A polyetheramine sodium ethanesulfonate, a process for its preparation and uses thereof

Abstract

The application provides a polyether amine sodium ethyl sulfonate with a structure as shown in formula (I). The application also provides a preparation method and use of the polyether amine sodium ethyl sulfonate. The polyether amine sodium ethyl sulfonate provided by the application has a novel structure, can be used as a chain extender and a surfactant of an aqueous polyurethane dispersion, has a simple preparation process, does not need to use high-toxicity and high-risk raw materials, is green and environment-friendly, has strong operability, has a simple post-treatment process, has multiple functions, is safe and simple to manufacture, is suitable for industrialized production, is favorable to improving preparation and application of the aqueous polyurethane, and thus has very important economic and social values, NaO3SCH2CH2NH-(CH2-CH2-O-) n -CH2-CH2-NH2 formula (I).

Description

Technical Field

[0001] This invention relates to the field of fine chemicals, specifically to a sodium polyetheramine ethyl sulfonate, its preparation method, and its uses. Background Technology

[0002] The chain extenders used in the synthesis of waterborne polyurethane are mainly hydrophilic chain extenders. The structure of the chain extender affects the bonding strength of the waterborne polyurethane, thus playing a very important role in the preparation process. Hydrophilic chain extenders are chain extenders containing hydrophilic groups. Among them, anionic hydrophilic chain extenders mainly include carboxylic acid type chain extenders and sulfonic acid type chain extenders.

[0003] Sodium ethylenediamine ethanesulfonate is a sulfonic acid-type chain extender with excellent hydrophilicity. As a hydrophilic chain extender, it can be used in the preparation of waterborne polyurethanes, suitable for industries such as coatings, inks, adhesives, and leather finishing agents. Polyurethane dispersions prepared using sodium ethylenediamine ethanesulfonate exhibit good hydrolytic stability and good compatibility with other anionic or nonionic waterborne dispersions. However, sodium ethylenediamine ethanesulfonate has almost no surface-active effect.

[0004] Chinese patent CN 107935892A discloses a method for preparing sodium ethylenediamine ethanesulfonate, which includes the following steps: taurine, nitromethane, and formaldehyde undergo a Mannich reaction to generate N-(2-nitroethyl)taurine, which is then neutralized with an alkali and hydrogenated to obtain sodium ethylenediamine ethanesulfonate. This reaction uses flammable and explosive raw materials such as nitromethane, posing a significant hazard, and involves numerous process steps. Chinese patent CN 106187829A discloses a method for preparing ethylenediamine ethanesulfonate, which uses hydroxyacetonitrile and taurine as raw materials, or hydroxyacetonitrile, taurine, and alkali metal hydroxide as raw materials, to prepare cyanoethyl taurine through a dehydration condensation reaction; then, hydrogenation is carried out under the action of a hydrogenation catalyst to obtain a hydrogenated solution of ethylenediamine ethanesulfonate; after solvent removal, the product ethylenediamine ethanesulfonate is obtained. The hydroxyacetonitrile used in this method is highly toxic, therefore, the reaction is also highly hazardous.

[0005] It is evident that while sodium ethylenediamine ethanesulfonate has achieved good results as a sulfonic acid-based chain extender, its performance is limited by its preparation process. Therefore, it is necessary to develop more novel sulfonic acid-based chain extenders to better meet the production needs of waterborne polyurethane. Summary of the Invention

[0006] To overcome the shortcomings of the prior art, one object of the present invention is to provide a sodium polyetheramine ethyl sulfonate, which can be used as a novel sulfonic acid chain extender for the synthesis of waterborne polyurethane, and also has good surface activity, and can be used as a novel surfactant.

[0007] Another object of the present invention is to provide a method for preparing the sodium polyetheramine ethyl sulfonate and its uses.

[0008] The first aspect of the present invention provides a sodium polyetheramine ethyl sulfonate having a structure as shown in formula (I):

[0009] NaO3SCH2CH2NH-(CH2-CH2-O-) n -CH2-CH2-NH2

[0010] Equation (I)

[0011] Where n represents 5 to 50.

[0012] The sodium polyetheramine ethyl sulfonate provided by this invention contains amine and imine groups in its molecular chain, giving it the ability to react with reactive substances such as isocyanates. Its reactivity is comparable to that of the common sulfonic acid chain extender, sodium ethylenediamine ethanesulfonate, making it suitable as a chain extender for aqueous polyurethane dispersions. Compared to sodium ethylenediamine ethanesulfonate, which suffers from high raw material hazards and a long preparation process, the sodium polyetheramine ethyl sulfonate provided by this invention has abundant raw material sources, good safety, and a simple preparation process, making it more suitable for large-scale industrial production.

[0013] Furthermore, the sodium polyetheramine ethyl sulfonate provided by this invention can also be used as a novel surfactant. Due to the presence of sulfonate groups in its molecular structure, it has excellent hydrophilicity, while the presence of organic segments gives it amphiphilicity. Compared with conventional polyether surfactants (such as polysorbate-80), the sodium polyetheramine ethyl sulfonate of this invention has better surface activity and is more suitable for dispersing O / W type emulsion systems.

[0014] In some preferred embodiments, n in formula (I) can represent 5 to 30, including 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, and 30. In some more preferred embodiments, n in formula (I) can represent 5 to 20. In some further preferred embodiments, n in formula (I) can represent 6 to 15.

[0015] The second aspect of the present invention provides a method for preparing sodium polyetheramine ethyl sulfonate according to any of the above technical solutions. The method is as follows: in the presence of water as a catalyst, a polyetheramine with the structure shown in formula (I') is reacted with sodium hydroxyethyl sulfonate to obtain the sodium polyetheramine ethyl sulfonate.

[0016] NH2-(CH2-CH2-O-) n -CH2-CH2-NH2

[0017] Equation (Ⅰ')

[0018] Wherein, n is as defined in any of the above technical solutions.

[0019] The chemical reaction equation for the preparation method provided by this invention is as follows:

[0020] H2N-(CH2-CH2-O-) n -CH2-CH2-NH2+HOCH2CH2SO3Na

[0021] →NaO3SCH2CH2NH-(CH2-CH2-O-) n -CH2-CH2-NH2+H2O

[0022] Wherein, n is as defined in any of the above technical solutions.

[0023] In some preferred embodiments, the polyetheramine may be one or both of propylene polyetheramine and butyl polyetheramine. In some more preferred embodiments, the polyetheramine may be one or both of polyetheramine D400 and D2000. In some further preferred embodiments, the polyetheramine may be polyetheramine D400.

[0024] In some preferred embodiments, the molar ratio of the polyetheramine to the sodium hydroxyethyl sulfonate can be 1.05 to 10:1, including but not limited to molar ratios of about 1.05:1, about 1.1:1, about 1.2:1, about 1.5:1, about 1.8:1, about 2:1, about 2.2:1, about 2.5:1, about 2.8:1, about 3:1, about 3.2:1, about 3.5:1, about 4:1, about 4.5:1, about 5:1, about 6:1, about 7:1, about 8:1, about 9:1, about 10:1, or any range of molar ratios. In some more preferred embodiments, the molar ratio of the polyetheramine to the sodium hydroxyethyl sulfonate can be 1.1 to 3.5:1. In some further preferred embodiments, the molar ratio of the polyetheramine to the sodium hydroxyethyl sulfonate can be 1.1 to 1.5:1. An appropriate excess of polyetheramine can improve the selectivity of sodium polyetheramine ethyl sulfonate (i.e., the monosubstituted product) and avoid the formation of a large amount of disubstituted byproducts (i.e., NaO3SCH2CH2NH-(CH2-CH2-O-)). n -CH2-CH2-NHCH2CH2SO3Na).

[0025] In some preferred embodiments, the amount of the catalyst (i.e., water) can be 0.1 to 30 wt.% of the polyetheramine, including but not limited to mass percentages of about 0.1 wt.%, about 0.5 wt.%, about 1 wt.%, about 2 wt.%, about 5 wt.%, about 8 wt.%, about 10 wt.%, about 12 wt.%, about 15 wt.%, about 18 wt.%, about 20 wt.%, about 22 wt.%, about 28 wt.%, about 30 wt.%, or any mass percentage range. In some more preferred embodiments, the amount of the catalyst can be 0.5 to 20 wt.% of the polyetheramine. In some further preferred embodiments, the amount of the catalyst can be 1 to 10 wt.% of the polyetheramine.

[0026] In some preferred embodiments, the reaction temperature can be 150–350°C. In some more preferred embodiments, the reaction temperature can be 160–300°C. In some even more preferred embodiments, the reaction temperature can be 170–250°C.

[0027] In some preferred embodiments, the reaction time can be 0.1 to 10 hours. In some more preferred embodiments, the reaction time can be 0.2 to 5 hours. In some even more preferred embodiments, the reaction time can be 0.3 to 1 hour.

[0028] The preparation method provided by this invention may further include: after the reaction is completed, injecting the obtained reactants into water, adding a filter aid and filtering to obtain an aqueous solution of sodium polyetheramine ethyl sulfonate with a concentration of 20-60 wt.%. The preparation method provided by this invention injects the reactants obtained from the reaction into water, utilizing the principle that sodium polyetheramine ethyl sulfonate is soluble in water while macromolecular polyetheramine has low water solubility. Unreacted polyetheramine raw materials and a small amount of disubstituted byproducts can be removed simply by filtration, thereby obtaining a product solution with high purity.

[0029] In some preferred embodiments, the mass ratio of water to reactants obtained from the reaction can be 0.2 to 5:1. In some more preferred embodiments, the mass ratio of water to reactants can be 0.5 to 3:1. In some even more preferred embodiments, the mass ratio of water to reactants can be 1 to 2:1.

[0030] In some preferred embodiments, the filter aid may be one or more of diatomaceous earth, activated carbon, and white carbon black, and the filter aid can adsorb impurities and assist in filtration.

[0031] In some preferred embodiments, the reactants can be injected below the water surface through a feed pipe with an insulated jacket. The reactants obtained by the present invention have a high melting point, are prone to solidification at low temperatures, and have a high viscosity. Directly introducing them into water can easily cause the portion below the liquid surface to solidify due to low temperature. By using a feed pipe with an insulated jacket, the solidification of the reactants at low temperatures can be effectively prevented. In some more preferred embodiments, the temperature of the insulating medium in the insulating jacket can be 130–200°C, and the insulating medium can be common insulating media such as water vapor or organic heat-conducting media.

[0032] The preparation method provided by this invention can be operated intermittently or continuously, and is applicable to common reaction devices, including but not limited to single-stage or multi-stage batch reactors, tubular reactors, tower reactors, etc.

[0033] A third aspect of the present invention provides the use of sodium polyetheramine ethyl sulfonate as a surfactant or chain extender according to any of the above-described technical solutions.

[0034] In some preferred embodiments, the chain extender is a chain extender used for synthesizing waterborne polyurethane.

[0035] The technical solution provided by this invention has the following advantages:

[0036] 1) The sodium polyetheramine ethyl sulfonate provided by the present invention has a novel structure and can be used as a chain extender and surfactant in waterborne polyurethane dispersions, thereby expanding the types of sulfonic acid chain extenders and surfactants and improving their performance.

[0037] 2) The preparation process of sodium polyetheramine ethyl sulfonate provided by the present invention is simple, the process route is short, there is no need to use highly toxic or dangerous raw materials, it is green and environmentally friendly, the cost is low and it is highly operable.

[0038] 3) The sodium polyetheramine ethyl sulfonate provided by the present invention also has a simple post-processing procedure. It can be easily purified by taking advantage of the difference in solubility of the product and raw materials in water, which further simplifies the preparation process, improves the preparation efficiency and reduces the preparation cost.

[0039] In summary, the sodium polyetheramine ethyl sulfonate provided by this invention has diverse functions, is safe and easy to manufacture, is suitable for industrial production, and is beneficial to improving the preparation and application of waterborne polyurethane. Therefore, it has very important economic and social value. Detailed Implementation

[0040] The technical solution of the present invention will be further described in detail below with reference to specific embodiments.

[0041] In the embodiments of the present invention, the polyetheramine D400 used is a terminal amine polyoxyethylene ether with a molecular weight of approximately 400. Unless otherwise specified, other raw materials or reagents are commercially available products.

[0042] Unless otherwise specified, all percentages used in the embodiments of the present invention are mass percentages.

[0043] Example 1

[0044] Add 80 kg of sodium hydroxyethyl sulfonate, 300 kg of polyetheramine D400 and 20 kg of water to the reaction vessel, mix and heat to 250 °C, and react for 0.75 h.

[0045] The reacted material in the reactor was continuously added to a stirred tank containing 400 kg of water through a feed pipe with an insulated jacket. The temperature of the insulation medium in the jacket was 130°C. The inlet of the feed pipe was inserted below the water surface, and the material was directly injected into the water. The temperature was lowered to 60°C, the reaction product dissolved, and unreacted polyetheramine and a small amount of disubstituted products precipitated. 0.5% of the total mass of diatomaceous earth and activated carbon were added to the water as a filter aid. After filtration, a polyetheramine ethyl sulfonate solution with a concentration of approximately 50% was obtained. The conversion rate of sodium hydroxyethyl sulfonate was 98%, and the selectivity of the target product (monosubstituted product) was 92%.

[0046] The target product structure is characterized as follows: 1 H-NMR (CDCl3, 300MHz) δ: 5.10~5.15 (m, 2H, NH), 3.75~3.76 (m, 2H, CH), 3.62~3.65 (m, 2H, CH) , 3.53~3.54(m,14H,CH), 3.07~3.11(m,4H,CH), 2.70~2.75(m,2H,CH), 1.95~2.03(m,1H,NH).

[0047] Example 2

[0048] Sodium hydroxyethyl sulfonate, polyetheramine D400, and water are mixed in a preheater at feed rates of 200 kg / h, 640 kg / h, and 20 kg / h, respectively, and heated to 170°C. The mixture is then fed into a tubular reactor for reaction, with a residence time of 0.5 h.

[0049] The reacted material from the tubular reactor was continuously added to a stirred tank containing water through a feed pipe with an insulated jacket. The temperature of the insulation medium in the jacket was 130°C. The inlet of the feed pipe was inserted below the water surface, allowing the material to be directly injected into the water. The temperature was lowered to 60°C, causing the reaction product to dissolve. Unreacted polyetheramine and a small amount of disubstituted products precipitated. 0.5% (by mass) of diatomaceous earth was added to the water as a filter aid, and the solution was filtered to obtain a product solution with a concentration of approximately 45%. The conversion rate of sodium hydroxyethyl sulfonate was 97%, and the selectivity of the target product was 90%.

[0050] Example 3

[0051] Sodium hydroxyethyl sulfonate, polyetheramine D400, and water are mixed in a preheater at feed rates of 25 kg / h, 100 kg / h, and 20 kg / h, respectively, and heated to 160°C. The mixture is then fed into a first-stage stirred tank reactor for reaction, with a residence time of 0.5 h.

[0052] In the first-stage stirred tank reactor, the reacted material is mixed with polyetheramine D400 fed at a rate of 120 kg / h through a preheater and heated to 180°C. The mixture then enters the second-stage stirred tank reactor for further reaction, with a residence time of 0.5 h.

[0053] The reacted material from the second-stage stirred tank reactor was continuously added to a water-containing stirred tank through a feed pipe equipped with an insulated jacket. The temperature of the insulation medium in the jacket was 130°C. The inlet of the feed pipe was inserted below the water surface, allowing the material to be directly injected into the water. The temperature was then lowered to 60°C, causing the reaction product to dissolve. Unreacted polyetheramine and a small amount of disubstituted products precipitated. 0.5% (by mass) of diatomaceous earth was added to the water as a filter aid, and the solution was filtered to obtain a product solution with a concentration of approximately 38%. The conversion rate of sodium hydroxyethyl sulfonate was 97%, and the selectivity of the target product was 93%.

[0054] Test Example 1

[0055] The product solutions prepared in Examples 1-3 were formulated into 0.1 wt% aqueous solutions with other common surfactants (sodium dodecylbenzenesulfonate SDBS, sodium dodecyl sulfate SDS, and polysorbate-80). Foam tests were conducted using a 1L rotary foam machine at a speed of 60 rpm. The foam height was recorded at the start of the test and after 5 minutes of rotation.

[0056] Table 1 Foam Test Results

[0057] sample Element Initial foam height Foam height after 5 minutes 1 SDBS 260 230 2 SDS 230 210 3 Product obtained in Example 1 185 165 4 Product obtained in Example 2 180 165 5 Product obtained in Example 3 190 170 6 Polysorbate-80 170 160

[0058] As shown in Table 1, using foam height as the benchmark for surface activity comparison, the sodium polyetheramine ethyl sulfonate product of the present invention has stronger surface activity than the traditional polyether surfactant polysorbate-80, and can play a strong surface activity role, while ethylenediamine ethanesulfonate has almost no surface activity role.

[0059] Test Example 2

[0060] The product solutions prepared in Examples 1-3 and sodium ethylenediamine sulfonate (comparative solution) were respectively prepared into solutions with a concentration of 10 wt.%, and then mixed and stirred with the same mass of polyurethane dispersion with a solid content of 50% at 30°C. The content of -NCO groups at different times was tested to test the chain extension effect.

[0061] Table 2 Results of chain extension test

[0062]

[0063] As shown in Table 2, based on the chain extension effect as a characterization of reactivity, the reactivity of the sodium polyetheramine ethyl sulfonate product of this invention is comparable to that of sodium ethylenediamine ethanesulfonate. Therefore, it can be used as a novel sulfonic acid-type chain extender for the synthesis of waterborne polyurethanes. Furthermore, the product of this invention also exhibits surface activity, and when used in dispersion systems, it can provide better dispersion performance and stability compared to the control solution.

[0064] Unless otherwise specified, the terms used in this invention have the meanings commonly understood by those skilled in the art.

[0065] The embodiments described in this invention are for illustrative purposes only and are not intended to limit the scope of protection of this invention. Those skilled in the art can make various other substitutions, changes and improvements within the scope of this invention. Therefore, this invention is not limited to the above embodiments, but is only defined by the claims.

Claims

1. A method for preparing sodium polyetheramine ethyl sulfonate, characterized in that, The preparation method of the sodium polyetheramine ethyl sulfonate is as follows: in the presence of water as a catalyst, a polyetheramine with the structure shown in formula (Ⅰ') is reacted with sodium hydroxyethyl sulfonate to obtain the sodium polyetheramine ethyl sulfonate. NH2-(CH2-CH2-O-) n -CH2-CH2-NH2 Equation (Ⅰ') Where n takes values ​​from 5 to 50; The amount of catalyst used is 0.1 to 30 wt% of the polyetheramine. The reaction temperature is 150–350°C; The preparation method further includes: after the reaction is completed, the obtained reactants are injected into water, a filter aid is added and the mixture is filtered to obtain an aqueous solution of sodium polyetheramine ethyl sulfonate with a concentration of 20-60 wt%; wherein the mass ratio of water to reactants is controlled at 0.5-3:

1. The reactants are injected into the water as follows: the reactants are injected into the water below the surface through a feed pipe with a heat-insulating jacket, and the temperature of the heat-insulating medium in the heat-insulating jacket is 130-200°C. The sodium polyetheramine ethyl sulfonate has the structure shown in formula (I): NaO3SCH2CH2NH-(CH2-CH2-O-) n -CH2-CH2-NH2 Equation (I) Where n represents 5 to 50.

2. The preparation method according to claim 1, characterized in that, The polyetheramine is one or both of polyetheramines D400 and D2000.

3. The preparation method according to claim 1, characterized in that, The molar ratio of the polyetheramine to the sodium hydroxyethyl sulfonate is 1.05 to 10:

1.

4. The preparation method according to claim 3, characterized in that, The molar ratio of the polyetheramine to the sodium hydroxyethyl sulfonate is 1.1 to 3.5:

1.

5. The preparation method according to claim 1, characterized in that, The amount of catalyst used is 0.5 to 20 wt% of the polyetheramine.

6. The preparation method according to claim 5, characterized in that, The amount of catalyst used is 1 to 10 wt% of the polyetheramine.

7. The preparation method according to any one of claims 1-6, characterized in that, The reaction temperature is 160–300°C; and / or The reaction time is 0.1 to 10 hours.

8. The preparation method according to claim 7, characterized in that, The reaction temperature is 170–250°C.

9. The preparation method according to claim 7, characterized in that, The reaction time is 0.2 to 5 hours.

10. The preparation method according to claim 7, characterized in that, The reaction time is 0.3 to 1 hour.

11. The preparation method according to claim 1, characterized in that, The filter aid is one or more of diatomaceous earth, activated carbon, and white carbon black.

12. The use of sodium polyetheramine ethyl sulfonate prepared by the method described in claim 1 as a surfactant; The sodium polyetheramine ethyl sulfonate is used as a surfactant in the dispersion of O / W emulsion systems.

Images