CN111635518B - Composite ionic polymer dispersant and preparation method thereof - Google Patents
Composite ionic polymer dispersant and preparation method thereof Download PDFInfo
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Abstract
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.
Description
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, the 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 using cost is saved, the harm of the pesticide loss to the environment can be reduced, and the high-efficiency, safe and environment-friendly pesticide auxiliary agent is listed as item 6 of encouragement in the industry structure adjustment instruction list (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 adjustment of the lengths and the arrangement sequence of three monomer chain segments, 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 monomers
The 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.
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 polymer I to produce polymer II, the reaction formula being:
s3: introduction of an anionic active group R3According to R3Can be divided into the following different steps a) R3The group 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 is
Wherein 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 groups may be the same or different from each other, and a plurality of R's are grafted to the polymer3The 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 dispersibility of the polymeric dispersant can be adjusted by the kind and number of the anionic active groups attached to the secondary amine groups.
Detailed Description
The present invention is further illustrated by the following examples.
Example 1
Preparation of composite ionic polymer dispersant shown in formula III
First step (polymerization): firstly, 1mol of butanol (initiator) is put into an experimental device provided with a stirrer, a thermometer, a water separator and a condenser pipe, the experimental device is thoroughly dried, the whole experimental device is inerted for 3 times, finally, nitrogen is introduced for protection, the condenser is opened, a catalyst is added, the temperature is raised to 105 ℃, 5mol of ethylene oxide is uniformly pumped into the reactor under liquid by a plunger pump, the reaction is carried out for 1 hour under heat preservation, 5mol of aziridine is uniformly pumped into the reactor under liquid by the plunger pump, the reaction is carried out for 1 hour under heat preservation, 10mol of propylene oxide is uniformly pumped into the reactor under liquid by the plunger pump, the reaction is carried out for 1 hour under heat preservation, 5mol of aziridine is uniformly pumped into the reactor under liquid by the plunger pump, 3mol of ethylene oxide is uniformly pumped into the reactor under liquid by the plunger pump, and the reaction is carried out for 1 hour under heat preservation.
And step two, sealing the end, cooling to 40 ℃, slowly adding 1mol of chloromethane (end-capping reagent) from the liquid, and reacting for 1 hour.
Third step (grafting of anionic group): and uniformly dropwise adding 6mol of diethyl maleate into the reactor within 4 hours at 40 ℃, and heating to 75 ℃ for reaction for 12-48 hours. Adding 4mol of maleic anhydride into a reactor, heating to 70-90 ℃, and reacting for 6-10 hours. Neutralizing with 32% NaOH solution until the pH value is 7 +/-0.5, adding 50% solution of 1.02mol of sodium metabisulfite, stirring, heating in an oil bath to 85-115 ℃, preserving heat, stirring vigorously, and reacting for 5-10 h. Adding 2.1mol (calculated by NaOH) of sodium hydroxide solution, and continuing to carry out heat preservation reaction for 5-12 hours to obtain the required product as shown in the formula III.
Example 2
Preparation of composite ionic polymer dispersant shown in formula IV
First step (polymerization): firstly putting 1mol of butanol into an experimental device provided with a stirrer, a thermometer, a water separator and a condenser pipe, thoroughly drying the experimental device, inerting the whole experimental device for 3 times, finally introducing nitrogen for protection, starting a condenser, adding a catalyst, heating to 105 ℃, uniformly pumping 5mol of ethylene oxide into a reactor under liquid by using a plunger pump, carrying out heat preservation reaction for 1 hour, pumping 5mol of aziridine into the reactor under liquid by using the plunger pump, carrying out heat preservation reaction for 1 hour, pumping 10mol of propylene oxide into the reactor under liquid by using the plunger pump, carrying out heat preservation reaction for 1 hour, pumping 5mol of aziridine into the reactor under liquid by using the plunger pump, pumping 3mol of ethylene oxide into the reactor under liquid by using the plunger pump, and carrying out heat preservation reaction for 1 hour.
And step two, sealing the end, cooling to 40 ℃, slowly adding 1mol of chloromethane from the liquid, and reacting for 1 hour.
Third step (grafting of anionic group): adding sodium chloroacetate into a reactor at 40 ℃, fully stirring, slowly adding 99 percent of sodium hydroxide, controlling the temperature to be not more than 50 ℃ by using cooling water in the process, keeping the temperature and stirring for 1 hour, and entering the next step. Adding 1.95mol of maleic anhydride into a reactor, heating to 70-90 ℃, and reacting for 6-10 hours. Neutralizing with 32% NaOH solution until the pH value is 7 +/-0.5, adding 50% solution of 1.02mol of sodium metabisulfite, stirring, heating in an oil bath to 85-115 ℃, preserving heat, stirring vigorously, and reacting for 5-10 h. Adding 1mol of sodium hydroxide solution (calculated by NaOH) and continuing to carry out heat preservation reaction for 5-12 hours to obtain the required product shown as formula IV.
Example 3
Preparation of composite ionic polymer dispersant shown as formula V
First step (polymerization): firstly, 1mol of isooctanol is put into an experimental device provided with a stirrer, a thermometer, a water separator and a condenser pipe, the experimental device is thoroughly dried, the whole experimental device is inerted for 3 times, finally, nitrogen is introduced for protection, the condenser is started, a catalyst is added, the temperature is raised to 105 ℃, 5mol of ethylene oxide is uniformly pumped into a reactor under liquid by a plunger pump, the heat preservation reaction is carried out for 1 hour, 5mol of aziridine is uniformly pumped into the reactor under liquid by the plunger pump, the heat preservation reaction is carried out for 1 hour, 10mol of propylene oxide is uniformly pumped into the reactor under liquid by the plunger pump, the heat preservation reaction is carried out for 1 hour, 5mol of aziridine is uniformly pumped into the reactor under liquid by the plunger pump, 3mol of ethylene oxide is uniformly pumped into the reactor under liquid by the plunger pump, and the heat preservation reaction is carried out for 1 hour.
And step two, sealing the end, cooling to 40 ℃, slowly adding 1mol of chloromethane from the liquid, and reacting for 1 hour.
Third step (grafting of anionic group): and uniformly dropwise adding 6mol of diethyl maleate into the reactor within 4 hours at 40 ℃, and heating to 75 ℃ for reaction for 12-48 hours. Adding 4mol of maleic anhydride into a reactor, heating to 70-90 ℃, and reacting for 6-10 hours. Neutralizing with 32% NaOH solution until the pH value is 7 +/-0.5, adding 50% solution of 1.02mol of sodium metabisulfite, stirring, heating in an oil bath to 85-115 ℃, preserving heat, stirring vigorously, and reacting for 5-10 h. Adding 2.1mol (calculated by NaOH) of sodium hydroxide solution, and continuing to carry out heat preservation reaction for 5-12 hours to obtain the required product as shown in the formula V.
Example 4
Preparation of composite ionic polymer dispersant shown as formula VI
First step (polymerization): firstly putting 1mol of butanol into an experimental device provided with a stirrer, a thermometer, a water separator and a condenser pipe, thoroughly drying the experimental device, inerting the whole experimental device for 3 times, finally introducing nitrogen for protection, starting a condenser, adding a catalyst, heating to 105 ℃, uniformly and hydraulically putting 5mol of ethylene oxide into a reactor by using a plunger pump, carrying out heat preservation reaction for 1 hour, uniformly and hydraulically putting 5mol of aziridine into the reactor by using the plunger pump, carrying out heat preservation reaction for 1 hour, uniformly and hydraulically putting 10mol of propylene oxide into the reactor by using the plunger pump, carrying out heat preservation reaction for 1 hour, uniformly and hydraulically putting 5mol of aziridine into the reactor by using the plunger pump, uniformly and hydraulically putting 3mol of ethylene oxide into the reactor by using the plunger pump, and carrying out heat preservation reaction for 1 hour.
And step two, sealing the end, cooling to 40 ℃, slowly adding 1mol of chloromethane from the liquid, and reacting for 1 hour.
Third step (grafting of anionic group): adding sodium chloroacetate into a reactor at 40 ℃, fully stirring, slowly adding 99% of sodium hydroxide, controlling the temperature to be not more than 50 ℃ by using cooling water in the process, keeping the temperature and stirring for 1 hour, and entering the next step. Adding 1.95mol of maleic anhydride into a reactor, heating to 70-90 ℃, and reacting for 6-10 hours. Neutralizing with a 32% NaOH solution until the pH value is 7 +/-0.5, adding a 50% solution of 1.02mol of sodium metabisulfite, stirring, heating in an oil bath to 85-115 ℃, preserving heat, stirring vigorously, and reacting for 5-10 h. Adding 1mol of sodium hydroxide solution (calculated by NaOH) and continuing to carry out heat preservation reaction for 5-12 hours to obtain the required product as the formula X.
Example 5
Preparation of composite ionic polymer dispersant shown as formula VII
First step (polymerization): firstly putting 1mol of octadecanol into an experimental device provided with a stirrer, a thermometer, a water separator and a condenser pipe, thoroughly drying the experimental device, inerting the whole experimental device for 3 times, finally introducing nitrogen for protection, starting a condenser, adding a catalyst, heating to 105 ℃, uniformly pumping 5mol of ethylene oxide into a reactor under liquid by using a plunger pump, carrying out heat preservation reaction for 1 hour, uniformly pumping 5mol of aziridine into the reactor under liquid by using the plunger pump, carrying out heat preservation reaction for 1 hour, pumping 10mol of propylene oxide into the reactor under liquid by using the plunger pump, carrying out heat preservation reaction for 1 hour, uniformly pumping 5mol of aziridine into the reactor under liquid by using the plunger pump, pumping 3mol of ethylene oxide into the reactor under liquid by using the plunger pump, and carrying out heat preservation reaction for 1 hour.
And step two, sealing the end, cooling to 40 ℃, slowly adding 1mol of chloromethane from the liquid, and reacting for 1 hour.
Third step (grafting of anionic group): and uniformly dropwise adding 6mol of diethyl maleate into the reactor within 4 hours at 40 ℃, and heating to 75 ℃ for reaction for 12-48 hours. Adding 4mol of maleic anhydride into a reactor, heating to 70-90 ℃, and reacting for 6-10 hours. Neutralizing with a 32% NaOH solution until the pH value is 7 +/-0.5, adding a 50% solution of 1.02mol of sodium metabisulfite, stirring, heating in an oil bath to 85-115 ℃, preserving heat, stirring vigorously, and reacting for 5-10 h. Adding 2.1mol (calculated by NaOH) of sodium hydroxide solution, and continuing to perform heat preservation reaction for 5-12 hours to obtain the required product shown in the formula XI.
Example 6.
Preparation of composite ionic polymer dispersant shown as formula VIII
First step (polymerization): firstly putting 1mol of butanol into an experimental device provided with a stirrer, a thermometer, a water separator and a condenser pipe, thoroughly drying the experimental device, inerting the whole experimental device for 3 times, finally introducing nitrogen for protection, starting a condenser, adding a catalyst, heating to 105 ℃, uniformly pumping 5mol of ethylene oxide into a reactor under liquid by using a plunger pump, carrying out heat preservation reaction for 1 hour, pumping 5mol of aziridine into the reactor under liquid by using the plunger pump, carrying out heat preservation reaction for 1 hour, pumping 10mol of propylene oxide into the reactor under liquid by using the plunger pump, carrying out heat preservation reaction for 1 hour, pumping 5mol of aziridine into the reactor under liquid by using the plunger pump, pumping 3mol of ethylene oxide into the reactor under liquid by using the plunger pump, and carrying out heat preservation reaction for 1 hour.
And step two, sealing the end, cooling to 40 ℃, slowly adding 1mol of chloromethane from the liquid, and reacting for 1 hour.
Third step (anionic group access): adding sodium chloroacetate into a reactor at 40 ℃, fully stirring, slowly adding 99% of sodium hydroxide, controlling the temperature to be not more than 50 ℃ by using cooling water in the process, keeping the temperature and stirring for 1 hour, and entering the next step. Adding 1.95mol of maleic anhydride into a reactor, heating to 70-90 ℃, and reacting for 6-10 hours. Neutralizing with 32% NaOH solution until the pH value is 7 +/-0.5, adding 50% solution of 1.02mol of sodium metabisulfite, stirring, heating in an oil bath to 85-115 ℃, preserving heat, stirring vigorously, and reacting for 5-10 h. Adding 1mol of sodium hydroxide solution (calculated by NaOH) and continuing to carry out heat preservation reaction for 5-12 hours to obtain the required product shown in the formula VIII.
Example 7
Preparation of composite ionic polymer dispersant shown as formula IX
First step (polymerization): firstly putting 1mol of octadecanol into an experimental device provided with a stirrer, a thermometer, a water separator and a condenser pipe, thoroughly drying the experimental device, inerting the whole experimental device for 3 times, finally introducing nitrogen for protection, starting a condenser, adding a catalyst, heating to 105 ℃, uniformly pumping 5mol of ethylene oxide into a reactor under liquid by using a plunger pump, carrying out heat preservation reaction for 1 hour, uniformly pumping 5mol of aziridine into the reactor under liquid by using the plunger pump, carrying out heat preservation reaction for 1 hour, pumping 10mol of propylene oxide into the reactor under liquid by using the plunger pump, carrying out heat preservation reaction for 1 hour, uniformly pumping 5mol of aziridine into the reactor under liquid by using the plunger pump, pumping 3mol of ethylene oxide into the reactor under liquid by using the plunger pump, and carrying out heat preservation reaction for 1 hour.
And step two, sealing the end, cooling to 40 ℃, slowly adding 1mol of benzyl chloride from the liquid, and reacting for 1 hour.
Third step (grafting of anionic group): and uniformly dropwise adding 6mol of diethyl maleate into the reactor within 4 hours at 40 ℃, and heating to 75 ℃ for reaction for 12-48 hours. Adding 4mol of maleic anhydride into a reactor, heating to 70-90 ℃, and reacting for 6-10 hours. Neutralizing with 32% NaOH solution until the pH value is 7 +/-0.5, adding 50% solution of 1.02mol of sodium metabisulfite, stirring, heating in an oil bath to 85-115 ℃, preserving heat, stirring vigorously, and reacting for 5-10 h. Adding 2.1mol of sodium hydroxide solution (calculated by NaOH) and continuing to carry out heat preservation reaction for 5-12 hours to obtain the required product as formula IX.
Example 8
Preparation of composite ionic polymer dispersant shown as formula IX
: first step (polymerization): firstly putting 1mol of butanol into an experimental device provided with a stirrer, a thermometer, a water separator and a condenser pipe, thoroughly drying the experimental device, inerting the whole experimental device for 3 times, finally introducing nitrogen for protection, starting a condenser, adding a catalyst, heating to 105 ℃, uniformly pumping 5mol of ethylene oxide into a reactor under liquid by using a plunger pump, carrying out heat preservation reaction for 1 hour, pumping 5mol of aziridine into the reactor under liquid by using the plunger pump, carrying out heat preservation reaction for 1 hour, pumping 10mol of propylene oxide into the reactor under liquid by using the plunger pump, carrying out heat preservation reaction for 1 hour, pumping 5mol of aziridine into the reactor under liquid by using the plunger pump, pumping 3mol of ethylene oxide into the reactor under liquid by using the plunger pump, and carrying out heat preservation reaction for 1 hour.
And step two, sealing the end, cooling to 40 ℃, slowly adding 1mol of benzyl chloride from the liquid, and reacting for 1 hour.
Third step (grafting of anionic group): adding sodium chloroacetate into a reactor at 40 ℃, fully stirring, slowly adding 99% of sodium hydroxide, controlling the temperature to be not more than 50 ℃ by using cooling water in the process, keeping the temperature and stirring for 1 hour, and entering the next step. Adding 1.95mol of maleic anhydride into a reactor, heating to 70-90 ℃, and reacting for 6-10 hours. Neutralizing with 32% NaOH solution until the pH value is 7 +/-0.5, adding 50% solution of 1.02mol of sodium metabisulfite, stirring, heating in an oil bath to 85-115 ℃, preserving heat, stirring vigorously, and reacting for 5-10 h. Adding 1mol of sodium hydroxide solution (calculated by NaOH) and continuing to carry out heat preservation reaction for 5-12 hours to obtain the required product as formula IX.
Example 9
Preparation of composite ionic polymer dispersant shown as formula X
First step (polymerization): firstly putting 1mol of octadecanol into an experimental device provided with a stirrer, a thermometer, a water separator and a condenser pipe, thoroughly drying the experimental device, inerting the whole experimental device for 3 times, finally introducing nitrogen for protection, starting a condenser, adding a catalyst, heating to 105 ℃, uniformly pumping 5mol of ethylene oxide into a reactor under liquid by using a plunger pump, carrying out heat preservation reaction for 1 hour, uniformly pumping 5mol of aziridine into the reactor under liquid by using the plunger pump, carrying out heat preservation reaction for 1 hour, pumping 10mol of propylene oxide into the reactor under liquid by using the plunger pump, carrying out heat preservation reaction for 1 hour, uniformly pumping 5mol of aziridine into the reactor under liquid by using the plunger pump, pumping 3mol of ethylene oxide into the reactor under liquid by using the plunger pump, and carrying out heat preservation reaction for 1 hour.
And secondly, sealing the end, reducing the temperature to 40 ℃, slowly adding 1mol of C12-14 fatty acyl chloride from the liquid to react for 1 hour.
Third step (grafting of anionic group): and uniformly dropwise adding 6mol of diethyl maleate into the reactor within 4 hours at 40 ℃, and heating to 75 ℃ for reaction for 12-48 hours. Adding 4mol of maleic anhydride into a reactor, heating to 70-90 ℃, and reacting for 6-10 hours. Neutralizing with 32% NaOH solution until the pH value is 7 +/-0.5, adding 50% solution of 1.02mol of sodium metabisulfite, stirring, heating in an oil bath to 85-115 ℃, preserving heat, stirring vigorously, and reacting for 5-10 h. Adding 2.1mol of sodium hydroxide solution (calculated by NaOH) and continuing to carry out heat preservation reaction for 5-12 hours to obtain the required product as formula XIIV.
Example 10
Preparation of composite ionic polymer dispersant shown in formula XI
First step (polymerization): firstly putting 1mol of butanol into an experimental device provided with a stirrer, a thermometer, a water separator and a condenser pipe, thoroughly drying the experimental device, inerting the whole experimental device for 3 times, finally introducing nitrogen for protection, starting a condenser, adding a catalyst, heating to 105 ℃, uniformly pumping 5mol of ethylene oxide into a reactor under liquid by using a plunger pump, carrying out heat preservation reaction for 1 hour, pumping 5mol of aziridine into the reactor under liquid by using the plunger pump, carrying out heat preservation reaction for 1 hour, pumping 10mol of propylene oxide into the reactor under liquid by using the plunger pump, carrying out heat preservation reaction for 1 hour, pumping 5mol of aziridine into the reactor under liquid by using the plunger pump, pumping 3mol of ethylene oxide into the reactor under liquid by using the plunger pump, and carrying out heat preservation reaction for 1 hour.
And secondly, sealing the end, cooling to 40 ℃, slowly adding 1mol of C12-14 fatty acyl chloride from the liquid to react for 1 hour.
Third step (grafting of anionic group): adding sodium chloroacetate into a reactor at 40 ℃, fully stirring, slowly adding 99% of sodium hydroxide, controlling the temperature to be not more than 50 ℃ by using cooling water in the process, keeping the temperature and stirring for 1 hour, and entering the next step. Adding 1.95mol of maleic anhydride into a reactor, heating to 70-90 ℃, and reacting for 6-10 hours. Neutralizing with a 32% NaOH solution until the pH value is 7 +/-0.5, adding a 50% solution of 1.02mol of sodium metabisulfite, stirring, heating in an oil bath to 85-115 ℃, preserving heat, stirring vigorously, and reacting for 5-10 h. Adding 1mol of sodium hydroxide solution (calculated by NaOH) and continuing to carry out heat preservation reaction for 5-12 hours to obtain the required product shown in the formula XI.
Test example 1
The emulsifying power was tested as follows: 150SN is base oil, the adding amount is 5-20%, 5% of the prepared sample is added, the sample is uniformly emulsified in pure water after being stirred, and milky white homogeneous phase does not allow oil to pass through.
| Sample (I) | 5％ | 10％ | 15％ | 20％ |
| Example 1 | By passing | By passing | By passing | By passing |
| Example 2 | By passing | By passing | By passing | By passing |
| Example 3 | By passing | By passing | By passing | By passing |
| Example 4 | By passing | By passing | By passing | By passing |
| Example 5 | By passing | By passing | By passing | Failed through |
| Example 6 | By passing | By passing | By passing | By passing |
| Example 7 | By passing | By passing | By passing | By passing |
| Example 8 | By passing | By passing | By passing | By passing |
| Example 9 | By passing | By passing | By passing | By passing |
| Example 10 | By passing | By passing | By passing | By passing |
Basically, the samples of all the examples have stronger emulsifying power and can be used for emulsifying and dispersing in an oil-in-water system.
Test example 2
For example 10, the test found that it is excellent in hard water resistance, the hard water resistance test method is as follows: and (3) adding 5000-30000 PPM of hard water into 3% of the sample prepared in the embodiment, and stirring for ten minutes, wherein the sample is in a milk white homogeneous phase state and is in a non-passing state when layering or soap precipitation occurs.
Basically, the hard water resistance of examples 1 to 10 is better than that of the comparative sample.
Test example 3
The dispersing performance test method comprises the following steps of synthesizing a dispersing solution according to the following formula, using the dispersing agent in examples 1-10, and comparing the performances as follows:
the data for the prepared dispersion samples are as follows:
it can be seen that all the examples can be used for preparing the dispersant of inorganic powder, and the stability is strong.
Claims (14)
1. A polymeric dispersant, characterized in that said polymeric dispersant has the following general formula:
wherein, in different chain segments of the dispersant, structural monomers
The 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 is1In alkanes, alkenes, or aromaticsA, R2Is one of straight-chain alkane, branched-chain alkane and aromatic hydrocarbon, R3Is composed of
Wherein M is Li, Na, K or NH4One or more of them, R in different chain segments3Are the same or different.
2. 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.
3. The polymeric dispersant of claim 2, wherein said initiator is R-containing1Saturated fatty alcohols, unsaturated fatty alcohols or phenols.
4. The polymeric dispersant of claim 2, wherein said end-capping agent is a compound containing R2Chloride R of2-Cl。
5. The polymeric dispersant of claim 4, wherein the end-capping agent is methyl chloride, ethyl chloride, or benzyl chloride.
6. A polymeric dispersant according to claim 2, characterized in that when R is3The radical is
When 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.
7. The polymeric dispersant of claim 6, wherein the maleate has the formula
Wherein R is5And R6Is saturated alkane with 1-6 carbon atoms.
8. The polymer dispersant of claim 6 or 7, wherein the molar number of the secondary amine groups of the polymer II is: 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.
9. A polymeric dispersant according to claim 2, characterized in that when R is3The radical is
When 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.
10. The polymeric dispersant according to claim 9, 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 ℃.
11. A polymeric dispersant according to claim 2, characterized in that when R is3The group is
When 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.
12. The polymeric dispersant according to claim 11, 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 ℃.
13. The polymeric dispersant according to claim 11, characterized in that the molar number of said amidation product is: sulfite 1: (0.4-0.68).
14. The polymeric dispersant of claim 11 or 13, wherein said sulfite is Li2SO3，Na2SO3，K2SO3，(NH4)2SO3，LiHSO3，NaHSO3，KHSO3，NH4HSO3，Li2S2O5，Na2S2O5，K2S2O5，(NH4)2S2O5One kind of (1).
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| US6156720A (en) * | 1998-06-23 | 2000-12-05 | Basf Aktiengesellschaft | Propoxylated/ethoxylated polyalkyleneimine dispersants |
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