CN103588684A - Glycol sulfonate used as hydrophilic chain-extender and its preparation method and application thereof - Google Patents
Glycol sulfonate used as hydrophilic chain-extender and its preparation method and application thereof Download PDFInfo
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- CN103588684A CN103588684A CN201310521955.7A CN201310521955A CN103588684A CN 103588684 A CN103588684 A CN 103588684A CN 201310521955 A CN201310521955 A CN 201310521955A CN 103588684 A CN103588684 A CN 103588684A
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Abstract
The invention belongs to the technical field of an aqueous polyurethane emulsion and discloses glycol sulfonate used as a hydrophilic chain-extender and its preparation method and application thereof. According to the invention, glycol sulfonate is prepared directly by an ester exchange method. The step is simple, and efficiency is high. The prepared glycol sulfonate which can be used as a hydrophilic chain-extender can be directly used in the preparation of waterborne polyurethane. The neutralization and salt formation step of carboxylate by a traditional technology is saved. Processes are simplified; efficiency is raised; an emulsion is very easy to disperse; there is little waste during the production process; and production cost is reduced. The prepared glycol sulfonate which can be used as a hydrophilic chain-extender is a transparent clear liquid at normal temperature, has low viscosity and is a benzene ring structure. With the introduction of a rigid group, heat stability of the waterborne polyurethane can be raised. The prepared glycol sulfonate hydrophilic chain-extender is an important water-soluble raw material. The prepared waterborne polyurethane has a wide application prospect in water-soluble environmental products.
Description
Technical field
The invention belongs to aqueous polyurethane emulsion technical field, particularly a kind of sulfonate dibasic alcohol that can be used as hydrophilic chain extender and its preparation method and application.
Background technology
Urethane refers to the general designation of the high molecular polymer of the amino-formate bond that contains repetition in molecular structure, and how it is obtained by the substance reaction of isocyanic ester and active dydrogen compounds.Traditional urethane mainly with organic solvent as dispersion medium.In recent years, along with environmental regulation increasingly stringent, petroleum products cost constantly raise, and made to using water to substitute organic solvent and was more paid close attention to as the aqueous polyurethane of dispersion medium.Aqueous polyurethane has been inherited a lot of excellent performances of solvent borne polyurethane, as adjustable in soft durometer, low temperature resistant, wear resistance is good, adhesive power is strong etc., in fields such as coating, finishing agent, dyeing and printing auxiliary, tackiness agent, is widely used.And in the preparation process of aqueous polyurethane, hydrophilic chain extender is the factor of most critical, in current suitability for industrialized production and laboratory study, what mainly adopt is that dimethylol propionic acid (DMPA) or dimethylolpropionic acid (DMBA) are hydrophilic monomer, and use these two kinds of hydrophilic monomers before adding emulsifying water, all need in and salify, at present use the most widely in and salt forming agent be triethylamine, and through triethylamine be neutralized in the aqueous polyurethane emulsion that emulsifying salt obtains may remaining triethylamine unpleasant irritating smell, and triethylamine may occur to decompose and volatilization in the storage process of emulsion, thereby cause aqueous polyurethane emulsion stability decreases.Chinese patent CN103254867A discloses a kind ofly take quadrol base ethyl sulfonic acid sodium (AAS) and prepares sulfonate type Aqueous Polyurethane Adhesives as hydrophilic chain extender, use this hydrophilic chain extender, very big in chain extension stage viscosity, need to add a large amount of acetone to reduce viscosity.US Patent No. 6017998 discloses a kind of preparation method of take the aqueous polyurethane emulsion that dimethylol propionic acid (DMPA) is hydrophilic chain extender, use carboxylic acid type hydrophilic chain extender need in and salify, processing step is many, energy consumption is large.
The disclosed aqueous polyurethane of prior art is mainly dimethylol propionic acid, dimethylolpropionic acid by the kind of hydrophilic chain extender, second diamino ethyl sulfonic acid sodium.Generally speaking hydrophilic chain extender is of less types, to the research of hydrophilic chain extender, is therefore also an important topic in aqueous polyurethane research.
Summary of the invention
In order to overcome the shortcoming and deficiency of above-mentioned prior art, primary and foremost purpose of the present invention is to provide a kind of sulfonate dibasic alcohol that can be used as hydrophilic chain extender.
Another object of the present invention is to provide the above-mentioned preparation method who can be used as the sulfonate dibasic alcohol of hydrophilic chain extender.It is main raw material that the present invention has adopted Sodium Dimethyl Isophthalate-5-sulfonate, and its hydrophilic radical that contains sulfonate has good wetting ability, for realizing object of the present invention, provides powerful guarantee, and present method raw material is easy to get, cheap, nontoxic, technique is simple.
Still a further object of the present invention is to provide the application of the above-mentioned sulfonate dibasic alcohol that can be used as hydrophilic chain extender in preparing aqueous polyurethane.Employing of the present invention and the exchange of small molecules binary alcohol esters obtain the sulfonate hydrophilic monomer containing activity hydroxy, compare with the synthesis process of aqueous polyurethane of traditional carboxylic acid type, in technique, omitted in carboxylic acid type and the step of salify, made the preparation technology of this aqueous polyurethane emulsion simple.
Object of the present invention realizes by following proposal:
A sulfonate dibasic alcohol for hydrophilic chain extender, has following chemical structure:
R is alkyl chain or the alkyl chain that contains ehter bond; M is monovalent metallic ion.
Sulfonate dibasic alcohol of the present invention is benzene ring structure, introduces rigid radical and can improve the aqueous polyurethane thermostability of utilizing it to prepare.
The above-mentioned preparation method who can be used as the sulfonate dibasic alcohol of hydrophilic chain extender, comprises following concrete steps:
Dimethyl isophthalate-5-sulfonate is mixed with dibasic alcohol, and under the effect of catalyzer, heated and stirred is reacted, and obtains can be used as the sulfonate dibasic alcohol of hydrophilic chain extender.
Preferably, described dibasic alcohol refers to ethylene glycol, glycol ether, triglycol, 1,2-PD, 1,3-PD, BDO, 1,3 butylene glycol, 1, at least one in 6-hexylene glycol and polyoxyethylene glycol (PEG).
More preferably, described dibasic alcohol refers at least one in PEG200, PEG400 and PEG600.
Preferably, described catalyzer refers at least one in Mono-n-butyltin, tetrabutyl titanate and zinc acetate.
More preferably, described catalyzer refers to FASCAT4100.
Dimethyl isophthalate-5-sulfonate used and the mol ratio of dibasic alcohol are 1:(2～4).
The amount of used catalyst is 0.5～1% of dimethyl isophthalate-5-sulfonate and dibasic alcohol total mass.
Described heated and stirred reaction refers to stirring reaction 2～7h at 180～250 ℃.
Preferably, after heated and stirred reaction, by least one in the methods such as underpressure distillation, washing or extraction, product is carried out to purifying.
More preferably, heated and stirred reaction is rear by underpressure distillation purified product.
The application of the above-mentioned sulfonate dibasic alcohol that can be used as hydrophilic chain extender in preparing aqueous polyurethane.
Mechanism of the present invention is:
The present invention directly adopts ester exchange method to prepare sulfonate dibasic alcohol, and step is simple, and efficiency is higher; The hydrophilic radical that dimethyl isophthalate-5-sulfonate used contains sulfonate, there is good wetting ability, the sulfonate dibasic alcohol of gained can be directly used in the preparation of aqueous polyurethane, omitted carboxylic acid type in traditional technology in and the step of salify, simplified step, improved efficiency, and emulsion is very easily disperseed, make production process less wastage, reduced production cost.
The present invention, with respect to prior art, has following advantage and beneficial effect:
(1) the present invention directly adopts ester exchange method to prepare sulfonate dibasic alcohol, and step is simple, and efficiency is high.
(2) the sulfonate dibasic alcohol that can be used as hydrophilic chain extender that prepared by the present invention is directly used in the preparation of aqueous polyurethane, omitted carboxylic acid type in traditional technology in and the step of salify, simplified step, improved efficiency, and emulsion is very easily disperseed, make production process less wastage, reduced production cost.
(3) existing sulfonate hydrophilic chain extender is AAS, for active amino, activity is larger, this chain extension process can only be rear chain extension mode, this chain extension method makes hydrophilic radical skewness on chain, and use AAS chain extension need to add a large amount of acetone, and need strong stirring, energy consumption and cost are higher.The sulfonate dibasic alcohol that can be used as hydrophilic chain extender prepared by the present invention is at normal temperatures for transparent clear liquid, has lower viscosity and is benzene ring structure, introduces rigid radical and can improve aqueous polyurethane thermostability.
(4) the sulfonate dibasic alcohol hydrophilic chain extender that prepared by the present invention can be directly used in the preparation of aqueous polyurethane, is the important water-soluble material of a class, and the aqueous polyurethane preparing has broad application prospects in water-soluble environment protective series products.
Accompanying drawing explanation
Fig. 1 is the infrared spectrum of the sulfonate dibasic alcohol that can be used as hydrophilic chain extender of embodiment 1 preparation.
Fig. 2 is the infrared spectrum of the sulfonate dibasic alcohol that can be used as hydrophilic chain extender of embodiment 2 preparations.
Fig. 3 is the infrared spectrum of the sulfonate dibasic alcohol that can be used as hydrophilic chain extender of embodiment 3 preparations.
Fig. 4 is the infrared spectrum of the sulfonate dibasic alcohol that can be used as hydrophilic chain extender of embodiment 4 preparations.
Fig. 5 is the infrared spectrum of the sulfonate dibasic alcohol that can be used as hydrophilic chain extender of embodiment 5 preparations.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
Embodiment 1: can be used as the preparation of the sulfonate dibasic alcohol of hydrophilic chain extender
Under heating, churned mechanically condition; 0.05mol Sodium Dimethyl Isophthalate-5-sulfonate, 0.4mol ethylene glycol and 0.5wt% Mono-n-butyltin are added in the there-necked flask that fractionation plant is housed; under nitrogen atmosphere protection, be slowly warming up to 180 ℃, at this temperature, react 7 hours.When still head steams without cut, change vacuum distillation apparatus, at 220 ℃, continue reaction 30min.Be down to room temperature discharging, obtain transparent liquid.By nuclear-magnetism infrared detection data analysis (see figure 1), this transparent liquid is sulfonate type dibasic alcohol prepared by the present invention.
In Fig. 1,629cm
-1, 753cm
-1, 877cm
-1for phenyl ring three replaces peak value, 1721cm
-1for carbonyl peak, 1091cm
-1for-C-O-C-peak, 1206cm
-1, 1046cm
-1, 980cm
-1for the absorption peak of sulfonate radical, 3480cm
-1going out broad peak is hydroxyl absorption peak.
Embodiment 2: can be used as the preparation of the sulfonate dibasic alcohol of hydrophilic chain extender
Under heating, churned mechanically condition; 0.05mol Sodium Dimethyl Isophthalate-5-sulfonate, 0.3mol glycol ether and 0.6wt% Mono-n-butyltin are added in the there-necked flask that fractionation plant is housed; under nitrogen atmosphere protection, be slowly warming up to 230 ℃, at this temperature, react 3 hours.When still head steams without cut, change vacuum distillation apparatus, at 230 ℃, continue reaction 30min.Be down to room temperature discharging, obtain transparent liquid, add dissolve with ethanol to clear solution product obtained above, add anhydrous diethyl ether, stratification, separatory takes off a layer transparent liquid, vacuum-drying product.By nuclear-magnetism infrared detection data analysis (see figure 2), this transparent liquid is sulfonate type dibasic alcohol prepared by the present invention.
In Fig. 2,630cm
-1, 760cm
-1, 878cm
-1for phenyl ring three replaces peak value, 1710cm
-1for carbonyl peak, 1079cm
-1for-C-O-C-peak, 1220cm
-1, 1040cm
-1, 980cm
-1for the absorption peak of sulfonate radical, 3480cm
-1place's broad peak is hydroxyl absorption peak.
Embodiment 3: can be used as the preparation of the sulfonate dibasic alcohol of hydrophilic chain extender
Under heating, churned mechanically condition; 0.05mol Sodium Dimethyl Isophthalate-5-sulfonate, 0.2mol Triethylene glycol and 0.7wt% zinc acetate are added in the there-necked flask that fractionation plant is housed; under nitrogen atmosphere protection, be slowly warming up to 230 ℃, at this temperature, react 3 hours.When still head steams without cut, change vacuum distillation apparatus, at 230 ℃, continue reaction 30min.Be down to room temperature discharging, obtain transparent liquid.By nuclear-magnetism infrared detection data analysis (see figure 3), this transparent liquid is sulfonate type dibasic alcohol prepared by the present invention.
In Fig. 3,629cm
-1, 753cm
-1, 877cm
-1for phenyl ring three replaces peak value, 1720cm
-1for carbonyl peak, 1010cm
-1for-C-O-C-peak, 1223cm
-1, 1036cm
-1, 980cm
-1for the absorption peak of sulfonate radical, 3480cm
-1going out broad peak is hydroxyl absorption peak.
Embodiment 4: can be used as the preparation of the sulfonate dibasic alcohol of hydrophilic chain extender
By 0.05mol Sodium Dimethyl Isophthalate-5-sulfonate, 0.35mol1,2-propylene glycol and 0.8wt% tetrabutyl titanate add in the there-necked flask that fractionation plant is housed, and under nitrogen atmosphere protection, are slowly warming up to 220 ℃, react 4 hours at this temperature.When still head steams without cut, change vacuum distillation apparatus, at 220 ℃, continue reaction 30min.Be down to room temperature discharging, obtain transparent liquid.By nuclear-magnetism infrared detection data analysis (see figure 4), this transparent liquid is sulfonate type dibasic alcohol prepared by the present invention.
In Fig. 4,629cm
-1, 753cm
-1, 877cm
-1for phenyl ring three replaces, 1741cm
-1for carbonyl peak, 1100cm
-1for-C-O-C-peak, 1226cm
-1, 1046cm
-1, 980cm
-1for the absorption peak of sulfonate radical, 3480cm
-1going out broad peak is hydroxyl absorption peak.
Embodiment 5: can be used as the preparation of the sulfonate dibasic alcohol of hydrophilic chain extender
0.05mol Sodium Dimethyl Isophthalate-5-sulfonate, 0.12mol PEG400 and 1wt%FASCAT4100 are added in the there-necked flask that fractionation plant is housed, under nitrogen atmosphere protection, be slowly warming up to 250 ℃, at this temperature, react 2 hours.When still head steams without cut, change vacuum distillation apparatus, at 250 ℃, continue reaction 30min.Be down to room temperature discharging, obtain transparent liquid.By nuclear-magnetism infrared detection data analysis (see figure 5), this transparent liquid is sulfonate type dibasic alcohol prepared by the present invention.
In Fig. 5,629cm
-1, 753cm
-1, 877cm
-1for phenyl ring three replaces, 1721cm
-1for carbonyl peak, 1101cm
-1for-C-O-C-peak, 1206cm
-1, 1046cm
-1, 980cm
-1for the absorption peak of sulfonate radical, 3480cm
-1going out broad peak is hydroxyl absorption peak.
Embodiment 6: can be used as the application of the sulfonate dibasic alcohol of hydrophilic chain extender
In three mouthfuls of reaction flasks of reflux exchanger, mechanical stirrer, nitrogen conduit are housed, the sulfonate dibasic alcohol that adds successively 10 gram of 1000 molecular weight polyoxyethylene propylene dibasic alcohol (N210), 6.67 grams of isophorone diisocyanates (IPDI), 1.92 grams of embodiment 4 preparations, at 75 ℃, react to NCO content and reach theoretical value, be cooled to 50 ℃, add 43.4 grams of deionized waters, high speed dispersion, add chain extension after 0.9 gram of quadrol, obtain the aqueous polyurethane emulsion of the oyster white blueing light of good dispersity.
Embodiment 7: can be used as the application of the sulfonate dibasic alcohol of hydrophilic chain extender
In three mouthfuls of reaction flasks of reflux exchanger, mechanical stirrer, nitrogen conduit are housed, the sulfonate dibasic alcohol that adds successively 10 gram of 1000 molecular weight polyoxyethylene propylene dibasic alcohol (N210), 6.67 grams of isophorone diisocyanates (IPDI), 5.16 grams of embodiment 5 preparations, at 75 ℃, react to NCO content and reach theoretical value, be cooled to 50 ℃, add 26.68 grams of deionized waters, high speed dispersion, add chain extension after 0.9 gram of quadrol, obtain the aqueous polyurethane emulsion of the oyster white blueing light of good dispersity.
The aqueous polyurethane emulsion that embodiment 6 and 7 is prepared carries out thermal stability analysis, the results are shown in Table 1.
From table 1, the aqueous polyurethane emulsion that the present invention prepares has better thermostability, this be due to, the sulfonate dibasic alcohol that the present invention prepares has benzene ring structure, introduce this rigid radical of phenyl ring and can improve and utilize its aqueous polyurethane thermostability preparing, thereby more adapt to industrial demand.
The thermal stability of table 1 aqueous polyurethane emulsion
Above-described embodiment is preferably embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and principle, substitutes, combination, simplify; all should be equivalent substitute mode, within being included in protection scope of the present invention.
Claims (10)
1. a sulfonate dibasic alcohol that can be used as hydrophilic chain extender, is characterized in that having following chemical structure:
R is alkyl chain or the alkyl chain that contains ehter bond; M is monovalent metallic ion.
2. a preparation method who can be used as the sulfonate dibasic alcohol of hydrophilic chain extender according to claim 1, it is characterized in that comprising following concrete steps: dimethyl isophthalate-5-sulfonate is mixed with dibasic alcohol, under the effect of catalyzer, heated and stirred is reacted, and obtains can be used as the sulfonate dibasic alcohol of hydrophilic chain extender.
3. the preparation method who can be used as the sulfonate dibasic alcohol of hydrophilic chain extender according to claim 2, it is characterized in that: described dibasic alcohol refers to ethylene glycol, glycol ether, triglycol, 1,2-propylene glycol, 1, ammediol, 1,4-butyleneglycol, 1,3-butyleneglycol, 1, at least one in 6-hexylene glycol and polyoxyethylene glycol.
4. the preparation method who can be used as the sulfonate dibasic alcohol of hydrophilic chain extender according to claim 2, is characterized in that: described catalyzer refers at least one in Mono-n-butyltin, tetrabutyl titanate and zinc acetate.
5. the preparation method who can be used as the sulfonate dibasic alcohol of hydrophilic chain extender according to claim 2, is characterized in that: dimethyl isophthalate-5-sulfonate used and the mol ratio of dibasic alcohol are 1:(2～4).
6. the preparation method who can be used as the sulfonate dibasic alcohol of hydrophilic chain extender according to claim 2, is characterized in that: the amount of used catalyst is 0.5～1% of dimethyl isophthalate-5-sulfonate and dibasic alcohol total mass.
7. the preparation method who can be used as the sulfonate dibasic alcohol of hydrophilic chain extender according to claim 2, is characterized in that: described heated and stirred reaction refers to stirring reaction 2～7h at 180～250 ℃.
8. the preparation method who can be used as the sulfonate dibasic alcohol of hydrophilic chain extender according to claim 2, is characterized in that: after described heated and stirred reaction, by least one in the methods such as underpressure distillation, washing or extraction, product is carried out to purifying.
9. the preparation method who can be used as the sulfonate dibasic alcohol of hydrophilic chain extender according to claim 2, is characterized in that: described heated and stirred reaction is rear by underpressure distillation purified product.
10. the application of the sulfonate dibasic alcohol that can be used as hydrophilic chain extender according to claim 1 in preparing aqueous polyurethane.
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Cited By (3)
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| CN107118318A (en) * | 2017-05-08 | 2017-09-01 | 广东德美精细化工集团股份有限公司 | Sulfuric ester salt form hydrophilic chain extender and preparation method thereof |
| CN107353392A (en) * | 2017-08-30 | 2017-11-17 | 瑞安市隆联新材料有限公司 | A kind of aqueous polyurethane thickener and the application in alcohol edition-0 moistening liquid is exempted from |
| CN112079752A (en) * | 2020-09-17 | 2020-12-15 | 陕西科技大学 | Hydroxysulfonic acid type hydrophilic chain extender, preparation method thereof, high-solid-content aqueous polyurethane prepared based on hydroxysulfonic acid type hydrophilic chain extender and preparation method of polyurethane |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107353392A (en) * | 2017-08-30 | 2017-11-17 | 瑞安市隆联新材料有限公司 | A kind of aqueous polyurethane thickener and the application in alcohol edition-0 moistening liquid is exempted from |
| CN107353392B (en) * | 2017-08-30 | 2020-11-20 | 瑞安市隆联新材料有限公司 | Water-based polyurethane thickener and application thereof in alcohol-free fountain solution |
| CN112079752A (en) * | 2020-09-17 | 2020-12-15 | 陕西科技大学 | Hydroxysulfonic acid type hydrophilic chain extender, preparation method thereof, high-solid-content aqueous polyurethane prepared based on hydroxysulfonic acid type hydrophilic chain extender and preparation method of polyurethane |
| CN112079752B (en) * | 2020-09-17 | 2022-11-08 | 陕西科技大学 | Hydroxysulfonic acid type hydrophilic chain extender, preparation method thereof, high-solid-content aqueous polyurethane prepared based on hydroxysulfonic acid type hydrophilic chain extender and preparation method of polyurethane |
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Application publication date: 20140219 |