CN113831430B - Production method of epoxidized SIS - Google Patents
Production method of epoxidized SIS Download PDFInfo
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- CN113831430B CN113831430B CN202111307260.XA CN202111307260A CN113831430B CN 113831430 B CN113831430 B CN 113831430B CN 202111307260 A CN202111307260 A CN 202111307260A CN 113831430 B CN113831430 B CN 113831430B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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Abstract
The invention belongs to the technical field of thermoplastic elastomer epoxidation of SIS (styrene-ethylene-styrene) containing double bonds, and particularly relates to a production method of an epoxidized SIS thermoplastic elastomer containing double bonds. The method mainly adopts a weak polar or nonpolar organic solvent as a reaction solvent, and under a certain temperature, SIS raw materials react with an epoxidation reagent, and the obtained product is neutralized by alkali liquor and is washed and purified by water. The method can prepare the epoxy SIS with controllable epoxy group content by selecting proper solvents, dispersion systems, epoxidation tests and the like and adjusting reaction conditions under the specified temperature and reaction time. The method realizes SIS epoxidation, the degree of epoxidation is controllable, the degree of epoxidation can reach more than 90%, the ring opening rate is small, and the problem that the prior art cannot epoxidize SIS is solved.
Description
Technical Field
The invention belongs to the technical field of polymer epoxidation, improves the dissolution performance of an epoxidation product, and particularly relates to a production method of an epoxidation SIS.
Background
SIS, polystyrene-polyisoprene-polystyrene triblock, is an important thermoplastic elastomer. It has the properties of vulcanized rubber at room temperature and exhibits plasticity at high temperatures. And thus has been attracting attention, mainly for raw materials of hot melt adhesives and pressure-sensitive adhesives. However, SIS has small polarity and poor oil resistance and solvent resistance, so that the application of the SIS is greatly limited; meanwhile, the anionic polymerization process cannot introduce polar groups in the polymerization, and in this case, chemical modification and introduction of polar groups become a feasible method.
The double bond in the polymer is easily oxidized into epoxy group under the action of proper oxidant, which not only can realize the polarization of the polymer, but also can introduce epoxy group with higher reactivity than the double bond into the polymer, thus endowing the polymer with new reactivity and converting the double-built polymer into a functional material, thus the epoxidation modification of the double-bond-containing polymer has important application value.
The epoxidation process of double bond-containing polymers has been studied for a long time, but has remained in the laboratory research stage so far, and large-scale commercial production has not been started. The main reason for limiting industrial production is that the epoxidation reaction is accompanied by serious crosslinking side reaction, which affects the dissolution performance of the epoxidation product.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a production method of an epoxidized SIS, which adopts a weak polar or nonpolar organic solvent as a reaction solvent to epoxidize the SIS, reacts with an epoxidation reagent under proper solvent, dispersion system and temperature conditions, and prepares a modified SIS product with controllable epoxy group content through proper reaction conditions.
The technical problems to be solved by the invention are produced by the following technical proposal. The invention relates to an epoxidation SIS production method, which comprises the following specific steps:
1) Dissolving SIS in a weak polar or nonpolar organic solvent for swelling, and stirring to obtain a solution;
2) Reacting the SIS solution with an epoxidation reagent in a dispersion;
the unsaturation degree of the SIS raw material is less than 8 percent, preferably 1 to 3 percent, and the weight average molecular weight is 10 ten thousand to 20 ten thousand, preferably 13 ten thousand to 18 ten thousand;
the epoxidation reagent is a water-soluble reagent or a non-water-soluble reagent, the water-soluble reagent comprises peroxy acid, tert-butyl alcohol peroxide or hydrogen peroxide/organic acid system (molar ratio of hydrogen peroxide to organic acid is 1:1), and the acid is organic acid such as formic acid, acetic acid and the like; the water-insoluble reagent comprises m-chloroperoxybenzoic acid;
the dispersion system is a system which can well mix an epoxidation reagent and SIS raw materials and is divided into a homogeneous system or a heterogeneous system, wherein the emulsifier of the heterogeneous system is a nonionic surfactant and an ionic surfactant such as sodium dodecyl benzene sulfonate, polyethylene glycol monolaurate and the like. When the epoxidation agent is a water-soluble agent, the dispersion system is a heterogeneous system, and when the epoxidation agent is a water-insoluble agent, the dispersion system is a homogeneous system. The solvents of the two systems are weak polar or nonpolar organic solvents, and are chloroform or dichloromethane or a mixture thereof, preferably chloroform/dichloromethane mixture;
the molar ratio of double bonds to epoxidizing agent in SIS feed was 1:0.5-1:2.5;
the reaction time is 15-160 minutes; preferably 50-140 minutes; more preferably 80-120 minutes;
the reaction temperature is 5-60 ℃; preferably 15-35 ℃;
3) Neutralizing the obtained product with alkali liquor, and washing and purifying with water.
In the present invention, if the dispersion is a homogeneous system, the steps are: the SIS raw material was dissolved using a solvent, and then an epoxidation reagent was added to carry out the reaction. If the dispersion is a heterogeneous system, the steps are: the SIS raw material is dissolved by using a solvent, then an emulsifying agent and water are added, and an epoxidation reagent is added for reaction.
In the present invention, the inventors found that:
the proportion of the mixed solvent and the reaction time have key influence on the epoxidation degree, the reaction time is too short, the epoxidation degree is less, and the ring-opening reaction is easy to occur in the overlong process; when the reaction time is 1.2-2 hours, the epoxidation degree is high and the ring opening is less; the greater the ratio of double bonds to epoxidation reagent, the greater the degree of epoxidation.
The structure of the epoxy SIS prepared by the method is as follows:
m and n are natural numbers, and the value is 1-20.
Preferably, the degree of epoxidation of the epoxy SIS is 5% to 95%; compared with the prior art, the invention has the following beneficial effects:
1. the method can prepare the epoxy SIS with controllable epoxy group content by selecting proper solvents, dispersion systems, epoxidation tests and the like and adjusting reaction conditions under the specified temperature and reaction time. The method realizes SIS epoxidation, the degree of epoxidation is controllable, the degree of epoxidation can reach more than 90%, the ring opening rate is small, and the problem that the prior art cannot epoxidize SIS is solved.
2. The method realizes SIS epoxidation, has controllable epoxidation degree, and solves the problem that the prior art cannot epoxidize SIS. The introduction of polar groups into the epoxidized SIS prepared by the method improves the compatibility and adhesiveness of SIS with other materials, and the like. Meanwhile, the epoxidized SIS can be vulcanized by adopting bio-diamine, diacid or anhydride at a lower temperature, so that the problem that the existing vulcanization system generates vulcanized smoke and smell is solved.
Detailed Description
The present invention will be described below with reference to specific examples, but is not limited to the contents of the invention. Unless otherwise specified, the reagents and instruments used in the present invention are all conventional reagents and instruments. The raw materials are all purchased commercially.
Example 1: production method of epoxidized SIS experiment 1
In this example, a mixed solvent of chloroform/methylene chloride of 80/20 was used as a reaction medium. 5g of SIS (weight average molecular weight: 170000, degree of unsaturation: 1.85%) was weighed, crushed and placed in a three-necked flask, and 125mL of a chloroform/methylene chloride mixed solvent was added to dissolve. After complete dissolution, the three-neck flask is slowly added with m-chloroperoxybenzoic acid/dichloromethane=2 g/100ml solution (molar ratio of double bond in SIS to peroxybenzoic acid is 1:1.3) at room temperature (25 ℃), reaction is started, after 80 minutes, neutralization is carried out by using sodium hydroxide solution with concentration of 1%, the pH value of the solution is adjusted to 7-10, and the solution is washed by a proper amount of distilled water for about 3 times, so that the solidified glue solution is a glue block. The prepared epoxy SIS is detected by a nuclear magnetic method, the double bond epoxidation degree is 94%, and the ring opening degree is 0.03%.
Example 2: production method of epoxidized SIS experiment 2
In this example, a mixed solvent of chloroform/methylene chloride of 70/30 was used as a reaction medium. 5g of SIS (weight average molecular weight: 170000, degree of unsaturation: 1.85%) was weighed, crushed and placed in a three-necked flask, and 125mL of a chloroform/methylene chloride mixed solvent was added to dissolve. After complete dissolution, the three-neck flask is slowly added with m-chloroperoxybenzoic acid/dichloromethane=2 g/100ml solution (molar ratio of double bond in SIS to peroxybenzoic acid is 1:1.3) at room temperature (25 ℃), reaction is started, after 110 minutes, neutralization is carried out by using sodium hydroxide solution with concentration of 1%, the pH value of the solution is adjusted to 7-10, and the solution is washed by a proper amount of distilled water for about 3 times, so that the solidified glue solution is a glue block. The prepared epoxy SIS is detected by a nuclear magnetic method, the double bond epoxidation degree is 90%, and the ring opening degree is 0%.
Example 3: production method of epoxidized SIS experiment 3
In this example, a mixed solvent of chloroform/methylene chloride of 80/20 was used as a reaction medium. 5g of SIS (weight average molecular weight: 170000, degree of unsaturation: 1.9%) was weighed, crushed and placed in a three-necked flask, and 125mL of a chloroform/methylene chloride mixed solvent was added to dissolve. After complete dissolution, the three-neck flask is slowly added with m-chloroperoxybenzoic acid/dichloromethane=2 g/100ml solution (molar ratio of double bond in SIS to peroxybenzoic acid is 1:1.1) at room temperature (25 ℃), reaction is started, after 120 minutes of reaction, neutralization is carried out by using sodium hydroxide solution with concentration of 1%, the pH value of the solution is adjusted to 7-10, and the solution is washed by using a proper amount of distilled water for about 3 times, so that the solidified glue solution is a glue block. The prepared epoxy SIS is detected by a nuclear magnetic method, the double bond epoxidation degree is 88%, and the ring opening degree is 0.15%.
Example 4: production method of epoxidized SIS experiment 4
In this example, a mixed solvent of chloroform/methylene chloride of 80/20 was used as a reaction medium. 5g of SIS (weight average molecular weight: 190000, degree of unsaturation: 1.85%) was weighed, crushed and placed in a three-necked flask, and 125mL of a chloroform/methylene chloride mixed solvent was added to dissolve. After complete dissolution, the three-neck flask is kept stable for 50 minutes at room temperature (25 ℃), 0.5ml of sodium dodecyl benzene sulfonate is slowly added, 0.35ml of acetic acid with the mass concentration of 99.9% and 0.70ml of 30% hydrogen peroxide are slowly added to start reaction (the molar ratio of the acetic acid to the hydrogen peroxide is 1:1.1), the reaction is started, after 80 minutes, the neutralization is carried out by using 1% sodium hydroxide solution, the PH value of the solution is regulated to 7-10, and the solution is washed for 3 times by using a proper amount of distilled water, so that the solidified glue solution is a glue block. The prepared epoxy SIS is detected by a nuclear magnetic method, the double bond epoxidation degree is 60.2%, and the ring opening degree is 0.12%.
Example 5: production method of epoxidized SIS experiment 5
In this example, a mixed solvent of chloroform/methylene chloride of 60/40 was used as a reaction medium. 5g of SIS (weight average molecular weight: 180000, degree of unsaturation: 1.85%) was weighed, crushed and placed in a three-necked flask, and 125mL of a chloroform/methylene chloride mixed solvent was added to dissolve. After complete dissolution, the three-neck flask is kept stable for 50 minutes at room temperature (25 ℃), 0.5ml of sodium dodecyl benzene sulfonate is slowly added, 0.35ml of acetic acid with the mass concentration of 99.9% and 0.70ml of 30% hydrogen peroxide are slowly added to start the reaction (the molar ratio of the acetic acid to the hydrogen peroxide is 1:1.1), the reaction is started, after 100 minutes, the neutralization is carried out by using 1% sodium hydroxide solution, the PH value of the solution is regulated to 7-10, and the solution is washed for 3 times by using a proper amount of distilled water, so that the coagulating solution is gel. The prepared epoxy SIS is detected by a nuclear magnetic method, the double bond epoxidation degree is 53.6%, and the ring opening degree is 0.09%.
Example 6: production method of epoxidized SIS experiment 6
In this example, methylene chloride was used as the reaction medium. 5g of SIS (weight average molecular weight: 180000, degree of unsaturation: 1.85%) was weighed, crushed and placed in a three-necked flask, and 125mL of a methylene chloride mixed solvent was added to dissolve. After complete dissolution, the three-neck flask is slowly added with m-chloroperoxybenzoic acid/dichloromethane=2 g/100ml solution (molar ratio of double bond in SIS to peroxybenzoic acid is 1:1.3) at room temperature (25 ℃), reaction is started, after 100 minutes, neutralization is carried out by using sodium hydroxide solution with concentration of 1%, the pH value of the solution is adjusted to 7-10, and the solution is washed by a proper amount of distilled water for about 3 times, so that the coagulated solution is gel. The prepared epoxy SIS is detected by a nuclear magnetic method, the double bond epoxidation degree is 82.5%, and the ring opening degree is 0.18%.
TABLE 1 comparison of epoxidation data
From the above experiments, it can be seen that: the mixed solvent of chloroform/dichloromethane is adopted, so that the epoxy SIS with high epoxidation degree can be obtained, and the ring opening rate is small. After SIS epoxidation, the solubility parameter of the rubber chain segment is increased compared with that before reaction, and the cohesive strength is increased; because the polarity of the epoxidized SIS is increased, the compatibility with the plasticizer and the tackifier with strong polarity is good; the peel strength and the holding viscosity of the epoxidized SIS hot-melt pressure-sensitive adhesive are better than those of the SIS hot-melt pressure-sensitive adhesive.
Claims (5)
1. The production method of the epoxidized SIS is characterized by comprising the following specific steps:
(1) Dissolving SIS in a weak polar organic solvent for swelling, and stirring to obtain a solution; the weak-polarity organic solvent is a mixture of chloroform and dichloromethane;
(2) Reacting SIS glue solution with an epoxidation reagent in a dispersion system at a certain temperature; the unsaturation degree of the SIS raw material is less than 8%, and the weight average molecular weight of the SIS raw material is 5 ten thousand to 30 ten thousand; the epoxidation reagent is a water-insoluble reagent, and the water-insoluble reagent is m-chloroperoxybenzoic acid; the dispersion system is a homogeneous system; the molar ratio of double bonds to epoxidizing agent in SIS feed was 1:0.5-1:2.5; the reaction time is 15-160 minutes; the reaction temperature is 5-60 ℃;
(3) Neutralizing the obtained product with alkali liquor, and washing and purifying with water.
2. The method according to claim 1, characterized in that: in the step (2), the unsaturation degree of the SIS raw material is 1-3%, and the weight average molecular weight is 10-20 ten thousand.
3. The method according to claim 1, characterized in that: in the step (2), the reaction time is 80-120 minutes.
4. The method according to claim 1, characterized in that: in the step (2), the reaction temperature is 15-35 ℃.
5. Use of an epoxidized SIS produced by the process of claim 4 in a modified material.
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