CN112250776A - Tetramethyl ammonium hydroxide catalytic thermoplastic material and preparation method thereof - Google Patents
Tetramethyl ammonium hydroxide catalytic thermoplastic material and preparation method thereof Download PDFInfo
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Abstract
The application provides a tetramethylammonium hydroxide catalyzed thermoplastic material and a preparation method thereof. The invention is directed to thermoplastic elastomers, represented by H2O2As an epoxidation reagent and tetramethylammonium hydroxide as a phase transfer catalyst, the catalyst catalyzes the epoxidation reaction of the thermoplastic elastomer, thereby improving the epoxidation reaction speed, increasing the compatibility of the thermoplastic material and the polar material, and improving the toughness and strength of the thermoplastic material.
Description
Technical Field
The application relates to the technical field of thermoplastic materials, in particular to a tetramethylammonium hydroxide catalyzed thermoplastic material and a preparation method thereof.
Background
The thermoplastic elastic material has the advantages of high stretching degree, low temperature resistance and easy processing, and can be used for waterproof materials, plastic modification, adhesives, LED light-emitting devices and the like.
Thermoplastic elastic materials have low molecular polarity and thus poor adhesion to polar materials, but are incompatible with the polar materials, but in practice, the thermoplastic elastic materials and the polar materials need to be used together, so that the thermoplastic elastic materials generally need to be modified to be polarized, so as to enhance the compatibility and adhesion with the polar materials.
At present, the polar modification method for thermoplastic elastic materials is mainly realized by organic acid and H2O2In-situ reaction to generate organic peroxide, so as to obtain thermoplastic elastic material solutionThe organic acid is oxidized to generate an epoxidation reaction, so that an epoxy group is introduced to a molecular chain of the thermoplastic elastic material, the introduction of the epoxy group obviously improves the polarity of the thermoplastic elastic material, and also can improve the mechanical property of the thermoplastic elastic material, and the thermoplastic elastic material has new reaction activity, and the application field of the thermoplastic elastic material is expanded.
Disclosure of Invention
In view of the above, the present application aims to provide a tetramethylammonium hydroxide catalyzed thermoplastic material and a preparation method thereof. The invention is directed to thermoplastic elastomers, represented by H2O2As an epoxidation reagent and tetramethylammonium hydroxide as a phase transfer catalyst, the catalyst catalyzes the epoxidation reaction of the thermoplastic elastomer, thereby improving the epoxidation reaction speed, increasing the compatibility of the thermoplastic material and the polar material, and improving the toughness and strength of the thermoplastic material.
The invention provides a preparation method of a tetramethylammonium hydroxide catalyzed thermoplastic material, which is characterized by comprising the following steps:
step 1, adding formic acid and tetramethyl ammonium hydroxide into a thermoplastic elastic material-containing solution, and uniformly stirring at room temperature;
step 2, adding H into the uniformly stirred solution2O2The solution and a proper amount of deionized water;
step 3, adding H2O2Heating the solution of deionized water to 50-75 ℃ to perform epoxidation reaction for 3-6 hours;
step 4, saturated aqueous solution of sodium bicarbonate or Na2S2O4Saturated aqueous solution, washing the reaction product in the step 3 until neutral; and extracting the organic layer of the reaction product by using a separating funnel, and volatilizing the solvent under a vacuum condition to obtain the epoxidized modified thermoplastic elastic material.
Preferably, the thermoplastic elastomer is a styrene-butadiene-styrene block copolymer.
Preferably, the solution used in step 1 has a styrene-butadiene-styrene block copolymer content of 15 to 25 wt%; 80-100 parts of thermoplastic elastic material-containing solution, 6-8 parts of added formic acid and 0.5-1.0 part of added tetramethylammonium hydroxide.
Preferably, step 2 is H2O2The concentration of the solution is 35-40 vol%, and H is added to the solution stirred uniformly in the step 12O28-10 parts of solution by weight, and then adding a proper amount of deionized water.
Preferably, in step 2, in said H2O2The solution and deionized water can also be added with a catalytic substance containing transition metal elements.
Preferably, the transition metal element-containing catalyst includes a catalyst containing any one of W, Mo, Mn, Ti, and Zr.
Preferably, said H2O2Adding Na into the solution and deionized water2WO40.5 to 1.5 weight portions.
Preferably, in step 2, in said H2O2A small amount of mineral acid may also be added to the solution and deionized water.
Preferably, in the step 2, the hydrogen is supplied to the hydrogen2O2Solution and deionized water to H3PO40.3-0.8 part by weight of H3PO4The concentration is 30-40 vol%.
The invention also claims the tetramethylammonium hydroxide catalyzed thermoplastic material prepared according to the above preparation method.
The preparation method and the prepared product have higher epoxidation value, show that the degree of polarization of the thermoplastic elastic material is achieved, the gelation degree is low, the reaction is sufficient, the reaction speed is high, the compatibility of the thermoplastic material and the polar material is increased, and the toughness and the strength of the thermoplastic material are improved.
Detailed Description
The invention adopts the following method to prepare the tetramethyl ammonium hydroxide catalytic thermoplastic material:
firstly, in step 1, a solution containing a thermoplastic elastomer material is taken, added with formic acid and tetramethylammonium hydroxide, and stirred uniformly at room temperature. Wherein the thermoplastic elastomer is a styrene-butadiene-styrene block copolymer; the styrene-butadiene-styrene block copolymer is an important thermoplastic elastic material and has the advantages of small friction coefficient, low temperature resistance, tensile resistance and good processability. The content of the styrene-butadiene-styrene block copolymer in the solution adopted in the step 1 is 15-25 wt%; 80-100 parts of thermoplastic elastomer-containing solution, 6-8 parts of added formic acid and 0.5-1.0 part of added tetramethylammonium hydroxide. Stirring at room temperature for 10-30 minutes until completely mixed.
In step 2, H is added into the solution after being stirred uniformly2O2The solution and a proper amount of deionized water. Wherein H2O2The concentration of the solution is 35-40 vol%, and H is added to the solution stirred uniformly in the step 12O28-10 parts of solution by weight, and then adding a proper amount of deionized water. By H2O2The solution and formic acid in the step 1 are subjected to in-situ reaction to generate peroxyformic acid; peroxyformic acid belongs to peroxyorganic acids. The thermoplastic elastic material solution and the organic acid peroxide generate an epoxidation reaction, so that an epoxy group is introduced into a molecular chain of the thermoplastic elastic material, the introduction of the epoxy group obviously improves the polarity of the thermoplastic elastic material, increases the compatibility of the thermoplastic elastic material and a polar material, and improves the mechanical property and the application function of the thermoplastic elastic material. The thermoplastic elastomer solution belongs to the organic phase solution, and H2O2The solution belongs to a water phase solution, and a phase transfer catalyst is needed to accelerate the epoxidation reaction; in addition, experiments show that the styrene-butadiene-styrene block copolymer is easy to generate gel reaction when reacting with organic acid peroxide, so that epoxidation cannot be fully realized, and more byproducts are generated; thus, the present application incorporates tetramethylammonium hydroxideThe tetramethylammonium hydroxide is used as a phase transfer catalyst, so that the reaction speed of the styrene-butadiene-styrene block copolymer and the peroxyformic acid can be accelerated, and experiments show that the generation of gel can be remarkably reduced, and the full realization of the epoxidation modification of the styrene-butadiene-styrene block copolymer is ensured.
And, the H2O2The solution and deionized water can also be added with a catalytic substance containing transition metal elements and inorganic acid. The catalyst containing a transition metal element includes a catalyst containing any one of W, Mo, Mn, Ti and Zr, and H2O2Firstly, reacting with a catalyst containing transition metal elements to form a peroxide metal transition state, and then transferring oxygen to a molecular chain of the styrene-butadiene-styrene block copolymer to form epoxy groups; among them, the reactivity of the Wo-series catalyst is the highest, and the reaction is the most stable; accordingly, the present invention is directed to said H2O2Adding Na into the solution and deionized water2WO40.5 to 1.5 weight portions. In addition, addition of a small amount of an inorganic acid can promote H2O2With formic acid to form a peroxygenated organic acid, and is therefore described herein as H2O2Solution and deionized water to H3PO40.3 to 0.8 part by weight, since the acidity of formic acid itself is strong, H is added3PO4The concentration is not necessarily too high, and is 30 to 40 vol%.
In step 3, H is added2O2And deionized water (or, alternatively, H is added)2O2Deionized water and Na2WO4And H3PO4The solution of (1) is heated to 50-75 ℃ to carry out epoxidation reaction for 3-6 hours.
In step 4, saturated aqueous solution of sodium bicarbonate or Na is used2S2O4Saturated aqueous solution, washing the reaction product in the step 3 until neutral; and extracting the organic layer of the reaction product by using a separating funnel, and volatilizing the solvent under a vacuum condition to obtain the epoxidized modified thermoplastic elastic material.
Examples and comparative examples of the process for preparing a tetramethylammonium hydroxide catalyzed thermoplastic material according to the present invention are described below:
example I
80 parts by weight of a solution containing a styrene-butadiene-styrene block copolymer in an amount of 15 wt%, 6 parts by weight of formic acid and 0.5 part by weight of tetramethylammonium hydroxide were added; stirring for 10-30 minutes at room temperature until the components are completely and uniformly mixed; addition of H2O28 parts of solution and a proper amount of deionized water H2O2The concentration of the solution is 35 vol%, and then the temperature of the solution is raised to 50 ℃ to carry out epoxidation reaction for 3.5 hours; saturated aqueous solution of sodium bicarbonate or Na2S2O4Saturated aqueous solution, washing the reaction product until reaching neutrality; and extracting the organic layer of the reaction product by using a separating funnel, and volatilizing under a vacuum condition to remove the solvent to obtain the epoxidation modified styrene-butadiene-styrene block copolymer as a final product.
Example II
90 parts by weight of a solution containing a styrene-butadiene-styrene block copolymer in an amount of 20 wt%, 8 parts by weight of formic acid and 0.8 part by weight of tetramethylammonium hydroxide were added; stirring for 10-30 minutes at room temperature until the components are completely and uniformly mixed; addition of H2O210 parts by weight of solution and a proper amount of deionized water, H2O2The concentration of the solution is 40 vol%, and then the temperature of the solution is raised to 60 ℃ to carry out epoxidation reaction for 6 hours; saturated aqueous solution of sodium bicarbonate or Na2S2O4Saturated aqueous solution, washing the reaction product until reaching neutrality; and extracting the organic layer of the reaction product by using a separating funnel, and volatilizing under a vacuum condition to remove the solvent to obtain the epoxidation modified styrene-butadiene-styrene block copolymer as a final product.
Example III
100 parts by weight of a solution containing a styrene-butadiene-styrene block copolymer in an amount of 25 wt%, 8 parts by weight of formic acid and 1 part by weight of tetramethylammonium hydroxide were added; stirring for 10-30 minutes at room temperature until the components are completely and uniformly mixed; addition of H2O210 parts by weight of solution and a proper amount of deionized water, H2O2The concentration of the solution is 40 vol%, then the temperature of the solution is raised to 75 ℃, and epoxidation reaction is carried out for 6 hours; saturated aqueous solution of sodium bicarbonate or Na2S2O4Saturated aqueous solution, washing the reaction product until reaching neutrality; and extracting the organic layer of the reaction product by using a separating funnel, and volatilizing under a vacuum condition to remove the solvent to obtain the epoxidation modified styrene-butadiene-styrene block copolymer as a final product.
Example IV
100 parts by weight of a solution containing a styrene-butadiene-styrene block copolymer in an amount of 25 wt%, 8 parts by weight of formic acid and 1 part by weight of tetramethylammonium hydroxide were added; stirring for 10-30 minutes at room temperature until the components are completely and uniformly mixed; addition of H2O210 parts by weight of solution, Na2WO40.8 weight portion and proper amount of deionized water H2O2The concentration of the solution is 40 vol%, then the temperature of the solution is raised to 75 ℃, and epoxidation reaction is carried out for 6 hours; saturated aqueous solution of sodium bicarbonate or Na2S2O4Saturated aqueous solution, washing the reaction product until reaching neutrality; and extracting the organic layer of the reaction product by using a separating funnel, and volatilizing under a vacuum condition to remove the solvent to obtain the epoxidation modified styrene-butadiene-styrene block copolymer as a final product.
Example V
100 parts by weight of a solution containing a styrene-butadiene-styrene block copolymer in an amount of 25 wt%, 8 parts by weight of formic acid and 1 part by weight of tetramethylammonium hydroxide were added; stirring for 10-30 minutes at room temperature until the components are completely and uniformly mixed; addition of H2O210 parts by weight of solution, Na2WO40.8 part by weight of H3PO40.6 part by weight of solution and a proper amount of deionized water, wherein H2O2The concentration of the solution was 40 vol%, H3PO4The concentration of the solution is 30 vol%, then the temperature of the solution is raised to 75 ℃, and epoxidation reaction is carried out for 6 hours; with hydrogen carbonateSaturated aqueous solution of sodium or Na2S2O4Saturated aqueous solution, washing the reaction product until reaching neutrality; and extracting the organic layer of the reaction product by using a separating funnel, and volatilizing under a vacuum condition to remove the solvent to obtain the epoxidation modified styrene-butadiene-styrene block copolymer as a final product.
Comparative example I
80 parts by weight of a solution containing 15 wt% of a styrene-butadiene-styrene block copolymer, 6 parts by weight of formic acid was added, and the mixture was stirred at room temperature for 10 to 30 minutes until completely and uniformly mixed; addition of H2O28 parts of solution and a proper amount of deionized water H2O2The concentration of the solution is 35 vol%, then the temperature of the solution is raised to 50 ℃ to carry out epoxidation reaction, gel colloid is generated after the reaction is carried out for more than 2 hours, the viscosity of a reaction system is obviously increased along with the time after the gel is generated, gel is formed during the reaction for 2-2.5 hours, the reaction cannot be continued, and the gel is obtained as a final product.
It can be seen that formic acid/H is used in the absence of tetramethylammonium hydroxide as a catalyst2O2The reaction of subjecting a styrene-butadiene-styrene block copolymer to epoxy group polarization treatment cannot be completed due to gel formation, and an effective epoxy-modified styrene-butadiene-styrene block copolymer cannot be obtained.
Comparative example II
90 parts by weight of a solution containing a styrene-butadiene-styrene block copolymer in an amount of 20 wt%, 8 parts by weight of formic acid and 0.5 part by weight of a quaternary ammonium salt catalyst; stirring for 10-30 minutes at room temperature until the components are completely and uniformly mixed; addition of H2O210 parts by weight of solution and a proper amount of deionized water, H2O2The concentration of the solution is 40 vol%, and then the temperature of the solution is raised to 60 ℃ to carry out epoxidation reaction for 5 hours; saturated aqueous solution of sodium bicarbonate or Na2S2O4Saturated aqueous solution, washing the reaction product until reaching neutrality; and, the organic layer was extracted from the reaction product by a separatory funnelAnd volatilizing the solvent under vacuum condition to obtain the epoxidation modified styrene-butadiene-styrene block copolymer as the final product.
The epoxy value and the gel percentage content were measured as experimental data for the obtained epoxidized modified styrene-butadiene-styrene block copolymer for the above examples I to V and comparative example II.
Wherein the epoxy value represents the concentration of epoxy groups in the epoxidized modified styrene-butadiene-styrene block copolymer, thereby reflecting the degree of polarization of the thermoplastic elastomer, the strategy for the epoxy value can be to determine the epoxy group concentration of the epoxidized modified styrene-butadiene-styrene block copolymer of examples I-V and comparative example II above by measuring the change in the ratio A884/A1600 of the absorption intensity of epoxy groups to that of phenyl groups using infrared spectroscopy, and averaging can be performed after a plurality of measurements in order to reduce errors. The epoxy values were measured as shown in Table I below. It can be seen that the epoxy value of the epoxidized modified styrene-butadiene-styrene block copolymer prepared in each example of the present application was improved as compared to comparative example II in which the conventional quaternary ammonium salt catalyst of the prior art was added. Among them, examples I to III showed that the epoxy value of the final product gradually increased with the increase in the amount of the tetramethylammonium hydroxide catalyst, the increase in the amount of formic acid, and the increase in the concentration of the styrene-butadiene-styrene block copolymer solution, wherein the increase in the epoxy value of the product was more significant when the amount of the tetramethylammonium hydroxide was in the range of 0.5 to 0.8 parts by weight, and the increase in the epoxy value of the product was not significant when the amount of the tetramethylammonium hydroxide was in the range of 0.8 to 1 part by weight. Examples IV and V separately, Na was added2WO4、Na2WO4And H3PO4In solution, a clear increase in the epoxide number of the preparation was observed.
The gel percentage content represents the gel content in the epoxidized modified styrene-butadiene-styrene block copolymer. To measure the percent gel content, the preparations of examples I-V and comparative example II above were extracted with toluene as the extraction solvent and refluxed in a Soxhlet extractorThe mass of the remaining gel solid was measured, and the gel percentage content was the percentage of the mass of the remaining gel solid with respect to the total mass of the epoxidized modified styrene-butadiene-styrene block copolymer before extraction. The percent gel content was measured as shown in table I below. Referring to comparative example I, gelation was severe during the reaction of the styrene-butadiene-styrene block solution with the peroxygenated organic acid, resulting in incomplete epoxidation; while examples I-V, in which tetramethylammonium hydroxide was added to reduce the gel content, it can be seen that as the amount of tetramethylammonium hydroxide catalyst added was increased from 0.5 to 0.8 parts by weight, the gel percentage content was significantly decreased, and the gel percentage content of the product was relatively stable over the range of 0.8 to 1 part by weight of tetramethylammonium hydroxide added. Examples IV and V separately, Na was added2WO4、Na2WO4And H3PO4The percentage of gel in the solution, the preparation, was stable compared to examples II and III. The gel percentage content of examples II-V was lower than that of comparative example II using the conventional catalyst quaternary ammonium salt.
TABLE I
The above description is only a preferred embodiment of the application and is illustrative of the principles of the technology employed. It will be appreciated by those skilled in the art that the scope of the invention herein disclosed is not limited to the particular combination of features described above, but also encompasses other arrangements formed by any combination of the above features or their equivalents without departing from the spirit of the invention. For example, the above features may be replaced with (but not limited to) features having similar functions disclosed in the present application.
Claims (10)
1. A method for preparing a tetramethylammonium hydroxide catalyzed thermoplastic material is characterized by comprising the following steps:
step 1, adding formic acid and tetramethyl ammonium hydroxide into a thermoplastic elastic material-containing solution, and uniformly stirring at room temperature;
step 2, adding H into the uniformly stirred solution2O2The solution and a proper amount of deionized water;
step 3, adding H2O2Heating the solution of deionized water to 50-75 ℃ to perform epoxidation reaction for 3-6 hours;
step 4, saturated aqueous solution of sodium bicarbonate or Na2S2O4Saturated aqueous solution, washing the reaction product in the step 3 until neutral; and extracting the organic layer of the reaction product by using a separating funnel, and volatilizing the solvent under a vacuum condition to obtain the epoxidized modified thermoplastic elastic material.
2. A process for preparing a tetramethylammonium hydroxide catalyzed thermoplastic material according to claim 1, wherein said thermoplastic elastomer is a styrene-butadiene-styrene block copolymer.
3. The process for the preparation of a tetramethylammonium hydroxide catalyzed thermoplastic material according to claim 2, wherein the solution used in step 1 has a styrene-butadiene-styrene block copolymer content of 15 to 25 wt%; 80-100 parts of thermoplastic elastic material-containing solution, 6-8 parts of added formic acid and 0.5-1.0 part of added tetramethylammonium hydroxide.
4. Process for the preparation of a tetramethylammonium hydroxide catalyzed thermoplastic material according to claim 3, wherein in step 2H2O2The concentration of the solution is 35-40 vol%, and H is added to the solution stirred uniformly in the step 12O28-10 parts of solution by weight, and then adding a proper amount of deionized water.
5. The process for preparing a tetramethylammonium hydroxide catalyzed thermoplastic material according to claim 4, characterized in thatCharacterized in that, in step 2, in said H2O2The solution and deionized water can also be added with a catalytic substance containing transition metal elements.
6. A process for the preparation of a tetramethylammonium hydroxide catalyzed thermoplastic material according to claim 5, wherein said transition metal element containing catalyst comprises a catalyst containing any of W, Mo, Mn, Ti, Zr.
7. Process for the preparation of a tetramethylammonium hydroxide catalyzed thermoplastic material according to claim 6, wherein said H is2O2Adding Na into the solution and deionized water2WO40.5 to 1.5 weight portions.
8. Process for the preparation of a tetramethylammonium hydroxide catalyzed thermoplastic material according to claim 7, wherein in step 2, in said H2O2A small amount of mineral acid may also be added to the solution and deionized water.
9. Process for the preparation of a tetramethylammonium hydroxide catalyzed thermoplastic material according to claim 8, wherein in step 2, said H is added2O2Solution and deionized water to H3PO40.3-0.8 part by weight of H3PO4The concentration is 30-40 vol%.
10. A tetramethylammonium hydroxide catalyzed thermoplastic material made by the method of any of the preceding claims.
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| CN101230112A (en) * | 2007-11-23 | 2008-07-30 | 广州宏昌胶粘带厂 | Method for preparing epoxidized styrene-isoprene-phenylethene block copolymer and use thereof |
| CN101538338A (en) * | 2009-04-09 | 2009-09-23 | 厦门大学 | Epoxidation method of gel-free double bond-contained polymer |
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