CN102304853A - Polyether polyurethane sulfate anionic macromolecular surfactant and preparation method and application thereof - Google Patents

Abstract

The invention provides a polyether polyurethane sulfate anionic macromolecular surfactant, a preparation method and an application thereof. The preparation method of the invention adopts the method of the invention with a total conversion rate of more than 80%, a mild and controllable process, easy-to-obtain raw materials, low cost, and few by-products and industrial "three wastes". The polyether polyurethane surfactant of the present invention can be used as an emulsifier to prepare a water-based epoxy resin emulsion by emulsifying a bisphenol A epoxy resin, and can be used as a carbon fiber sizing agent and in a carbon fiber manufacturing project. Compared with the existing polyether sulfate anionic surfactants, the introduction of carbamate groups in the molecular structure of polyether polyurethane sulfate can improve the abrasion resistance, water resistance, heat resistance and film-forming elasticity of carbon fibers. , which is conducive to the preparation of high-performance fiber-reinforced resin-based composites.

Description

Polyether polyurethane sulfate anionic macromolecular surfactant, preparation method and use thereof

technical field

The invention relates to the field of synthetic functional polyurethane and special functional macromolecular surfactants, in particular to a polyether polyurethane sulfate salt, a preparation method and its preparation as an anionic special functional surfactant in a high-performance fiber water-based emulsion sizing agent in the application.

Background technique

Anionic surfactants are a class of surfactants that can be ionized in aqueous media and become negatively charged. They are the most traditional, largest output, most diverse and most widely used surfactants. They are used in daily detergents, It is widely used as an important emulsifier formula component in the research and development and production of coatings, adhesives, pesticides, synthetic fiber surface treatment agents, biomedical emulsions and personal care products. Among the commonly used anionic surfactants, anionic surfactants containing sulfate ester salt structure (-OSO ₃ ^- M ⁺ ) currently play an important role in practical production and application. Due to the characteristics of this type of surfactant, it has good wettability and surface activity, low irritation, etc., and the cost of synthesis and preparation is low, so it is suitable for large-scale industrial production and application promotion (Edited by Huang Hongzhou, "Chinese Surfactant Overview", Chemical Industry Press, 2003). Japanese Patent Laid-Open 2003-342873 and World Patent WO2003-010383 disclose the use of styrenated aryl polyoxyethylene ether sulfate salt (ammonium salt, sodium salt, etc.) special surfactants as emulsifying dispersants to prepare epoxy resin-based combinations A water-soluble sizing agent for materials and its application in carbon fiber sizing. However, in the current technical research and development and practical application of water-based emulsion-type high-performance fiber surface treatment agents (such as carbon fiber sizing agents, glass fiber sizing agents, etc.), it is found that anionic polyether sulfate salts are used as emulsifiers. After the water-based emulsion sizing agent is sized and dried on the fiber surface to form a film, the wear resistance, clustering property, resilience, water resistance, moisture absorption of the fiber product, the wettability of the matrix resin of the composite material on the fiber surface and the degree of fiber-reinforced composite material are common. Insufficient in interface high temperature resistance and wet heat strength. Therefore, how to make full use of the advantages of high emulsification efficiency of polyether sulfate anionic surfactants, and further optimize their molecular structure, design and synthesize new special functional surfactants, and improve the application of water-based emulsion fiber surface treatment agents Process performance and the processing and application performance of fibers and high-performance fiber-reinforced resin matrix composites (FRP) have become one of the important directions of technological development in related fields at home and abroad.

Amphiphilic (hydrophilic/hydrophobic) polyurethane can be dispersed and emulsified to prepare water-based functional polymer coatings. Its carbamate structure and molecular polarity endow dry polymer coatings with good wear resistance, water resistance, and high temperature resistance. With high substrate surface adhesion, neutral or anionic water-soluble polyurethane is also an important class of macromolecular emulsifiers, which can be used for the development and production of high storage stability water-based polymer emulsions. Commonly used amphiphilic polyurethanes mainly include side chain anionic (such as carboxylate, phosphate, etc.) polyurethanes, and nonionic polyurethanes with water-soluble polyether polyol structures (such as polyethylene oxide, etc.). U.S. patent US4190567A discloses a method for preparing a uniform and stable self-emulsifying cationic polyurethane aqueous emulsion, which is characterized in that polyurethane groups are introduced into the molecular structure of cationic surfactants, and good application results have been achieved. However, cationic surfactants The high preparation cost of the agent restricts the large-scale industrial application. Chinese invention patents CN200610020330.2 and CN200610020328.5 disclose a method for preparing a diblock and triblock structure polymerizable nonionic polyurethane surfactant, which is characterized by introducing carbamate groups. Because its water solubility as a nonionic surfactant is significantly affected by temperature, when the solution temperature is higher than the cloud point temperature, the solution will be in a turbid state, which will affect the emulsification process and limit its application range. Anionic surfactants are low in cost, less affected by the external environment, and have controllable viscosity. They can be used as emulsifiers to emulsify epoxy resin compositions to prepare high-performance fiber surface treatment agents (carbon fiber sizing agents, glass fiber sizing agents, etc.). In particular, the epoxy resin emulsion prepared by the polyurethane surfactant with a sulfate salt structure as an emulsifier will likely have the matrix resin permeability, wettability and antistatic properties endowed by the sulfate anion at the same time, and due to the structure of the polyurethane It can improve the bundledness, resilience, abrasion resistance and high temperature resistance of fibers, improve the deficiencies of existing polyether sulfate anionic surfactants in the application of fiber surface treatment agents, and prepare high-performance fibers and fibers for production. Reinforced polymer matrix composites provide the basis. The above is also the goal that the present invention strives to solve.

Contents of the invention

One of purposes of the present invention aims to provide a kind of water-soluble polyether urethane sulfate anionic surfactant.

The second object of the present invention aims to provide a kind of preparation method of water-soluble polyether urethane sulfate anionic surfactant.

Three of the object of the present invention aims to provide a kind of water-soluble polyether polyurethane sulfate anion surfactant as formula emulsifier component in water-based high-performance fiber (carbon fiber, glass fiber, inorganic fiber etc.) surface treatment agent preparation application.

Polyether polyurethane sulfate sodium salt anionic surfactant of the present invention has following structural formula:

In the above structure, m is 2-16; n is 1-16; x is 1-20, preferably x is 1-6; R groups are as follows:

According to the preparation method of a kind of water-soluble polyether polyurethane sulfate ester salt anionic surfactant provided by the present invention, adopt polypropylene oxide-polyethylene oxide-polypropylene oxide triembedding as shown in formula (I) Segmented copolyether PPG-PEG-PPG is used as the starting material for addition reaction with diisocyanate components to prepare hydroxyl-terminated polyether polyurethane.

In the above formula (I) PPG-PEG-PPG polyether structure, the polyethylene oxide block is a water-soluble structural segment, and the ratio of its degree of polymerization n to the degree of polymerization of polypropylene oxide m determines the molecular weight and the molecular weight of the polyether block. For the water solubility of the addition product polyether polyurethane, the n value is preferably 1-16, and the m value is preferably 2-16.

OCN——R——NCO

(II)

In the method of the present invention, the structure of the reactive diisocyanate component added to the polyether component of formula (I) is shown in formula (II), wherein the R group is shown in formula (III). The isocyanate can be 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, diphenylmethane diisocyanate (MDI), hydrogenated dibenzylidene diisocyanate, 2,6-hexamethylene diisocyanate (HDI) or isophorone diisocyanate (IPDI) etc. and their 2-3 component mixtures, preferably toluene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate.

The preparation reaction steps of the present invention are as follows:

Among them, Catalyst represents the catalyst; solution represents the solution.

(IV)

Step 1: Add the previously dehydrated and dried PPG-PEG-PPG tri-block polyether to the isocyanate component in a molar ratio of 2:1.1-1.5 into a closed reaction vessel, fill it with a high-purity nitrogen atmosphere, and control the reaction temperature to 60 ~90°C. The reaction progress was monitored by real-time sampling of the mixture in the reaction system and titration of the mass fraction WNCO of residual isocyanate ( _NCO ) functional groups. When the W _NCO decreased to half of the initial value, the temperature was raised to 90°C, and the reaction was stopped when the W _NCO titration value was close to 0, and the hydroxyl-terminated polyether polyurethane was prepared.

Step 2: Add sulfamic acid and catalyst components to the hydroxyl-terminated polyether polyurethane intermediate prepared in step 1, raise the reaction temperature to 100-130° C. and react for 100-120 minutes to prepare polyether polyurethane ammonium sulfate. The molar ratio of the polyether polyurethane intermediate, the sulfamic acid and the catalyst component is 1:1.1-1.2:0.1-0.3.

Step 3: Gradually lower the temperature of the polyether polyurethane ammonium sulfate obtained in Step 2 to below 50°C, vacuumize to remove the volatile components, then drop in 20-30% sodium hydroxide aqueous solution for neutralization, and adjust the pH of the mixed solution system The value reaches 7.5-9.0, and the polyether urethane sulfate sodium salt anionic surfactant is finally prepared.

According to the synthetic preparation method of a kind of water-soluble polyether polyurethane sulfate anionic surfactant provided by the present invention, in the polyether polyurethane sulfate molecular structure shown in formula (IV), the degree of polymerization of polyether polyurethane segment ( x) should not be too high, so as to facilitate the control and adjustment of the product liquid viscosity, the degree of polymerization x can be 1-20, preferably 1-6.

In the above preparation step 2, sulfamic acid is used as the sulfation reaction reagent, which has the advantages of maintaining the activity of polyurethane groups, and the reaction process is mild and controllable. In the presence of a reaction temperature of 100-130 ° C and a catalyst, the reaction only needs 100-100 °C. After 120 minutes, the polyether urethane sulfate ammonium salt product can be prepared. In addition to a small amount of inorganic salts, the generated products have no other by-products and industrial "three wastes", and there are no highly corrosive substances. The operation is safe and simple, and the conversion rate of the single-step reaction is over 85%.

The possible catalysts used in the above preparation step 2 are amide organic compounds, such as urea, methylurea, N, N'-dimethylurea, ethyl urea, N, N'-diethylurea, N-phenyl Urea etc. The catalytic reaction mechanism is that during the sulfation reaction process, the intermediates formed by decomposition at high temperature can promote the formation of complex NH ₃ ·SO ₃ , and further obtain polyether sulfate through transesterification. The presence of the catalyst accelerates the reaction rate and increases the final conversion rate. Urea is a preferred catalyst, which has high catalytic efficiency, low cost, and is easy to be applied in industrial production.

According to the synthetic preparation method of a kind of water-soluble polyether urethane sulfate anionic surfactant provided by the present invention, the polyether urethane sulfate salt of synthesis preparation gained is used as emulsifier, and bisphenol A epoxy resin is as follows The mass ratio of materials, and with reference to the generally public and well-known water-based epoxy resin emulsion preparation process ("New Application of Emulsion and Emulsification Technology-Preparation and Application of Special Emulsion Chemicals", edited by Jiao Xueshun and He Mingbo, Chemical Industry Press , 2005), the water-based epoxy resin emulsion sizing agent was prepared by high-speed mixing, shearing, dispersion, emulsification and homogeneity, the resin solid content was 25-50%, the average particle size of the emulsion was 120-330 nanometers, and the surface tension was 33-47mN/m , The rotational viscosity of the emulsion at room temperature is 30-400 centipoise.

Bisphenol A type epoxy resin 55～80 parts

Polyether polyurethane sulfate 5-25 parts

Deionized water 105～240 parts

The above-mentioned bisphenol A epoxy resin has a molecular weight of 350-2500 g/mol, such as Shell's epoxy resins E826, E828, E1001, E1002, E1004, etc., or domestic epoxy resins E51, E44, E20, E21, etc. , The above bisphenol A epoxy resins can be used alone or mixed in a certain proportion.

According to the water-soluble polyether polyurethane sulfate provided by the present invention as a water-based emulsion sizing agent obtained by emulsifying bisphenol A epoxy resin with a surfactant, sizing carbon fibers can be prepared by a generally known carbon fiber sizing process. Taking the sizing application of carbon fiber with a tensile strength of 3.5GPa as an example, the sizing amount is 1.0±0.2%, the drying temperature is 120-170°C, preferably 130-160°C, and the drying time is 30 seconds to 5 minutes. The prepared carbon fiber sizing is uniform and shiny. Fiber toughness and resilience are good.

Advantages of the invention

According to a kind of water-soluble polyether urethane sulfate anionic surfactant provided by the present invention has the following advantages:

(1) The structure of polyether urethane sulfate salt can be used to improve the high-performance fiber prepared as an emulsifier component by introducing a carbamate structure on the basis of maintaining the advantages of commonly used sulfate anionic surfactants The film-forming toughness of the surface treatment agent, the resilience of the fiber, the clustering property and the wettability of the matrix resin of the composite material at the fiber interface.

(2) The resin emulsification efficiency is high, the preparation process is simple, the source of raw materials is abundant, the production process industry has less "three wastes", and it is convenient for large-scale production.

^{The 1} H nuclear magnetic resonance molecular structure analysis of the intermediate product and the final product synthesized and prepared in the present invention adopts a Varian VXR-300 Fourier transform nuclear magnetic resonance instrument, the solvent is deuterated chloroform, and TMS is used as a chemical shift reference. The reaction was stirred using a German IKA Eurostar high-speed mixer. The _SO3 content of the polyether polyurethane sulfate salt prepared by the reaction is obtained by potentiometric titration test analysis and calculation of the 905 type automatic potentiometric titrator of Metrohm Company in Switzerland. The analysis of the mass fraction of residual isocyanate NCO functional groups in the reaction system mixture is based on the standard method of China HG/T 2409-92 "Determination of Isocyanate Group Content in Polyurethane Prepolymers". The specific analysis steps are as follows: Weigh about 2g of the sample, accurate to 0.1mg, put it into a 250mL iodine measuring bottle, add 25mL anhydrous toluene, cover the bottle stopper, heat to dissolve the sample completely, pipette 25mL 0.1mol/L di-n-butylamine-toluene solution in the above In the Erlenmeyer flask, cover the cork and continue shaking for 15 minutes, then add 100mL of isopropanol, and add 4 to 6 drops of bromophenol blue indicator, and titrate the solution from blue to yellow with 0.1mol/L hydrochloric acid standard solution. as the end point. And do blank control experiment by above-mentioned method simultaneously, the content W _NCO of isocyanate functional group is calculated by following formula.

${\mathrm{<span\; class="notranslate">\; W</span>}}_{\mathrm{<span\; class="notranslate">\; NCO</span>}}<span\; class="notranslate">\; =</span>\frac{<span\; class="notranslate">\; (</span>{\mathrm{<span\; class="notranslate">\; V</span>}}_{\mathrm{<span\; class="notranslate">\; 0</span>}}<span\; class="notranslate">\; -</span>{\mathrm{<span\; class="notranslate">\; V</span>}}_{\mathrm{<span\; class="notranslate">\; 1</span>}}<span\; class="notranslate">\; )</span><span\; class="notranslate">\; \&times;</span>\mathrm{<span\; class="notranslate">\; C</span>}<span\; class="notranslate">\; \&times;</span>\mathrm{<span\; class="notranslate">\; 42</span>}}{\mathrm{<span\; class="notranslate">\; 1000</span>}<span\; class="notranslate">\; \&times;</span>\mathrm{<span\; class="notranslate">\; m</span>}}<span\; class="notranslate">\; \&times;</span>\mathrm{<span\; class="notranslate">\; 100</span>}<span\; class="notranslate">\; \%</span>$

In the formula, V ₀ and V ₁ are the volume (ml) of the hydrochloric acid standard solution consumed by blank titration and sample titration, C is the concentration (mol/l) of the hydrochloric acid standard solution, and m is the mass (g) of the sample.

Description of drawings

Fig. 1, the ¹ H NMR spectrum of the hydroxyl-terminated polyether polyurethane obtained by reacting the triblock polyether PPG ₂ -PEG ₂ -PPG ₂ (P ₂ E ₂ P ₂ ) with toluene diisocyanate in Example 8.

_{Figure 2 , Example 8} The ammonium sulfate _product SN- ¹ H NMR spectrum of 8.

Detailed ways

The present invention will be described in detail through the following examples, which will help the understanding of the present invention, but do not limit the content of the present invention.

In the following specific examples, the formulation of the gained aqueous epoxy resin emulsion prepared by water-soluble polyether urethane sulfate as surfactant emulsifying bisphenol A epoxy resin is as follows:

Bisphenol A type epoxy resin 55～80 parts

Polyether polyurethane sulfate 5-25 parts

Deionized water 105～240 parts

For example, the bisphenol A epoxy resin of the above formula can be obtained by mixing the grades E44 and E21 epoxy resins in a mass ratio of 0-100:100-0, and further place it with a predetermined mass ratio of polyether polyurethane sulfate In the high-speed shear mixing reactor, after heating to 75-95 degrees and fully mixed, according to the generally known polymer emulsion preparation process, gradually add deionized water with a predetermined material ratio in the high-speed shear emulsification tank, and finally emulsify evenly Aqueous epoxy resin emulsion was prepared.

Example 1

Add 81.80 g (0.1 mol) of self-made tri-block PPG ₄ -PEG ₈ -PPG ₄ (P ₄ E ₈ P ₄ ) polyether into a 500 ml four-neck flask, raise the temperature to 90° C., and vacuum to remove residual moisture. Then the temperature was lowered to below 50° C., and 8.71 g (0.05 mol) of toluene diisocyanate (2,4-TDI) was slowly added dropwise under a flowing high-purity nitrogen atmosphere. After the isocyanate component was added dropwise, the temperature of the reaction system was raised to 60° C. and stirred, and samples were taken at intervals of 20 minutes for titration analysis of the isocyanate functional group content W _NCO . When W _NCO was close to half of the initial value, the temperature of the reaction system was raised to 90 °C, and the sampling and titration analysis of W _NCO were continued. When W _NCO is close to 0, the reaction system continues to heat up to 130°C, and 5.82 grams (0.06mol) of sulfamic acid and 0.53 grams (0.006mol) of catalyst N,N'-dimethyl Urea, feed rate controlled to prevent clumping. Determine, analyze and monitor the reaction process by measuring ¹ H NMR method, stop the reaction when the conversion rate reaches 86.2%, and cool to below 80°C to remove volatile by-products by vacuuming, adjust the pH value of the solution to 7.0~ with 20% NaOH aqueous solution 8.0, continue to add about 10 grams of activated carbon for decolorization treatment, filter, separate, and dry to obtain polyether polyurethane sulfate sodium salt SN-1, with a total yield of 81.4%, and _the SO content of the product obtained by potentiometric titration analysis is 3.81%.

Example 2

Add 81.80 g (0.1 mol) of self-made tri-block PPG ₄ -PEG ₈ -PPG ₄ (P ₄ E ₈ P ₄ ) polyether into a 500 ml four-neck flask, raise the temperature to 90° C., and remove residual moisture by vacuuming. Then the temperature was lowered to below 50° C., and 10.08 g (0.06 mol) of hexamethylene diisocyanate (HDI) was slowly added dropwise under a flowing high-purity nitrogen atmosphere. After the isocyanate component was added dropwise, the temperature of the reaction system was raised to 60°C and stirred, and samples were taken at 20-minute intervals for titration analysis of the isocyanate functional group content _WNCO . When W _NCO was close to half of the initial value, the temperature of the reaction system was raised to 90 °C, and the sampling and titration analysis of W _NCO were continued. When W _NCO was close to 0, the reaction system was continued to be warmed up to 130°C, and 7.76 grams (0.08mol) of sulfamic acid and 0.72 grams (0.012mol) of sulfamic acid and 0.72 grams (0.012mol) of catalyst urea were added to be ground and thoroughly mixed in advance, and the feed rate was controlled to Prevent caking. Determine, analyze and monitor the reaction process by measuring ¹ H NMR method, stop the reaction when the conversion rate reaches 86.0%, and cool to below 80°C to remove volatile by-products by vacuuming, adjust the pH value of the solution to 7.0~ with 20% NaOH aqueous solution 8.0. Finally, 11 grams of activated carbon was added for decolorization, filtered, separated, and dried to obtain polyether polyurethane sulfate sodium salt SN-2, with a total yield of 82.7%. _The SO content of the product obtained by potentiometric titration analysis was 5.33%.

Example 3

Add 49.80 g (0.1 mol) of self-made tri-block PPG ₂ -PEG ₆ -PPG ₂ (P ₂ E ₆ P ₂ ) polyether into a 500 ml four-necked flask, raise the temperature to 90° C., and remove residual moisture by vacuuming. Then the temperature was lowered to below 50° C., and 8.71 g (0.05 mol) of toluene diisocyanate (2,6-TDI) was slowly added dropwise under a flowing high-purity nitrogen atmosphere. After the isocyanate component was added dropwise, the temperature of the reaction system was raised to 60°C and stirred, and samples were taken at 20-minute intervals for titration analysis of the isocyanate functional group content _WNCO . When W _NCO was close to half of the initial value, the temperature of the reaction system was raised to 90 °C, and the sampling and titration analysis of W _NCO were continued. When W _NCO was close to 0, the reaction system was heated up to 130°C, and 4.85 grams (0.05 mol) of sulfamic acid and 0.30 gram (0.005 mol) of sulfamic acid and 0.30 gram (0.005 mol) of catalyst urea, which had been ground and thoroughly mixed in advance, were added at a speed of no condensation. block is appropriate. Determine, analyze and monitor the reaction process by measuring ¹ H NMR method, stop the reaction when the conversion rate reaches 87.1%, and cool to below 80°C to remove volatile by-products by vacuuming, adjust the pH value of the solution to 7.0~ with 20% NaOH aqueous solution 8.0. Finally, about 6 grams of activated carbon was added for decolorization treatment, filtered, separated, and dried to obtain polyether polyurethane sulfate sodium salt SN-3, with a total yield of 82.3%. The _SO3 content of the product obtained by potentiometric titration analysis was 4.80%.

Example 4

Add 81.80 g (0.1 mol) of self-made tri-block PPG ₄ -PEG ₈ -PPG ₄ (P ₄ E ₈ P ₄ ) polyether into a 500 ml four-neck flask, raise the temperature to 90° C., and remove residual moisture by vacuuming. Then the temperature was lowered to below 50° C., and 8.71 g (0.05 mol) of toluene diisocyanate (2,6-TDI) was slowly added dropwise under a flowing high-purity nitrogen atmosphere. After the isocyanate component was added dropwise, the temperature of the reaction system was raised to 60°C and stirred, and samples were taken at 20-minute intervals for titration analysis of the isocyanate functional group content _WNCO . When W _NCO was close to half of the initial value, the temperature of the reaction system was raised to 90 °C, and the sampling and titration analysis of W _NCO were continued. When W _NCO is close to 0, the reaction system continues to heat up to 130°C, and 4.85 grams (0.05mol) of sulfamic acid and 0.45 grams (0.005mol) of catalyst N, N'-dimethyl For base urea, the feeding speed should not be agglomerated. Determine, analyze and monitor the reaction process by measuring ¹ H NMR method, stop the reaction when the conversion rate reaches 87.1%, and cool to below 80°C to remove volatile by-products by vacuuming, adjust the pH value of the solution with 20-30% NaOH aqueous solution 7.0～8.0. Finally, about 10 grams of activated carbon was added for decolorization treatment, filtered, separated, and dried to obtain polyether polyurethane sulfate sodium salt SN-4, with a total yield of 81.7%. _The SO content of the product obtained by potentiometric titration analysis was 5.17%.

Example 5

Add 49.80 g (0.1 mol) of self-made tri-block PPG ₂ -PEG ₆ -PPG ₂ (P ₂ E ₆ P ₂ ) polyether into a 500 ml four-necked flask, raise the temperature to 90° C., and remove residual moisture by vacuuming. Then the temperature was lowered to below 50° C., and 18.76 g (0.075 mol) of diphenylmethane diisocyanate (MDI) was slowly added dropwise under a flowing high-purity nitrogen atmosphere. After the isocyanate component was added dropwise, the temperature of the reaction system was raised to 60°C and stirred, and samples were taken at 20-minute intervals for titration analysis of the isocyanate functional group content _WNCO . When W _NCO was close to half of the initial value, the temperature of the reaction system was raised to 90 °C, and the sampling and titration analysis of W _NCO were continued. When W _NCO was close to 0, the reaction system was continued to heat up to 130°C, and 5.82 grams (0.06 mol) of sulfamic acid and 0.60 gram (0.01 mol) of sulfamic acid and 0.60 gram (0.01 mol) of catalyzer urea that had been ground and thoroughly mixed in advance were added, and the feed rate was at a speed of no condensation. block is appropriate. Determine, analyze and monitor the reaction process by measuring ¹ H NMR method, stop the reaction when the conversion rate reaches 87.8%, and cool to below 80°C to remove volatile by-products by vacuuming, adjust the pH value of the solution to 7.0~ with 20% NaOH aqueous solution 8.0. Finally, about 6 grams of activated carbon was added for decolorization, filtered, separated, and dried to obtain polyether polyurethane sulfate sodium salt SN-5, with a total yield of 84.5%. The _SO3 content of the product obtained by potentiometric titration analysis was 5.02%.

Example 6

Add 49.80 g (0.1 mol) of self-made tri-block PPG ₂ -PEG ₆ -PPG ₂ (P ₂ E ₆ P ₂ ) polyether into a 500 ml four-necked flask, raise the temperature to 90° C., and remove residual moisture by vacuuming. Then the temperature was lowered to below 50° C., and 10.56 g (0.06 mol) of toluene diisocyanate (2,4-TDI) was slowly added dropwise under a flowing high-purity nitrogen atmosphere. After the cyanate component was added dropwise, the temperature of the reaction system was raised to 60°C and stirred, and samples were taken at 20-minute intervals for titration analysis of the isocyanate functional group content _WNCO . When W _NCO was close to half of the initial value, the temperature of the reaction system was raised to 90 °C, and the sampling and titration analysis of W _NCO were continued. When W _NCO was close to 0, the reaction system was continued to heat up to 130°C, and 7.28 grams (0.075 mol) of sulfamic acid and 0.60 gram (0.01 mol) of sulfamic acid and 0.60 gram (0.01 mol) of catalyst urea that had been ground and thoroughly mixed in advance were added, and the feed rate was at a rate of no condensation. block is appropriate. Determine, analyze and monitor the reaction process by measuring ¹ H NMR method, stop the reaction when the conversion rate reaches 85.3%, and cool to below 80°C to remove volatile by-products by vacuuming, adjust the pH value of the solution to 7.0~ with 20% NaOH aqueous solution 8.0. Finally, add 6 grams of activated carbon for decolorization, filter, separate, and dry to obtain polyether polyurethane sulfate sodium salt SN-6, with a total yield of 80.4%. _The SO content of the product obtained by potentiometric titration analysis is 8.91%.

Example 7

Add 49.80 g (0.1 mol) of self-made tri-block PPG ₂ -PEG ₆ -PPG ₂ (P ₂ E ₆ P ₂ ) polyether into a 500 ml four-necked flask, raise the temperature to 90° C., and remove residual moisture by vacuuming. Then the temperature was lowered to below 50° C., and 10.56 g (0.06 mol) of toluene diisocyanate (2,4-TDI) was slowly added dropwise under a flowing high-purity nitrogen atmosphere. After the cyanate component was added dropwise, the temperature of the reaction system was raised to 60°C and stirred, and samples were taken at 20-minute intervals for titration analysis of the isocyanate functional group content _WNCO . When W _NCO was close to half of the initial value, the temperature of the reaction system was raised to 90 °C, and the sampling and titration analysis of W _NCO were continued. When W _NCO is close to 0, the reaction system continues to heat up to 130°C, and 7.28 grams (0.075mol) of sulfamic acid and 0.88 grams (0.01mol) of catalyst N,N'-dimethyl For base urea, the feeding speed should not be agglomerated. Determine, analyze and monitor the reaction process by measuring ¹ H NMR method, stop the reaction when the conversion rate reaches 85.0%, and cool to below 80°C to remove volatile by-products by vacuuming, adjust the pH value of the solution to 7.0~ with 20% NaOH aqueous solution 8.0. Finally, about 6 grams of activated carbon was added for decolorization treatment, filtered, separated, and dried to obtain polyether polyurethane sulfate sodium salt SN-7, with a total yield of 80.1%. _The SO content of the product obtained by potentiometric titration analysis was 9.10%.

Example 8

Add 32.41 g (0.1 mol) of self-made tri-block PPG ₂ -PEG ₂ -PPG ₂ (P ₂ E ₂ P ₂ ) polyether into a 500 ml four-necked flask, raise the temperature to 90° C., and remove residual moisture by vacuuming. Then the temperature was lowered to below 50° C., and 10.56 g (0.06 mol) of toluene diisocyanate (2,4-TDI) was slowly added dropwise under a flowing high-purity nitrogen atmosphere. After the cyanate component was added dropwise, the temperature of the reaction system was raised to 60°C and stirred, and samples were taken at 20-minute intervals for titration analysis of the isocyanate functional group content _WNCO . When W _NCO was close to half of the initial value, the temperature of the reaction system was raised to 90 °C, and the sampling and titration analysis of W _NCO were continued. When W _NCO is close to 0, the reaction system continues to heat up to 130 ° C, and 7.28 grams (0.075 mol) of sulfamic acid and 0.88 g (0.01 mol) of catalyst N, N'-dimethyl For base urea, the feeding speed should not be agglomerated. Determine, analyze and monitor the reaction process by measuring ¹ H NMR method, stop the reaction when the conversion rate reaches 85.0%, and cool to below 80°C to remove volatile by-products by vacuuming, adjust the pH value of the solution to 7.0~ with 20% NaOH aqueous solution 8.0. Finally, about 6 grams of activated carbon was added for decolorization treatment, filtered, separated, and dried to obtain polyether polyurethane sulfate sodium salt SN-8, with a total yield of 80.1%. _The SO content of the product obtained by potentiometric titration analysis was 11.20%.

Example 9

With embodiment 8 gained polyether urethane sulfate sodium salt (SN-8) as emulsifying agent 20 mass parts, bisphenol A type epoxy resin mixture 80 mass parts, deionized water 150 mass parts, through mixing, homogeneous, emulsifying Finally, a milky white water-based emulsion sizing agent was prepared, with an average particle size of 225.2±4.0nm, a particle size dispersion index PDI of less than 0.05, and a surface tension of 43.2mN/m. Further diluting it with water to 1.8-2.2% mass concentration of sizing agent dilute liquid, viscosity at room temperature 1.1-1.6 centipoise, applied to the sizing of carbon fibers with a tensile strength of 3.5 GPa. In the sizing process, the immersion time of carbon fiber in the sizing solution is 10 to 30 seconds, the hot air drying temperature of the sizing carbon fiber is 130 to 160 degrees, and the drying time is 1 to 5 minutes. The final sizing layer accounts for 1.0±0.2% of the total mass of the sizing carbon fiber , the strength of sizing carbon fiber is 3.63GPa.

Place the dried and sized carbon fiber in a constant temperature and humidity test chamber at 60-70% RH at 25 degrees for 6-24 hours, and the saturated moisture absorption and moisture return rate of the carbon fiber is less than 0.1%. Further use epoxy resin E828 as matrix resin, according to the test method specified in GB/T3357-1982, the interlaminar shear strength of the carbon fiber reinforced composite material is 75-100MPa, which meets the application requirements.

Although the present invention has disclosed the preferred embodiments as above, it is not intended to limit the present invention. Any person familiar with this art can make various changes and modifications without departing from the spirit and scope of the present invention. Therefore, the present invention The scope of protection should be based on the scope of claims of the patent application.

Claims (10)

1. a kind of polyether polyurethane sulfate sodium salt anionic surfactant, it is characterized in that having following structural formula:

In the above structure, m is 2-16; n is 1-16; x is 1-20; the R group is as follows:

2. a kind of polyether urethane sulfate sodium salt anionic surfactant as claimed in claim 1, is characterized in that described x is 1～6. 3. a kind of preparation method of a kind of polyether polyurethane sulfate sodium salt anionic surfactant as claimed in claim 1, is characterized in that being made up of following reaction steps: Step 1: Add the previously dehydrated and dried PPG-PEG-PPG tri-block polyether to the isocyanate component in a molar ratio of 2:1.1-1.5 into a closed reaction vessel, fill it with a high-purity nitrogen atmosphere, and control the reaction temperature to 60 ~90°C; monitor the reaction progress by real-time sampling of the mixture in the reaction system and titration of the mass fraction _WNCO of the residual isocyanate NCO functional group. When the _WNCO is reduced to half of the initial value, the temperature is raised to 90°C, and the titration value of the _WNCO is close to 0 When the reaction is stopped, the hydroxyl-terminated polyether polyurethane is prepared; Step 2: Add sulfamic acid and catalyst components to the hydroxyl-terminated polyether polyurethane intermediate prepared in step 1, and react at 100-130° C. for 100-120 minutes to obtain polyether polyurethane ammonium sulfate; polyether polyurethane intermediate, The molar ratio of sulfamic acid to the catalyst component is 1:1.1～1.2:0.1～0.3; the catalyst is an amide organic compound; Step 3: Gradually lower the temperature of the polyether polyurethane ammonium sulfate obtained in Step 2 to below 50°C to room temperature, vacuumize to remove volatile components, then drop in 20-30% sodium hydroxide aqueous solution for neutralization, and adjust the mixed solution system pH value to 7.5-9.0, finally obtained polyether urethane sulfate sodium salt anionic surfactant; The PPG-PEG-PPG three-block polyether has the following structural formula:

In the formula, the polyoxyethylene ether block is a water-soluble structural segment, the degree of polymerization n is 1-16, the degree of polymerization m of polyoxypropylene ether is 2-16, and the molecular weight is 400-2000 g/mol. 4. the preparation method of a kind of polyether urethane sulfate sodium salt anionic surfactant as claimed in claim 3 is characterized in that the isocyanate adopted in the step 1 is 2,4-toluene diisocyanate, 2,6-toluene Diisocyanate, diphenylmethane diisocyanate (MDI), hydrogenated dibenzylidene diisocyanate, 2,6-hexamethylene diisocyanate (HDI) or isophorone diisocyanate (IPDI) or 2~ 3-component blend. 5. the preparation method of a kind of polyether polyurethane sulfate sodium salt anionic surfactant as claimed in claim 3 is characterized in that the catalyzer of the sulfated reaction adopted in step 2 can be urea, methyl urea, N,N'-dimethylurea, ethylurea, N,N'-diethylurea or N-phenylurea. 6. a purposes of polyether urethane sulfate sodium salt anionic surfactant as claimed in claim 1, is characterized in that being used for preparing carbon fiber sizing agent. 7. the purposes of polyether polyurethane sulfate sodium salt anionic surfactant as claimed in claim 1, it is characterized in that described carbon fiber sizing agent is to be emulsifying agent with polyether polyurethane sulfate sodium salt anionic surfactant Homogeneously emulsified bisphenol A epoxy resin to prepare the obtained aqueous epoxy resin emulsion. 8. the purposes of polyether polyurethane sulfate sodium salt anionic surfactant as claimed in claim 1, it is characterized in that described aqueous epoxy resin emulsion formula is as follows: Bisphenol A type epoxy resin 55～80 parts Polyether polyurethane sulfate sodium salt anionic surfactant 5-25 parts Deionized water 105-240 parts. 9. the purposes of polyether urethane sulfate sodium salt anionic surfactant as claimed in claim 8, it is characterized in that the molecular weight of described bisphenol A type epoxy resin is 350～2500 grams/mole. 10. the purposes of polyether urethane sulfate sodium salt anionic surfactant as claimed in claim 8, it is characterized in that in described aqueous epoxy resin emulsion, resin solid content is 25～50%, and emulsion average particle diameter is 120-330 nanometers, surface tension 33-47mN/m, emulsion rotational viscosity at room temperature 30-400 centipoise, its dilution can be used as a carbon fiber sizing agent.

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