阅读说明：本技术 一种复合离子型聚合物分散剂及其制备方法 (Composite ionic polymer dispersant and preparation method thereof ) 是由 杨全文 于 2020-05-06 设计创作，主要内容包括：本发明涉及一种复合离子型聚合物分散剂及其制备方法,属于分散剂领域,通过三种单体链段长度和排列顺序的调整,可以针对不同的原药,提供相匹配的分散剂结构,从而获得良好的分散体；通过封端和输水段的排布,可以控制分散剂的起泡,不需再另加消泡剂；通过仲胺基上接入阴离子活性基团的种类和数量,可以调整聚合物分散剂的抗硬水能力、水溶性和分散能力。(The invention relates to a composite ionic polymer dispersant and a preparation method thereof, belonging to the field of dispersants, wherein a matched dispersant structure can be provided for different raw medicines by adjusting the lengths and the arrangement sequence of chain segments of three monomers, so that a good dispersant is obtained; the foaming of the dispersing agent can be controlled by the arrangement of the end capping and the water delivery section, and no additional defoaming agent is needed; the hard water resistance, water solubility and dispersing ability of the polymer dispersant can be adjusted by the kind and number of the anionic active groups grafted on the secondary amine groups.)

1. A polymeric dispersant, characterized in that said polymeric dispersant has the following general formula:

wherein, in different chain segments of the dispersantStructural unitThe positions of a, b and c are the same or different, c is not zero and a and b are not zero at the same time, R is₁Is one of alkane, alkene or aromatic hydrocarbon, R₂Is one of straight-chain alkane, branched-chain alkane and aromatic hydrocarbon, R₃Is composed of

One of (1), R in different chain segments₃Are identical or different.

2. The polymeric dispersant of claim 1, wherein R is selected from the group consisting of₃M in the structural formula is Li, NA, K or NH₄One or more of them.

3. A method of preparing the polymeric dispersant of claim 1, comprising the steps of:

s1: will contain R₁Adding the initiator, ethylene oxide, propylene oxide and aziridine into a reactor, and carrying out ring-opening polymerization reaction at a polymerization temperature under the action of a catalyst to obtain a polymer I;

s2: cooling, adding a solvent containing R₂The end capping agent is subjected to polymerization reaction for end capping to obtain a polymer II;

s3: introduction of R₃And (c) obtaining the polymeric dispersant.

4. A polymer composition according to claim 3The powder is characterized in that the initiator contains R₁Saturated fatty alcohols, unsaturated fatty alcohols, phenols or fatty acids.

5. The polymeric dispersant of claim 3, wherein said end-capping agent is R-containing₂Chloride R of₂-Cl。

6. The polymeric dispersant of claim 5, wherein said end-capping reagent is methyl chloride, ethyl chloride, benzyl chloride or fatty acid chloride.

7. A polymeric dispersant according to claim 3, characterized in that when R is₃The radical isWhen R is introduced into S3₃The method of the group is as follows: adding maleate to perform Michael addition reaction with the secondary amine group of the polymer II, adding a hydrolysis reagent containing M, and hydrolyzing the obtained product under alkaline conditions.

8. The polymeric dispersant of claim 7, wherein the maleate ester has the formula

Wherein R is₅And R₆Is saturated alkane with 1-6 carbon atoms.

9. The polymeric dispersant according to claim 7 or 8, characterized in that the molar number of secondary amine groups of the polymer II: mole number of maleate 1: (0.25-1), the reaction temperature is 30-150 ℃, and the maleic ester is dropwise added for 3-6 h.

10. A polymeric dispersant according to claim 3, characterized in that when R is₃The radical isWhen R is introduced into S3₃The method of the group is as follows: chloroacetate was added to carry out elimination reaction with the secondary amine group of polymer II.

11. The polymeric dispersant according to claim 10, wherein the molar number of secondary amine groups of the polymer II is: the mole number of the chloracetate is 1 (0.25-1), and the reaction temperature is 90-100 ℃.

12. A polymeric dispersant according to claim 3, characterized in that when R is₃The radical isWhen R is introduced into S3₃The method of the group is as follows: adding maleic anhydride, carrying out amidation reaction with the secondary amine group of the polymer II, and adding sulfite containing M into the amidation product to carry out sulfonation reaction.

13. The polymeric dispersant according to claim 12, wherein the molar number of secondary amine groups of the polymer II is: mole number of maleic anhydride 1: (0.25-1) and the reaction temperature is 50-150 ℃.

14. The polymeric dispersant according to claim 12, characterized in that the molar number of said amidation product is: sulfite 1: (0.4-0.68).

15. The polymeric dispersant of claim 12 or 14, wherein said sulfite is Li₂SO₃，Na₂SO₃，K₂SO₃，(NH₄)₂SO₃，LiHSO₃，NaHSO₃，KHSO₃，NH₄HSO₃，Li₂S₂O₅，Na₂S₂O₅，K₂S₂O₅，(NH₄)₂S₂O₅One kind of (1).

Technical Field

The invention relates to a composite ionic polymer dispersant and a preparation method thereof, belonging to the field of dispersants.

Background

The dispersant has wide application, particularly in the field of pesticides, a proper functional dispersant can greatly improve the utilization efficiency of pesticides on crops, reduce the using amount of the pesticides and reduce the loss rate of the pesticides, so that the use cost is saved, the harm of the pesticide loss to the environment can be reduced, and the efficient, safe and environment-friendly pesticide auxiliary agent is listed as item 6 of encouragement in the industrial structure adjustment guidance catalog (2019) of the national development and reform Commission.

The dispersant is one of the key components of the water dispersible granule, and is adsorbed on an oil-water interface or the surface of solid particles, so that the aggregation of solid or liquid particles in a dispersion system is hindered and prevented, and the uniform dispersion is kept for a long time.

The polymer dispersant widely used at present is polyacid salts, the synthesis mode of the polymer dispersant is mostly alternate copolymerization initiated by free radicals, the molecular structure is relatively fixed, and the polymer dispersant is difficult to adapt to the application requirements of different raw medicines.

Disclosure of Invention

In order to obtain better performance and adapt to the requirement of different raw pesticide on dispersibility, the invention adopts more flexible polymerization and reaction, and utilizes the characteristic that the ring-opening polymerization reaction of ethylene oxide, propylene oxide and aziridine can not be automatically terminated to synthesize the polymer of alkyl-terminated ethylene oxide-propylene oxide-aziridine, which is used as the framework of the dispersing agent. The chain segment length and the arrangement sequence of the three monomers and the end capping group of the polymer can be adjusted according to different application requirements, and the dispersing agent which is more matched with the original medicine can be obtained by linking the active group containing anions through active hydrogen in the secondary amino.

According to the invention, through adjusting the lengths and the arrangement sequence of the chain segments of the three monomers, matched dispersant structures can be provided for different raw medicines, so that a good dispersion is obtained; the foaming of the dispersing agent can be controlled by the arrangement of the end capping and the water delivery section, and no additional defoaming agent is needed; the hard water resistance, water solubility and dispersing ability of the polymer dispersant can be adjusted by the kind and number of the anionic active groups grafted on the secondary amine groups.

The polymer dispersant of the invention can show different ionicity under different medium conditions, has certain adsorption and desorption functions on the dispersed medium, and can meet certain special processes.

The invention is realized by the following technical scheme:

a polymeric dispersant, characterized in that said polymeric dispersant has the following general formula:

wherein, in different chain segments of the dispersant, structural monomersThe positions of a, b and c are the same or different, c is not zero and a and b are not zero at the same time, R is₁Is one of alkane, alkene or aromatic hydrocarbon, R₂Is one of straight-chain alkane, branched-chain alkane and aromatic hydrocarbon, R₃Is composed ofOne of (1), R in different chain segments₃Are identical or different.

The reaction mechanism employed in the present invention is (the number of the secondary amine to which the anionic group is attached depends on the secondary amine group and the molar ratio of the reaction, not specifically indicated in the reaction formula)

S1: from saturated or unsaturated fatty alcohols, or phenols, or fatty acids (containing R)₁And) as initiator, initiating polymerization under the action of catalyst, according to the characteristic that the reaction of polyethylene oxide, propylene oxide and polyethylenimine can not be terminated spontaneously, the order and proportion of monomer addition can be changed according to the requirements of different applications, so as to obtain different chain segment lengths and chain segment arrangement, and obtain polymer I, wherein the reaction formula is as follows:

wherein, the catalyst is strong base, alkali metal salts such as NaOH, KOH, sodium methoxide, sodium ethoxide and the like are preferred, the polymerization temperature is 100-120 ℃, the order and proportion of adding monomers can be changed according to the characteristic that the reaction of polyethylene oxide, propylene oxide and polyethylenimine can not be terminated spontaneously, and polymers with different chain segment distribution, HLB value and secondary amine content can be obtained, thereby being suitable for the requirements of different application scenes.

S2: selecting a suitable blocking agent R₂-Cl (e.g. methyl chloride, ethyl chloride, benzyl chloride, fatty acid chloride, etc.) under suitable reaction conditions to cap the polymer I to produce a polymer II, andthe formula is as follows:

s3: introduction of an anionic active group R₃According to R₃Can be divided into the following different steps a) R₃The radical is

The Michael addition reaction is carried out on the secondary amine group on the polymer II and maleic acid ester, and maleic acid ester group is introduced into the polymer II

And then the pH value of the product is increased to hydrolyze ester groups in the maleic acid ester, a hydrolysis reagent containing M is added under the alkaline condition to hydrolyze ester groups in the reactant orthomaleic acid ester to obtain the dispersant, and the hydrolyzed alkyl alcohol is left in the reactant as a solvent.

Wherein the maleate used isWherein R is₅And R₆Is saturated alkane with 1-6 carbon atoms.

Wherein, the mole number of the secondary amine groups of the polymer II: mole number of maleate 1: (0.25-1), the reaction temperature is 0-300 ℃, and preferably 30-150 ℃; in order to prevent side reaction, maleic acid ester is dropwise added for 3-6 hours; the reaction is protected by nitrogen; the catalyst can be selected from alkali metal salts such as NaOH, KOH, sodium methoxide, sodium ethoxide and the like; the hydrolytic reagent can be selected from KOH, LiOH, NH3.H2O, Na2CO3, K2CO3, (NH)₄)₂CO3, and the like.

b)R₃The radical is

Removing polymer II and chloroacetate containing M to obtain the dispersant by grafting acetic acid group on the secondary amine group in the polymer II, wherein the reaction formula is

Wherein, the mole number of the secondary amine groups of the polymer II: mole number of maleic anhydride 1: (0.25-1), the reaction temperature is 80-110 ℃, and preferably 90-100 ℃.

c)R₃The radical is

Carrying out amidation reaction on the polymer II and maleic anhydride to obtain an amidated product, adding different alkalis to neutralize the amidated product to be neutral according to needs, and carrying out sulfonation reaction on the amidated product and a sulfite solution to obtain the dispersing agent, wherein the reaction formula is

Wherein, the mole number of the secondary amine groups of the polymer II: mole number of maleic anhydride 1: (0.25-1), the reaction temperature is 30-220 ℃, preferably 50-150 ℃, and nitrogen is introduced for protection; moles of amidation product: sulfite 1: (0.4-0.68), the sulfonation reaction is protected by nitrogen to reduce the product chroma, and the sulfite can use Li₂SO₃，Na₂SO₃，K₂SO₃，(NH₄)₂SO₃，LiHSO₃，NaHSO₃，KHSO₃，NH₄HSO₃，Li₂S₂O₅，Na₂S₂O₅，K₂S₂O₅，(NH₄)₂S₂O₅And the like.

Wherein R in each segment monomer is present throughout the polymeric dispersant₃The radicals, which may be identical or different from one another, are polymerizedIn which plural kinds of R are grafted₃The groups may give better performance to the dispersant.

The invention has the beneficial effects that: (1) the invention adopts more flexible polymerization reaction, and utilizes the characteristic that the ring-opening polymerization reaction of ethylene oxide, propylene oxide and aziridine can not be automatically terminated to synthesize the polymer of ethylene oxide-propylene oxide-aziridine which is terminated by alkyl and is used as the framework of the dispersant. The chain segment length and the arrangement sequence of the three monomers and the end capping group of the polymer can be adjusted according to different application requirements, and the dispersing agent which is more matched with the original medicine can be obtained by linking the active group containing anions through active hydrogen in the secondary amino; (2) the foaming of the dispersing agent can be controlled by the arrangement of the end capping and the water delivery section, and no additional defoaming agent is needed; (3) the hard water resistance, water solubility and dispersing ability of the polymer dispersant can be adjusted by the kind and number of the anionic active groups grafted on the secondary amine groups.

Detailed Description

The present invention is further illustrated by the following examples.