CN116375936A - Preparation and application of allyl trimethyl silane-vinyl pyrrolidone-maleic anhydride terpolymer - Google Patents

Abstract

式Ⅰ。本发明化合物优点是：该类三元共聚物由于羧酸基团和吡咯烷酮的存在使得共聚物具有优异的分散性，而且有机硅基团使得共聚物同时具有优异的润湿性。The invention relates to the preparation and application of a class of allyltrimethylsilane-vinylpyrrolidone-maleic anhydride terpolymer. In addition to the pyrrolidone and carboxylate groups in the side chain of the terpolymer of the present invention, the organosilicon group is also introduced into the comb polymer system, so that the comb polymer dispersant not only has a good dispersant, but also has excellent Wettability, represented by general formula I:

Formula I. The advantage of the compound of the present invention is that the terpolymer has excellent dispersibility due to the presence of carboxylic acid groups and pyrrolidone, and the organosilicon group makes the copolymer have excellent wettability at the same time.

Description

Allyltrimethylsilane-vinylpyrrolidone-maleic anhydride terpolymer Preparation and application

technical field

The invention belongs to the preparation and application of carboxylate wetting and dispersing agents, in particular to the preparation and application of allyltrimethylsilane-vinylpyrrolidone-maleic anhydride terpolymer obtained through free radical initiation polymerization application.

Background technique

Carboxylate dispersants can be stably adsorbed on the surface of particles due to their special molecular structure, effectively hindering the aggregation and sedimentation of particles in the suspension system, so this type of compound is widely used in the fields of pesticide preparations, coatings and dyes. However, the dispersibility of carboxylate is relatively poor compared to the small molecule wettability of polyether or sulfate, while silicon-containing compounds tend to have better wettability, which can better wet the surface of pesticide particles, so the improved The hardened carboxylate compound (allyltrimethylsilane-vinylpyrrolidone-maleic anhydride) has both dispersibility and wetting properties.

The characteristics and performance applications of the technically synthesized comb-shaped polymer are as follows: the comb-shaped polycarboxylic acid is widely used as a water reducer for cement-based materials due to the mechanism of electrostatic adsorption of the main chain and steric effect of the side chain. Select the bulk polymerization method, use isopentenyl polyethylene glycol or isobutenyl polyethylene glycol as the monomer, and azobisisobutyronitrile as the initiator to synthesize a comb-shaped polymer dispersant and study it as a water reducer in concrete Applications. The results show that the weakness of concrete for water-cement separation has almost disappeared. A comb-shaped polycarboxylic acid dispersant was designed for coal-water slurry, and a comb-shaped compound was obtained by solution polymerization using methacrylic acid, methoxypolyethylene glycol methacrylate, and sodium methylpropyl sulfonate as monomers Dispersant. (Electrochimica Acta, 2017, 255, 396-404). Among them, the carboxyl group has a strong adsorption effect on the surface of coal particles, the sulfonate group is a hydrophilic group, and provides electronegativity on the surface of coal particles, and the polyoxyethylene branch chain forms a thick hydration layer in the solution. The interaction of clusters provides steric hindrance and electrostatic repulsion for suspended particles. Therefore, the performance of the comb copolymer dispersant in reducing the apparent viscosity of CWS is better than that of the commercial naphthalenesulfonic acid formaldehyde condensate dispersant (Journal of the American Chemical Society, 2009, 131, 1628-1629.).

Extending this concept to the field of ceramic industry, for the first time, free radical polymerization was used to obtain styrene-maleic anhydride copolymer grafted with polyethylene glycol monomethyl ether, and the comb polymer was used as a high-efficiency dispersant for alumina suspension , to study the effect of polymer groups on the suspending system. The specific method is to synthesize styrene and maleic anhydride copolymer first, and then use 4-dimethylaminopyridine as an ester catalyst to graft MPEG on the carboxyl group of SMA chain to form SMA-g-MPEG. This study also discusses the effect of comb polymer side chain length on the dispersibility of Al2O3 suspensions. The results show that as the length of the side chain increases, the number of adsorbed molecules of the dispersant decreases, and the comb polymer with shorter side chains makes the Zeta potential of the aluminum oxide suspension more negative, and the suspension system is more stable (Applied Surface Science, 2012, 258, 2447-2453).

The disadvantages of the prior art are: although this type of comb-shaped polymer dispersant exhibits excellent dispersibility in application, wettability is required in the process of preparing pesticide formulations to better grind the original drug to a certain particle size In addition, due to poor wettability, a large amount of foam is often produced during the sanding process, which brings certain difficulties to the preparation process.

The present invention adopts three monomers of allyltrimethylsilane, vinylpyrrolidone and maleic anhydride to obtain a terpolymer through free radical initiation. This type of comb-shaped polymer dispersant not only has good dispersibility, but also has low surface tension. Therefore, it has very good wettability at the same time.

The method of the invention can be used to synthesize the allyltrimethylsilane-vinylpyrrolidone-maleic anhydride wetting and dispersing agent which has not been reported in the literature of the prior art.

Contents of the invention

The object of the present invention is to provide allyltrimethylsilane-vinylpyrrolidone-maleic anhydride terpolymer, which has better surface wettability and dispersibility during the preparation of pesticide formulations.

Another object of the present invention is to provide a synthetic method for synthesizing allyltrimethylsilane-vinylpyrrolidone-maleic anhydride.

The object of the present invention is achieved in that a kind of allyltrimethylsilane-vinylpyrrolidone-maleic anhydride wetting and dispersing agent is expressed by general formula I:

式Ⅰ

Formula Ⅰ

In formula I _, R and _R are one of methyl, ethyl and isopropyl;

R is _one of methyl, ethyl, isopropyl and tert-butyl;

Step is as follows: 1. a kind of preparation method of allyltrimethylsilane-vinylpyrrolidone-maleic anhydride terpolymer dispersant, it is characterized in that, raw material comprises following material:

(a) Use allyltrimethylsilane, vinylpyrrolidone and maleic anhydride as monomers, the total mass of monomers is 100 parts, allyltrimethylsilane is 5-30 parts, vinylpyrrolidone is 10- 60 parts, maleic anhydride is 10-80 parts;

(b) chain transfer agent, the dosage is 0.5%-10% of the total amount of monomers;

(c) Initiator, choose azobisisobutyronitrile, 1.1'-azobis(cyclohexanecarbonitrile), 2,2'-azobisisobutylamidine dihydrochloride, 2,2'- One of azobis(2-methylpropionitrile) and 4,4'-azobis(4-cyanovaleric acid), the dosage is 0.1%-10% of the monomer;

(d) Organic solvents, the dosage is 50%-200% of the total amount of monomers;

(e) Neutralizer, the dosage is 50%-100% of the moles of carboxylic acid;

The steps include: put the chain transfer agent and solvent at the bottom of the four-necked flask, raise the temperature to 60-100°C, add the initiator and the monomer dropwise to it at the same time, react for 2-4 hours after the dropwise addition, and dropwise add Neutralizing agent, the solvent is distilled off to obtain a terpolymer dispersant product.

2. The preparation method of allyltrimethylsilane-vinylpyrrolidone-maleic anhydride terpolymer dispersant described in step 1 is characterized in that, described chain transfer agent is tri-(N, N-dimethyl One of aminoethyl)amine, tris(2-pyridylmethyl)amine, pentamethyldiethylenetriamine and N,N-dimethyldipropylenetriamine.

3. the preparation method of allyltrimethylsilane-vinylpyrrolidone-maleic anhydride terpolymer dispersant described in step 1, is characterized in that, described organic solvent is chloroform, butanone, Virahol , n-hexane, tetrahydrofuran, cyclohexanone and N,N-dimethylformamide. The neutralizing agent is one or both of sodium hydroxide, potassium hydroxide, ammonia water, sodium carbonate, triethanolamine and triethylamine.

Main points of the present invention are:

Dissolve the alkene chain transfer agent in the solvent and raise the temperature; add allyltrimethylsilane, vinylpyrrolidone and maleic anhydride solution dropwise to it, and at the same time add the solution of the initiator dropwise, and obtain an alkene chain transfer agent after a certain period of time. Propyltrimethylsilane-vinylpyrrolidone-maleic anhydride terpolymer dispersant Wetting and dispersing agent.

Existing comb polymer dispersants are mainly formed by radical polymerization of maleic anhydride, acrylic acid, hydroxyethyl acrylate, diisobutylene, styrene and allyl polyoxyethylene ether. This type of compound has excellent dispersibility but the main disadvantage is poor wettability. The present invention polymerizes the silicone monomer into the comb-type polymer dispersant so that this type of silicone-containing comb-type dispersant has a strong wetting agent.

After extensively consulting patent documents and published publications at home and abroad, no compound with the same structure as the present invention is found, nor is there any technical solution completely identical to the preparation method of the present invention. The present invention has novelty and creativity; the product of the present invention is in The pesticide industry and coating industry have broad application prospects and are practical.

The innovation point of the present invention is.

1. Allyltrimethylsilane-vinylpyrrolidone-maleic anhydride terpolymer dispersant has a novel wetting and dispersing structure.

2. The preparation process is simple and there is no environmental pollution.

3. In the process of preparing pesticide formulations, the sanding time is reduced and the production efficiency is increased.

4. During the use of pesticides, due to the strong wettability of silicone, the efficacy of pesticides is increased.

Implementation

The present invention will be further described below by way of examples, but it is not intended to limit the present invention.

Example 1:

1) Preparation of the dispersant:

Put 0.1 part of tris-(N,N-dimethylaminoethyl)amine and 20 parts of chloroform at the bottom of a four-neck flask, raise the temperature to 80°C, and dropwise add 0.5 parts of azobisisobutyronitrile dissolved in 30 parts of chloroform The obtained solution and 8 parts of allyltrimethylsilane, 15 parts of vinylpyrrolidone and 40 parts of maleic anhydride are dissolved in 80 parts of chloroform to obtain a solution, and the dropwise addition is completed to react for 2-4 hours. After the reaction is completed, add 80 parts of 30% sodium hydroxide aqueous solution, after distilling off the solvent, add water to make it 35wt% to obtain a terpolymer wetting and dispersing agent product.

2) described dispersant is measured to the dispersibility of pesticide:

Prepare imidacloprid suspension with above-mentioned dispersant, weigh 48.5 grams of imidacloprid former medicine, 4 grams self-made wetting and dispersing agent, 1 gram of magnesium aluminum silicate, 3 grams of ethylene glycol, 3 grams of 2% xanthan gum aqueous solution and 40.5 grams of water Sufficient sand grinding to a particle size of 2-5 microns to obtain imidacloprid suspension.

Weigh 2.5g of this water suspension into a beaker, add 20mL of deionized aqueous solution, stir it with a glass catalpa to disperse it evenly, then transfer the suspension to a 100L measuring cylinder with a stopper, rinse the beaker three times with deionized water, and rinse The solution is also poured into the stoppered measuring cylinder, add water until the suspension in the stoppered measuring cylinder reaches 100L, cover the stopper, and turn the stoppered measuring cylinder upside down 30 times within 1 minute. Place the graduated cylinder in a 30°C super constant temperature aqueous solution bath, and keep it still without vibration for 30 minutes. Use a straw to remove 90mL of the upper layer of suspension, and ensure that the stoppered graduated cylinder does not shake. Transfer the remaining 10L suspension to a weighed Petri dish, and rinse the measuring cylinder with distilled water to ensure that all the sediment at the bottom of the measuring cylinder is transferred to the Petri dish, and put the Petri dish in an oven at 50°C for drying , weigh m2, calculate the mass of insoluble matter M = (m2—m1), and then calculate the suspension rate according to the following formula:

Suspension rate =

Among them, 1.00 is the mass (g) of the suspension liquid added; M is the mass (g) of the sediment at the bottom of the graduated cylinder with a stopper, and N is the mass fraction (%) of the prepared suspending agent.

According to the above operation steps, the suspension ratio of the prepared dispersant to the pesticide dispersant was measured to be 95.35%.

Example 2:

1) Preparation of the dispersant:

Put 0.4 parts of tris(2-pyridylmethyl)amine and 20 parts of butanone at the bottom of a four-neck flask, raise the temperature to 80°C, and simultaneously add dropwise 0.6 parts of azobisisobutyronitrile dissolved in 30 parts of butanone and Dissolve 10 parts of allyltrimethylsilane, 18 parts of vinylpyrrolidone and 35 parts of maleic anhydride in 80 parts of methyl ethyl ketone to obtain a solution. After the dropwise addition, react for 2-4 hours. After the reaction is completed, add 70 parts of 30% Sodium hydroxide aqueous solution, after distilling off the solvent, add water to configure it to 35wt% to obtain a terpolymer wetting and dispersing agent product.

2) described dispersant is measured to the dispersibility of pesticide:

According to the operation steps described in Example 1, the suspension ratio of the above-mentioned dispersant to the pesticide dispersant was measured to be 96.45%.

Example 3:

1) Preparation of the dispersant:

Put 0.4 parts of tris(2-pyridylmethyl)amine and 20 parts of isopropanol at the bottom of a four-necked flask, raise the temperature to 80°C, and drop 0.6 parts of 1.1'-azobis(cyclohexanecarbonitrile) into it at the same time ) is dissolved in 30 parts of isopropanol and obtained solution and 8 parts of allyltrimethylsilane, 15 parts of vinylpyrrolidone and 38 parts of maleic anhydride are dissolved in 75 parts of isopropanol to obtain a solution, and the reaction 2- After 4 hours, after the reaction was completed, 85 parts of 30% sodium hydroxide aqueous solution was added thereto, and after the solvent was evaporated, water was added to make it 35wt% to obtain a terpolymer wetting and dispersing agent product.

2) described dispersant is measured to the dispersibility of pesticide:

According to the operation steps described in Example 1, the suspension rate of the above-mentioned dispersant to the pesticide dispersant was measured to be 96.07%.

Example 4:

1) Preparation of the dispersant:

Put 0.3 parts of pentamethyldiethylenetriamine and 20 parts of n-hexane at the bottom of a four-necked flask, raise the temperature to 90°C, and drop 0.5 parts of 2,2'-azobis(2-methylpropionitrile) into it at the same time Dissolve the obtained solution in 40 parts of n-hexane, 12 parts of allyltrimethylsilane, 18 parts of vinylpyrrolidone and 28 parts of maleic anhydride in 75 parts of n-hexane to obtain a solution, and react for 2-4 hours after the dropwise addition is completed. After the reaction was completed, 65 parts of 30% sodium hydroxide aqueous solution was added thereto, and after the solvent was evaporated, water was added to make it 35wt% to obtain a terpolymer wetting and dispersing agent product.

2) described dispersant is measured to the dispersibility of pesticide:

According to the operation steps described in Example 1, the suspension rate of the above-mentioned dispersant to the pesticide dispersant was measured to be 95.75%.

Example 5:

1) Preparation of the dispersant:

Put 0.2 parts of N,N dimethyldipropylenetriamine and 20 parts of tetrahydrofuran at the bottom of a four-neck flask, raise the temperature to 78°C, and drop 0.4 parts of 4,4'-azobis(4-cyanopentyl acid) dissolved in 30 parts of tetrahydrofuran, and 20 parts of allyltrimethylsilane, 15 parts of vinylpyrrolidone and 45 parts of maleic anhydride were dissolved in 90 parts of tetrahydrofuran to obtain a solution, and the dropwise reaction was completed for 2-4 hours. After the reaction was completed, 120 parts of 30% sodium hydroxide aqueous solution was added thereto, after the solvent was evaporated, water was added to make it 35wt% to obtain a terpolymer wetting and dispersing agent product.

2) described dispersant is measured to the dispersibility of pesticide:

According to the operation steps described in Example 1, the suspension rate of the above-mentioned dispersant to the pesticide dispersant was measured to be 97.22%.

Claims (7)

1. The preparation method of the allyl trimethyl silane-vinyl pyrrolidone-maleic anhydride terpolymer dispersing agent is characterized by comprising the following raw materials:

(a) Taking allyltrimethylsilane, vinyl pyrrolidone and maleic anhydride as monomers, wherein the total mass of the monomers is 100 parts, the allyltrimethylsilane is 5-30 parts, the vinyl pyrrolidone is 10-60 parts, and the maleic anhydride is 10-80 parts;

(b) Chain transfer agent, the dosage is 0.5% -10% of the total monomer;

(c) An initiator which is one of azodiisobutyronitrile, 1.1 '-azobis (cyclohexane carbonitrile), 2' -azobisisobutylamidine dihydrochloride, 2 '-azobis (2-methylpropanenitrile) and 4,4' -azobis (4-cyano valeric acid) and the dosage is 0.1% -10% of monomer;

(d) The dosage of the organic solvent is 50% -200% of the total monomer;

(e) The dosage of the neutralizer is 50% -100% of the mole number of carboxylic acid;

the method comprises the following steps: and (3) placing the chain transfer agent and the solvent at the bottom of the four-neck flask, heating to 60-100 ℃, simultaneously dripping the initiator and the monomer into the four-neck flask, reacting for 2-4 hours after the dripping, dripping the neutralizer into the four-neck flask after the reaction is finished, and evaporating the solvent to obtain the terpolymer dispersing agent product.

2. The method for preparing the allyl trimethylsilane-vinyl pyrrolidone-maleic anhydride terpolymer dispersing agent according to claim 1, wherein the dispersing agent comprises the following components in parts by weight: 5-30 parts of allyl trimethyl silane, 10-60 parts of vinyl pyrrolidone and 10-80 parts of maleic anhydride.

3. The method for preparing an allyltrimethylsilane-vinylpyrrolidone-maleic anhydride terpolymer dispersant of claim 1, wherein the chain transfer agent is one of tris- (N, N-dimethylaminoethyl) amine, tris (2-pyridyl) amine, pentamethyldiethylenetriamine and N, N-dimethyldipropylenetriamine.

4. The method for preparing the allyl trimethylsilane-vinyl pyrrolidone-maleic anhydride terpolymer dispersing agent according to claim 1, wherein the organic solvent is one of chloroform, butanone, isopropanol, N-hexane, tetrahydrofuran, cyclohexanone and N, N-dimethylformamide. The neutralizing agent is one or two of sodium hydroxide, potassium hydroxide, ammonia water, sodium carbonate, triethanolamine and triethylamine.

5. A process for the preparation of an allyltrimethylsilane-vinylpyrrolidone-maleic anhydride terpolymer dispersant, characterized in that the molecular formula before neutralization is of formula i, the relative molecular weight is 3000-50000, prepared by the process according to any one of claims 1-5:

formula I.

6. Use of the allyltrimethylsilane-vinylpyrrolidone-maleic anhydride terpolymer dispersant of claim 5 in the preparation of pesticide formulations and coatings.

7. Use of the allyltrimethylsilane-vinylpyrrolidone-maleic anhydride terpolymer dispersant of claim 6 in the preparation of pesticide formulations and coatings, wherein the allyltrimethylsilane-vinylpyrrolidone-maleic anhydride terpolymer dispersant is present in an amount of 2wt% to 10wt%.