CN104650337A - Method for ring opening polymerization of 2,3-glycidyltrimethyl ammonium chloride - Google Patents

Abstract

The present invention provides the reaction process of 2,3-epoxypropyltrimethylammonium chloride direct ring-opening polymerization to generate polyether quaternary ammonium salt, select organic phase polymerization reaction system, use methanol as starter, ethyl acetate as Solvent, stannous chloride is the initiator, and the one-step polymerization method of the solution system is selected, which can effectively avoid the side reaction of the aqueous phase polymerization, the purity of the obtained product is high, and the molecular weight distribution becomes narrow; It will cause environmental pollution; the selected initiator, solvent, and initiator raw materials of the present invention are cheap and easy to get, the process operation is simple, the polyether conversion rate is high, and the product has good defoaming performance and electrical conductivity, and is used in sewage treatment and liquid electrolyte The field of research and development has broad prospects.

Description

A kind of method of ring-opening polymerization of 2,3-epoxypropyltrimethylammonium chloride

technical field

The present invention relates to the field of polymer materials, specifically a method for ring-opening polymerization of 2,3-epoxypropyltrimethylammonium chloride.

Background technique

2,3-Epoxypropyltrimethylammonium chloride (ETA) is a reactive substance. There are both quaternary ammonium cations and highly reactive epoxy groups in the molecule. Under certain conditions, it can pass through Ring-opening polymerization produces polyether quaternary ammonium salt polymers. Polyether quaternary ammonium salt is a new type of polymer material with positive charges on its molecular chain, good water solubility, high efficiency and low toxicity, no corrosion and irritation to human organ skin, good bactericidal effect, and is a new type of non-oxidizing Sexual fungicides. This product also has the functions of slime stripping, flotation, erosion and demulsification, etc. It can be used in industrial circulating water, and can also be used as a multifunctional sewage treatment agent in industrial sewage treatment, especially in the treatment of reinjection water in the process of oil recovery in oil fields. have important applications. The research on the ring-opening polymerization method of 2,3-epoxypropyltrimethylammonium chloride has been reported in recent years, but there are many reaction by-products, the degree of unsaturation of the polyether product is large, and the molecular weight distribution is also very wide, and the The defoaming performance of the prepared polyether quaternary ammonium salt is not good.

Contents of the invention

In view of the above-mentioned existing 2,3-epoxypropyltrimethylammonium chloride ring-opening polymerization method, there are many reaction by-products, the polyether product has a large degree of unsaturation, and the molecular weight distribution is also very wide, and the prepared polyether Defects such as poor defoaming properties of quaternary ammonium salts, the present invention provides a method for ring-opening polymerization of 2,3-epoxypropyltrimethylammonium chloride.

In order to solve the problems of the technologies described above, the technical solution adopted in the present invention is:

A method for ring-opening polymerization of 2,3-epoxypropyltrimethylammonium chloride, comprising the following steps:

Step 1: Get 2,3-epoxypropyltrimethylammonium chloride, dissolve it with ethyl acetate, and set aside, the consumption of said ethyl acetate is every 8g of 2,3-epoxypropyltrimethylammonium chloride Ammonium plus 15~25mL;

Step 2: Add initiator methanol to the solution obtained in Step 1, stir at 55-75°C, 100KPa, under nitrogen protection, and reflux for 30 minutes, then add initiator SnCl ₂ and react for 5-10 hours until there is a light yellow transparent homogeneous phase When the solution appears, add hydrochloric acid dropwise to adjust the pH to neutral, and the reaction solution is obtained for subsequent use. The addition amount of the starter methanol is 0.5-1.5 mL per 8 g of 2,3-epoxypropyltrimethylammonium chloride. Said initiator _SnCl The add-on is 0.1～0.6% of 2,3-epoxypropyltrimethylammonium chloride weight;

Step 3: Distill the reaction solution obtained in Step 2 under reduced pressure until there is no more distillate, and dry the obtained product to obtain the target product;

The consumption of ethyl acetate in described step 1 is every 8g 2,3-epoxypropyltrimethyl ammonium chloride 20mL;

The add-on of initiator methyl alcohol in described step 2 is every 8g 2,3-epoxypropyltrimethyl ammonium chloride 1mL;

Initiator SnCl in described step ₂ Add-on is 0.45% of 2,3-epoxypropyltrimethylammonium chloride weight;

The reaction temperature in the step 2 is 70°C;

The reaction time in the step two is 7h.

Beneficial effects of the present invention:

The invention provides the reaction process of direct ring-opening polymerization of 2,3-epoxypropyltrimethylammonium chloride (ETA) to generate polyether quaternary ammonium salt (PETA). The organic phase polymerization reaction system is selected, starting with methanol agent, ethyl acetate as the solvent, stannous chloride as the initiator, and the one-step polymerization method of the solution system can effectively avoid the side reaction of the aqueous phase polymerization. The resulting product has high purity and narrow molecular weight distribution; and the polymerization temperature is low, organic The solvent can be recycled without causing environmental pollution; the selected initiator, solvent and initiator raw materials in the present invention are cheap and easy to obtain, the process operation is simple, the conversion rate of polyether is high, and the product has good defoaming performance and electrical conductivity, It has broad prospects in the research and development of sewage treatment and liquid electrolytes.

Description of drawings

Figure 1 Effect of reaction temperature on the relative viscosity of polyether quaternary ammonium salt (PETA) products;

Fig . 2 Effect diagram of the reaction temperature on the conversion rate of polyether quaternary ammonium salt (PETA);

Fig . 3 Effect diagram of reaction time on relative viscosity of polyether quaternary ammonium salt (PETA) product;

Fig . 4 Effect diagram of the reaction time on the conversion rate of polyether quaternary ammonium salt (PETA);

Fig. 5 Effect diagram of the amount of initiator on the product conversion rate of polyether quaternary ammonium salt (PETA);

Fig. 6 Effect diagram of the amount of initiator on the relative viscosity of polyether quaternary ammonium salt (PETA) products;

Figure 7. Experimental data table of defoaming efficiency of polyether quaternary ammonium salt (PETA);

Figure 8 Conductivity data of polyether quaternary ammonium salt (PETA) at different temperatures;

Figure 9 IR spectrum of 2,3-epoxypropyltrimethylammonium chloride (ETA);

Figure 10 IR spectrum of polyether quaternary ammonium salt (PETA).

Detailed ways

The present invention will be further elaborated below in combination with specific embodiments.

Example 1

A method for ring-opening polymerization of 2,3-epoxypropyltrimethylammonium chloride, comprising the following steps:

Step 1: Take 8g of 2,3-epoxypropyltrimethylammonium chloride, dissolve it in 20mL of ethyl acetate, and set aside;

Step 2: Add 1 mL starter methanol to the solution obtained in Step 1, stir at 70°C, 100KPa, under nitrogen protection, and reflux for 30 minutes, then add 0.45% 2,3-epoxypropyltrimethylammonium chloride by weight Initiator SnCl ₂ , react for 7 hours, until a light yellow transparent homogeneous solution appears, add hydrochloric acid dropwise to adjust the pH to neutral, and obtain the reaction solution for later use;

Step 3: Distill the reaction liquid obtained in Step 2 under reduced pressure until there is no more distillate, and dry the obtained product to obtain the target product.

Example 2

A method for ring-opening polymerization of 2,3-epoxypropyltrimethylammonium chloride, comprising the following steps:

Step 1: Take 8g of 2,3-epoxypropyltrimethylammonium chloride, dissolve it in 15mL ethyl acetate, and set aside;

Step 2: Add 0.5mL starter methanol to the solution obtained in Step 1, stir at 55°C, 100KPa, under nitrogen protection, and reflux for 30min, then add 0.6% 2,3-epoxypropyltrimethylammonium chloride by weight The initiator SnCl ₂ was reacted for 5 hours, and when a light yellow transparent homogeneous solution appeared, hydrochloric acid was added dropwise to adjust the pH to neutral, and the reaction solution was obtained for use;

Step 3: Distill the reaction liquid obtained in Step 2 under reduced pressure until there is no more distillate, and dry the obtained product to obtain the target product.

Example 3

A method for ring-opening polymerization of 2,3-epoxypropyltrimethylammonium chloride, comprising the following steps:

Step 1: Take 8g of 2,3-epoxypropyltrimethylammonium chloride, dissolve it in 25mL of ethyl acetate, and set aside;

Step 2: Add 1.5mL starter methanol to the solution obtained in Step 1, stir at 75°C, 100KPa, under nitrogen protection, and reflux for 30min, then add 0.1% 2,3-epoxypropyltrimethylammonium chloride by weight The initiator SnCl ₂ was reacted for 10 hours, and when a light yellow transparent homogeneous solution appeared, hydrochloric acid was added dropwise to adjust the pH to neutral, and the reaction solution was obtained for use;

Step 3: Distill the reaction liquid obtained in Step 2 under reduced pressure until there is no more distillate, and dry the obtained product to obtain the target product.

(1) Determination of relative viscosity

Take 30mL of distilled water and add it to the Uber-Luther viscometer, keep the temperature at 25°C for a period of time, and then measure the flow time t ₀ of the distilled water flowing from the scale line a to the scale line b.

Accurately weigh 2.0g of the prepared sample, pour it into a 50mL volumetric flask, dilute to the mark with distilled water, shake well, put it in constant temperature water at 25°C, and measure the flow rate of the solution from the a scale line to the b scale line elapsed time t;

The relative viscosity of the sample is calculated according to the following formula: relative viscosity η _r = t / t ₀ .

(2) Determination of epoxy value

Take 2.0g of the prepared sample, put it in a 50mL volumetric flask, add 4mL of 1.0mol.L ^-1 sodium hydroxide aqueous solution, dilute with distilled water to constant volume, let it stand for 1h, take 4mL of the solution in the above volumetric flask, add 8mL Water, titrated with 0.5 mol.L ^-1 hydrochloric acid standard solution until thymolphthalein fades, the volume of consumed hydrochloric acid standard solution is b ml; take another 4 ml of the solution in the above volumetric flask, add 8 ml of saturated sodium sulfite aqueous solution, and mix well React at room temperature for half an hour, and then titrate with 0.5 mol.L ^-1 hydrochloric acid standard solution until the color of thymolphthalein fades, and the volume of consumed hydrochloric acid standard solution is a ml. Calculate the epoxy value according to the following formula:

E=[(a-b)×M×N/1000]/(m×4/50)×100%

In the formula: E—epoxy value, %;

M—the molecular weight of the measured sample;

N—concentration of standard hydrochloric acid solution, mol.L ⁻¹ ;

m—the mass of the sample to be weighed, g.

(3)

Under the conditions of ETA mass 6.0g, initiator SnCl ₂ dosage 1.0%, and reaction time 7h, the effects of different reaction temperatures on the relative viscosity and conversion rate of polyether quaternary ammonium salt (PETA) products are shown in Figure 1 and Figure 2;

It can be seen from Figure 1 and Figure 2 that with the increase of reaction temperature between 55 ° C and 75 ° C, the relative viscosity and conversion rate of PETA gradually increase, and reach a peak at 70 ° C, which is due to the low temperature. The reaction rate is slow, and the polymerization is incomplete; the temperature is too high, resulting in violent polymerization, and the observed color will deepen, so the reaction temperature is selected at 70°C for the best.

(4) Influence of reaction time

Under the conditions of ETA mass 6.0g, initiator SnCl ₂ dosage 1.0%, and reaction temperature 70°C, the effects of different reaction times on the relative viscosity and conversion rate of polyether quaternary ammonium salt (PETA) products are shown in Figure 3 and Figure 4;

It can be seen from Figure 3 and Figure 4 that between the reaction time of 5 and 7 hours, the relative viscosity and conversion rate of the product showed an upward trend. The relative viscosity at 5 hours was 1.0431, and the conversion rate was 76.9%; the relative viscosity at 7 hours was 1.0787, and the conversion rate 82.5%, reached the peak value, and then decreased. Therefore, considering the time-effect ratio, the optimal reaction time was selected as 7h.

(5) Influence of initiator dosage

Under the conditions of ETA mass 6.0g, reaction time 7h, and reaction temperature 70°C, the effects of different initiator dosages on the conversion rate and relative viscosity of polyether quaternary ammonium salt (PETA) products are shown in Figure 5 and Figure 6;

It can be seen from Figure 5 and Figure 6 that the amount of initiator accounts for 0.1717% (0.0103g) to 0.45% (0.0270g) of the mass of ETA. With the increase of initiator, the relative viscosity and conversion rate of PETA are on the rise. It reached the maximum at 0.45%, and then increased the amount of initiator, then it showed a downward trend, so the optimal amount of initiator was selected as 0.45% of the mass of ETA.

To sum up, when ethyl acetate is used as solvent and SnCl ₂ is used as initiator, the optimum process conditions are: reaction temperature 70°C, reaction time 7h, initiator dosage 0.45% of ETA mass.

(6) Defoaming performance test of polyether quaternary ammonium salt PETA

Add 2mL of 1% sodium dodecylbenzenesulfonate solution and 20mL of distilled water into a 100mL stoppered measuring cylinder, record the foam volume after mechanically shaking at room temperature for 30s, then add different volumes of polyether quaternary ammonium salt solution in sequence, and record the foam after shaking for 30s Volume, the defoaming efficiency is calculated according to the following formula:

Defoaming efficiency = (initial foam volume - foam volume after defoaming) ÷ initial foam volume × 100%

The experimental data of the defoaming efficiency of polyether quaternary ammonium salt (PETA) is shown in Figure 7. It can be seen from Figure 7 that with the addition of defoamer PETA, the defoaming efficiency gradually increases. When the polyether quaternary ammonium salt solution is added to a certain When measuring, no air bubbles will be generated after the graduated cylinder oscillates for 30s, that is, the defoaming efficiency reaches 100%.

In the production process of chemical industry, petroleum exploration, microbial fermentation, sewage treatment and papermaking, foam will be generated, which will reduce production capacity, bring difficulties to operation and affect product quality. Therefore, effectively eliminating foam will improve product quality, ensure normal production, and reduce consumption. The best way to eliminate foam is to add defoamers, which range from natural to synthetic. In the past, mineral oil, animal and vegetable oil, etc. have been used as defoamers, but the effect is poor. The use of synthetic defoaming agents is much better, especially the use of polyether defoaming agents is currently an economical and effective defoaming method.

(7) Determination of conductivity of polyether quaternary ammonium salt PETA

Take a DDS-11A conductivity meter, insert its platinum electrode into the viscous fluid polyether quaternary ammonium salt PETA, slowly raise the temperature of the oil bath, and record the conductivity of the polyether quaternary ammonium salt at different temperatures. For the test data, see Figure 8;

It can be seen from the test data in Figure 8 that as the temperature rises, the conductivity gradually increases. From room temperature to 65°C, the conductivity increases slowly; Faster; when the temperature reaches 90°C, the increase in conductivity slows down. At the same time, it is found that the color of polyether quaternary ammonium salt is deepening at this moment, and finally a dark brown paste appears. It may be that the temperature rises to a critical point, which is suspected to be caused by oxidative deterioration.

(8) IR spectrum characterization of polyether quaternary ammonium salt PETA structure

As shown in Figure 9, it is the IR spectrum of 2,3-epoxypropyltrimethylammonium chloride (ETA), and as shown in Figure 10, it is the IR spectrum of polyether quaternary ammonium salt (PETA);

Comparing and analyzing the IR spectra of 2,3-epoxypropyltrimethylammonium chloride (ETA) and polyether quaternary ammonium salt (PETA), it can be seen that there are two characteristic absorption peaks (1264.94cm ^{- 1} asymmetric stretching vibration V _as C—O—C, sharp peak; 1046.93 cm ^-1 asymmetric stretching vibration V _as C—O—C, sharp peak ) only one absorption peak (1264.42 cm ^-1 ), the latter absorption peak evolves into a broad and strong absorption peak at 1125.05 cm ^-1 , which is the characteristic absorption peak of the stretching vibration of the ether bond “—CH ₂ —O—CH ₂ —” of the chain ether, and the broadening of the peak shape indicates the The degree of polymerization becomes larger, which shows that the ring-opening polymerization of epoxy quaternary ammonium salt (ETA) forms chain polyether quaternary ammonium salt (PETA), and the structure of the synthesized product meets the requirements.

Claims (6)

1. the method for an epoxypropyltrimethylchloride chloride ring-opening polymerization, is characterized in that, comprises the following steps:

Step one: get 2,3-epoxypropyltrimethylchloride chloride, with acetic acid ethyl dissolution, for subsequent use, the consumption of described ethyl acetate is that every 8g 2,3-epoxypropyltrimethylchloride chloride adds 15 ~ 25mL;

Step 2: add initiator methyl alcohol in step one gained solution, in 55 ~ 75 DEG C, 100KPa, stirred under nitrogen atmosphere, after backflow 30min, add initiator SnCl ₂, reaction 5 ~ 10h, when occurring to there being pale yellow transparent homogeneous phase solution, drip salt acid for adjusting pH to neutral, obtain reaction solution for subsequent use, the amount of described initiator methyl alcohol is that every 8g 2,3-epoxypropyltrimethylchloride chloride adds 0.5 ~ 1.5mL, described initiator SnCl ₂add-on be 0.1 ~ 0.6% of 2,3-epoxypropyltrimethylchloride chloride weight;

Step 3: get step 2 gained reaction solution vacuum decompression and be distilled to and no longer include overhead product, get products obtained therefrom drying, obtain target product.

2. the method for 2,3-epoxypropyltrimethylchloride chloride ring-opening polymerizations as claimed in claim 1, is characterized in that: in described step one, the consumption of ethyl acetate is that every 8g 2,3-epoxypropyltrimethylchloride chloride adds 20mL.

3. the method for 2,3-epoxypropyltrimethylchloride chloride ring-opening polymerizations as claimed in claim 1, is characterized in that: in described step 2, the amount of initiator methyl alcohol is that every 8g 2,3-epoxypropyltrimethylchloride chloride adds 1mL.

4. the method for 2,3-epoxypropyltrimethylchloride chloride ring-opening polymerizations as claimed in claim 1, is characterized in that: initiator SnCl in described step 2 ₂add-on be 0.45% of 2,3-epoxypropyltrimethylchloride chloride weight.

5. the method for 2,3-epoxypropyltrimethylchloride chloride ring-opening polymerizations as claimed in claim 1, is characterized in that: the temperature of reaction in described step 2 is 70 DEG C.

6. the method for 2,3-epoxypropyltrimethylchloride chloride ring-opening polymerizations as claimed in claim 1, is characterized in that: the reaction times in described step 2 is 7h.