high-speed stirring to be dispersed into emulsion in the polymkeric substance of upper step gained, then add low-molecular-weight polyamine to carry out the secondary chain extension reaction, the reaction times is 0.5～1h;
(5) decompression steams acetone, namely makes pyridine-sulfonic acid type aqueous polyurethane emulsion.
2. the preparation method of pyridine-sulfonic acid type aqueous polyurethane emulsion as claimed in claim 1, the molar ratio that it is characterized in that organic diisocyanate and polyester polyol in the prepolymerization reaction in described (1) step is 1.2～2.0, and the quality of the dimethylol propionic acid that adds is 0.3～2% of prepolymer total mass; Described catalyzer is dibutyl tin laurate or stannous octoate, and add-on is 0.01～0.03% of prepolymer total mass; In (2) step the acetone quality that adds be contained solid in emulsion quality 50～100%; The salt-forming reagent that adds is triethylamine, and degree of neutralization is 70～100%; In (3) step, the quality of the pyridine-sulfonic acid sodium diamines hydrophilic chain extender that adds is that the 1～5%, the (4) step of the quality of the contained solid of emulsion to add the quality of water be 40～60% of total aqueous polyurethane emulsion quality; The low-molecular-weight polyamine that adds is quadrol, the amount of the quadrol that adds through molar ratio computing be: the amido in quadrol: the isocyano in aqueous polyurethane emulsion=1: 0.6～1.8.
3. the preparation method of pyridine-sulfonic acid type aqueous polyurethane emulsion as claimed in claim 2, it is characterized in that organic diisocyanate in the prepolymerization reaction in described (1) step is the mixture of a kind of in isophorone diisocyanate or hexamethylene diisocyanate or two kinds; Described polyester polyol is polyester glycol, and this polyester glycol makes by method of condensing for one or both di-carboxylic acid and a kind of or two kinds of low molecular weight polyols, and molecular weight is 1000～3000.
4. the preparation method of pyridine-sulfonic acid type aqueous polyurethane emulsion as claimed in claim 2, it is characterized in that organic diisocyanate in the prepolymerization reaction in described (1) step is the mixture of a kind of in isophorone diisocyanate or hexamethylene diisocyanate or two kinds; Described polyester polyol is the polylactone glycol, and this polylactone glycol is made by the ring-opening polymerization of cyclic ester monomer, and molecular weight is 1000～3000.
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| CN110862506A (en) * | 2019-10-29 | 2020-03-06 | 中国科学院山西煤炭化学研究所 | Synthetic method of waterborne polyurethane primer |
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| CN109251291A (en) * | 2017-07-12 | 2019-01-22 | 广州冠志新材料科技有限公司 | A kind of alicyclic sulfonic acid type hydrophilic chain extending agent and preparation method thereof |
| CN110330618B (en) * | 2019-07-30 | 2021-05-18 | 嘉兴学院 | Waterborne polyurethane emulsion, preparation method and application thereof |
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| GB2235927B (en) * | 1989-09-14 | 1992-10-21 | Asahi Chemical Ind | A sulfonic acid group-containing polyurethane and a photosensitive resin composition containing the same |
| US8148462B2 (en) * | 2006-07-07 | 2012-04-03 | Tosoh Corporation | Aqueous polyurethane fluid dispersion and method for producing the same |
| CN101597369B (en) * | 2008-06-06 | 2011-12-14 | 佛山市南海霸力化工制品有限公司 | High solid content polyurethane emulsion containing alicyclic sulfonic acid type hydrophilic chain extending agent and preparation method thereof |
| CN101638468B (en) * | 2009-09-04 | 2011-11-09 | 安徽大学 | Preparation method of sulfonate amphoteric polyurethane emulsion |
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