CN105153382A - Continuous production method of polymer surfactant for pesticides - Google Patents
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Abstract
The present invention relates to a continuous production method of a polymer surfactant for pesticides. The continuous production method comprises: 1) pouring reactants into a pre-mixing kettle, uniformly mixing, and replacing with nitrogen to obtain a premix; 2) pouring the premix in the step (1) into a polymerization kettle, replacing with nitrogen, heating to a temperature of 50-150 DEG C, controlling the pressure at -0.05-1.0 MPa until forming a macromolecule monomer chain transfer agent, and continuously introducing the premix in the step (1) into the polymerization kettle until achieving a full state and overflowing, wherein the time is controlled to 1-5 h; 3) adding the overflowing material in the step 2) into an aging kettle, continuously carrying out a polymerization reaction, and maintaining the residence time at 1-2 h; and 4) making the material in the step 3) alternately enter at least two subsequent neutralization kettles, adding an alkali aqueous solution in a dropwise manner, and carrying out neutralization to obtain the product. A purpose of the present invention is to provide the continuous production method of the polymer surfactant for pesticides, wherein the polymer surfactant prepared through the method has characteristics of narrow molecular weight distribution, stable product quality, energy consumption saving, and the like.
Description
Technical field
The present invention relates to agricultural chemicals polymeric surface active agent preparation method, specifically, is a kind of method that the programmable agricultural chemicals polymeric surface active agent of molecular structure is prepared in serialization.
Background technology
Based on the theory of safety, ecology, environment and Sustainable development, people propose higher requirement just day by day to agricultural chemicals and pesticide preparation.To the requirement of pesticide preparation, can be summarized as: safety, friendly, efficient, economical and convenient.For realizing this target, water baseization of pesticide preparation, it is wherein one of most important developing direction.The pesticide formulation of water baseization have water suspending agent (SC), aqueous emulsion (EW), suspension emulsion (SE), suspension seed-coating agent (FS), micro-capsule suspension (CS), aqua (SL), microemulsion (ME) etc.So-called water baseization, is by the matrix of water as pesticide preparation, obviously can derives a series of strong point: (1) can save considerable aromatic hydrocarbon resource, significantly reduces the tooling cost of preparation; (2) processing and the environment for use of preparation is improved; (3) reduce the toxicity of preparation, alleviate preparation to residual in crop of the poisoning of crop and toxic substance; (4) preparation no longer has inflammable, explosive danger, improves the security of preparation in storing and use procedure, and corresponding reduction is to the requirement of packaging, storing; (5) pollution that the ecotope such as soil, underground water is caused is alleviated; (6) solvent-free smell, alleviates the stimulation etc. to eye, larynx, nasal mucosa and skin; This is undoubtedly a desirable choice.But most pesticidal active substance is also water insoluble, even can there is degraded and reaction in some, this just needs us to overcome many technical barriers for this reason in water.
Polymeric surface active agent is a very important auxiliary agent in water base chemical preparation, and efficient polymeric surface active agent can solve chemistry and the physical stability of water-based pesticide preparation.Usually, polymeric surface active agent is by different vinyl monomers, under initiator effect, be polymerized, neutralization is formed again, product has the side chain of the hydrophobic Long carbon chain of skeleton and different functional groups, and can be prepared the dispersion agent or emulsifying agent that meet the different needs of water-based pesticide chemical preparation by Molecular regulator amount, side chain functionalities and distribution thereof, molecular formula is shown in Fig. 1.The distinctive structure of polymeric surface active agent, can in pesticide processing process under sand milling, shearing or instant airflow pulverizing External Force Acting, realize multi-point-anchoring with agricultural chemicals particle or drop, multilayer is adsorbed, adsorption thickness is large, reduce the surface of former medicine " exposed ", improve intergranular lubrication, polymeric surface active agent side chain can stretch in water medium, greatly sterically hindered, reduce auxiliary dosage, reduce Ostwald ripening degree, facilitate the stable of water base chemical preparation system.
Traditional agricultural chemicals polymeric surface active agent generally adopts intermittence type polymerization method, the distribution of product skeletal chain and functional group produces larger change because of the microvariations of reaction conditions (as temperature, pressure, rate of addition etc.), is unfavorable for the stable of quality product; As CN200710025659.2 has reported, polymeric monomer is disposable to add at the bottom of still, other function monomer once or is continuously added dropwise in still, solution polymerization is there is under initiator effect, what formed through neutralization can be used for agricultural chemicals suspension agent macromolecule dispersing agent, because reaction causes rate of polymerization wayward with the different meeting of the concentration of late monomer early stage, finally cause product quality variance larger; As realized the serialization of polymeric surface active agent polymerization process, effectively can improve plant factor, shorten the production cycle, reducing energy consumption, the stability of improving the quality of products.
Traditional free-radical polymerized technology, reaction conditions is gentle, but molecular weight is uncontrollable, molecular weight distribution is wider, and the molecular sequence structure of needs effectively cannot be obtained by control feed rate or order, because functional group's distribution can not effectively control, this dispersion agent can not effectively provide stable dispersing property, and facts have proved that its resistance to ionic strength is more weak.Unsaturated carboxylic acid and unsaturated monomer is adopted to issue raw free radical random copolymerization in initiator effect as CN200810146660.5 discloses, the class polycarboxylate polymeric dispersant formed, adopt product molecular weight distribution index reached more than 2.5 prepared by the method, traditional free-radical polymerized technology is initiation soon, soon growth, height shifts, stops soon, the macromolecular compound of specified structure cannot be obtained, product molecular weight distribution is wide, to raw material and catalyst selectivity wide.And the free-radical polymerized technology of reversible addition cleavage activity (RAFT technology) combines conventional free radical copolymerization and ionic polymerization feature, by forming dormancy kind to the reversible transfer of special chain transfer agent, and the concentration of hierarchy of control dormancy kind and spike is carried out with the quick permutoid reaction that this reversible chemical balances, realize polymer molecular structure can design, molecular mass and molecule segment controllable object.
summary of the invention:
The object of this invention is to provide a kind of agricultural chemicals polymeric surface active agent continuous preparation method, the agricultural chemicals polymeric surface active agent narrow molecular weight distribution prepared by the method, constant product quality, the features such as energy efficient.More outstanding is that the present invention adopts reversible addition cleavage activity radical polymerization technique (RAFT technology), enhances the designability of molecular structure.
Adopt tank reactor in the present invention, and premix still should be comprised, polymerization reaction kettle, aging still, selectivity increase drip still, in and still and spray-dryer.The premix still of product, polymerization reaction kettle and aging still preferably more to be overlapped, to realize the preparation of block product.
Technical scheme of the present invention is as follows: a kind of agricultural chemicals polymeric surface active agent continuous prodution way, and it is made up of following steps:
Step 1: premix, drops into the chain-transfer agent (RAFT reagent) of metering, initiator, solvent and polymerization single polymerization monomer in premix still, mixes, and with nitrogen replacement, temperature controls at-20 ~ 50 degree, pressure 0 ~ 1.0MPa;
Step 2: step 1 mixture dropping into metering in polymerization reaction kettle, with nitrogen replacement, be warming up to 50 ~ 150 degree, pressure-controlling is at-0.05 ~ 1.0MPa, when polymerization single polymerization monomer quality reaches the requirement of target product, pass into polymerization reaction kettle inner bottom part the mixed solution that step 1 configures, control temperature is at 50-150 degree, and pressure is at-0.05 ~ 1.0MPa;
Step 3: after polymerization reaction kettle liquid is full, reaction solution flows out from reactor top, flows into bottom aging still, and continue polyreaction, the temperature of aging still controls at 50 ~ 150 degree, pressure-0.05 ~ 1.0MPa;
Step 4: after aging still liquid is full of, reaction solution flows out from aging still top, in entering and still, temperature 0 ~ 100 degree, pressure is 0 ~ 1MPa, is added dropwise to alkali neutralization, needs distillation with water displacement organic solvent if desired, obtains water-soluble polymers;
Step 5: as need segmented copolymer be obtained, step 4 terminates after aging still liquid is full of, reaction solution flows out from aging still top, the second polymerization reaction kettle is entered from bottom, bottom the second polymerization reaction kettle, be added dropwise to initiator and polymerization single polymerization monomer 2 mixture continuously, enter the second aging still from the second polymeric kettle material out aging; Repeating step 3 and 4 can obtain many block compounds.
In above-mentioned agricultural chemicals polymeric surface active agent continuous preparation method, step 1 be premix still optionally, can be multiple, preferable temperature 0 ~ 20 degree; pressure 0 ~ 0.2MPa, step 2 is polymeric kettle, and step 3 is aging still; step 4 be in and transformation pot, preferable temperature 60 ~ 95 degree, pressure 0 ~ 0.4MPa;
In above-mentioned agricultural chemicals polymeric surface active agent continuous preparation method, described polymerization process is reversible addition cleavage activity radical polymerization (RAFT technology), and realize molecular weight product and the adjustable control of molecular structure, RAFT reagent refers to have Fig. 1 structural formula:
In formula:
R comprises alkyl or aryl or alkylaryl or containing heteroatomic group, preferable methyl or ethyl or sec.-propyl or phenyl or naphthyl or propyloxy phenyl base or itrile group sec.-propyl or alkyl dimethyl acetate groups;
Z comprises R or RS or RO or secondary amine R(R1) N, wherein R or R1 is alkyl or aryl or alkylaryl or containing heteroatomic group, R or R1 preferable methyl or ethyl or sec.-propyl or phenyl or naphthyl;
In above-mentioned agricultural chemicals polymeric surface active agent continuous preparation method, initiator or be heat decomposition type peroxide initiator, preferred Potassium Persulphate or hydrogen peroxide or ammonium persulphate or benzoyl peroxide or the benzoyl peroxide tert-butyl ester or methylethyl ketone peroxide;
Or be azoic compound initiator, preferred Diisopropyl azodicarboxylate or 2,2'-Azobis(2,4-dimethylvaleronitrile) or azo-bis-iso-dimethyl or azo diisobutyl amidine hydrochloride;
Or for redox decomposition type initiator, the system that preferred dibenzoyl peroxide (BPO)-N or N-xylidene(s) (DMA) and BPO-N or N-dimethyl-para-totuidine (DMT) form or the organic oxidation reduction system be made up of organic hydroperoxide (as isopropyl benzene hydroperoxide) and DMT or the system be made up of water miscible persulphate and aliphatic amide;
In above-mentioned agricultural chemicals polymeric surface active agent continuous preparation method, described solvent can be one or more combinations in the low mass molecule alcohols such as water, methyl alcohol, ethanol, Virahol, acetone, butanone, pentanone, vinyl acetic monomer, n-propyl acetate, dimethylbenzene, toluene, ketone, ester, aromatic hydrocarbons etc.;
In above-mentioned agricultural chemicals polymeric surface active agent continuous preparation method, described monomer comprises hydrophilic monomer and lipophilicity monomer, wherein hydrophilic monomer comprises unsaturated carboxylic acid, or the carboxylate of the low son amount alcohol of unsaturated carboxylic acid, or unsaturated Polyoxyalkylene ethers, or unsaturated heterocyclic compound, preferred vinylformic acid, methacrylic acid, MALEIC ANHYDRIDE, the carboxylate of toxilic acid, the carboxylate of fumaric acid, the carboxylate of methyl, the carboxylate of ethyl, the carboxylate of sec.-propyl, the carboxylate of alkyl polyoxyethylene ether (polymerization degree 0-50), allyl polyethenoxy ether (polymerization degree 0-50), polyoxyethylene base Soxylat A 25-7 (polymerization degree 0-50), the combination of any one or any kind in vinyl pyrrolidone,
Described lipophilicity monomer comprises containing the unsaturated compound of terminal double bond or containing double bond heterogeneous ring compound, the combination of any one or any kind in optimization styrene, α-methylstyrene, vinylformic acid Long carbon chain ester, methacrylic acid Long carbon chain ester, vinyl carbinol, vinyl carbinol polyethenoxy ether, 1-butylene, 1-octene, dicyclopentadiene;
In block polymerization process, in different block order, polymerization single polymerization monomer can be one-component, also can be one or more combinations in hydrophilic, oleophylic monomer.
In above-mentioned agricultural chemicals polymeric surface active agent continuous preparation method, described polymerization reaction kettle and aging still are preferably equipped with the external circulating device with refrigerating unit, to improve the control of temperature in Product mix mixing effect and reaction process;
The present invention adopts full still overflow discharge method, polymeric kettle is identical with discharging speed with the input speed of aging still, so that wherein any one calculates residence time of material, the suitable residence time is related to quality, monomer effective rate of utilization and the production efficiency of producing product, general 5 liters of polymeric kettle residence time are 0.5 ~ 10 kg/hour, 5 liters of aging still residence time are 0.5 ~ 20 kg/hour, realize being connected of polymeric kettle and aging still by controlling the size of still.
Advantage of the present invention is: by the serialization of polymeric surface active agent polymerization process, effectively can improve plant factor, shortens the production cycle, reduce energy consumption, the stability of improving the quality of products; The free-radical polymerized technology of reversible addition cleavage activity (RAFT technology) is adopted to combine conventional free radical copolymerization and ionic polymerization feature, by forming dormancy kind to the reversible transfer of special chain transfer agent, and the concentration of hierarchy of control dormancy kind and spike is carried out with the quick permutoid reaction that this reversible chemical balances, realize polymer molecular structure can design, molecular mass and molecule segment controllable object.
Accompanying drawing explanation
Fig. 1 is the molecular structure of target product of the present invention.
In formula:
The ester group that R1, R2 are H or alkyl or heterocycle or carboxyl or are connected with alcohol;
R3, R4 are H or CH3;
M is alkaline-earth metal ions or organic bases, the preferred trolamine of organic bases or diethanolamine or Monoethanolamine MEA BASF or triethylamine;
X, Y are the group that chain-transfer agent cracking remains, preferable methyl, ethyl, sec.-propyl, phenyl, cumyl, dodecyl etc.
Embodiment
Comparative example 1:
Pre-composition 1: 10 kilograms of acetone, 0.375 kilogram of Diisopropyl azodicarboxylate (AIBN), 29 kilograms of MALEIC ANHYDRIDE, 21 kilograms of vinylformic acid and 1.5 kilograms of lauryl mercaptans are fully mixed; Pre-composition 2: 15.4 kilograms of vinylbenzene, 20.1 kilograms of dicyclopentadiene, 0.375 kilogram of AIBN, 10 kilograms of acetone, 14.5 kilograms of MALEIC ANHYDRIDE and 1.5 kilograms of lauryl mercaptans are fully mixed.
Polymerization: 60 kilograms of acetone are placed in still, nitrogen replacement air, start stirring and be warming up to 48-52 DEG C, start evenly to drip pre-composition and dropwise for 1,10 hours, 60-65 DEG C is incubated 5 hours;
Block polymerization: drip pre-composition 2 under 70-75 DEG C of condition, dropwises, is warming up to 80-82 DEG C for 8 hours, is incubated aging 4 hours.
Neutralization displacement: with water replacement solvent acetone (potassium hydroxide is neutralized to pH value 7 ~ 8), spraying dry obtains block type polymer dispersant of the present invention.
Product: adopt same process, differ greatly between batch, statistics shows molecular weight Mw=8500, molecular weight distribution index 2.56, tap density 0.49g/l, and apply in 90% atrazine water dispersible granule, suspensibility reaches 73%, and indices is poor.
Comparative example 2:
Pre-composition 1: 10 kilograms of acetone, 0.375 kilogram of Diisopropyl azodicarboxylate (AIBN), 29 kilograms of MALEIC ANHYDRIDE, 21 kilograms of vinylformic acid and 1.5 kilograms of S-dodecyl-S (methyl acetic acid) trithiocarbonate are fully mixed; Pre-composition 2: 15.4 kilograms of vinylbenzene, 20.1 kilograms of dicyclopentadiene, 0.375 kilogram of AIBN, 10 kilograms of acetone, 14.5 kilograms of MALEIC ANHYDRIDE and 1.5 kilograms of S-dodecyl-S (methyl acetic acid) trithiocarbonate are fully mixed.
Polymerization: 60 kilograms of acetone are placed in still, nitrogen replacement air, start stirring and be warming up to 48-52 DEG C, start evenly to drip pre-composition and dropwise for 1,10 hours, 60-65 DEG C is incubated 5 hours;
Block polymerization: drip pre-composition 2 under 70-75 DEG C of condition, dropwises, is warming up to 80-82 DEG C for 8 hours, is incubated aging 4 hours.
Neutralization displacement: with water replacement solvent acetone (potassium hydroxide is neutralized to pH value 7 ~ 8), spraying dry obtains block type polymer dispersant of the present invention.
Product: adopt same process, slightly fluctuate between batch, statistics shows molecular weight Mw=9890, molecular weight distribution index 1.21, tap density 0.46g/l, and apply in 90% atrazine water dispersible granule, suspensibility reaches 96%, and indices is better.Adopt batch operation, stability slightly difference between batch.
Embodiment 1:
Pre-composition 1: 40 kilograms of acetone, 0.375 kilogram of Diisopropyl azodicarboxylate (AIBN), 29 kilograms of MALEIC ANHYDRIDE, 21 kilograms of vinylformic acid and 1.5 kilograms of S-dodecyl-S (methyl acetic acid) trithiocarbonate are fully mixed; Pre-mixing 2: 15.4 kilograms of vinylbenzene, 14.5 kilograms of MALEIC ANHYDRIDE, 20.1 kilograms of dicyclopentadiene, 0.375 kilogram of AIBN, 40 kilograms of acetone and 1.5 kilograms of S-dodecyl-S (methyl acetic acid) trithiocarbonate are fully mixed.
Polymerization: pre-composition 1 is pressed into 5 liters of stainless steel cauldrons from static mixer ingress, when press-in about 3 kilograms, start stirring and be warming up to 48-52 DEG C, pressure 0 ~ 0.1MPa, be incubated 4 hours, start to pass into premix continuously by 0.1 kg/hour of speed, polymeric kettle is full of rear spilling material and enters 2.5 liters of aging stills by aging still bottom, aging still keeps temperature 60-65 DEG C, pressure 0 ~ 0.1MPa.
Block polymerization: the material overflowed from above-mentioned aging still enters second 5 liters of polymeric kettle, premixture 2 is pressed in stainless steel cauldron continuously from static mixer, press-in speed controls at 0.4 kg/hour, temperature 70-75 DEG C, pressure 0 ~ 0.5MP, polymeric kettle is full of rear spilling material by entering 2.5 liters of aging stills, and aging still keeps temperature 80-82 DEG C, pressure 0 ~ 0.5MPa.
Splicing neutralization is replaced with still in two 2.5 liters, with water replacement solvent acetone (sodium hydroxide is neutralized to pH value 7 ~ 8), spraying dry obtains block type polymer dispersant of the present invention, molecular weight Mw=10500, molecular weight distribution index 1.13, tap density 0.45g/l, applies in 90% atrazine water dispersible granule, suspensibility reaches 97%, fine properties.
Embodiment 2
Premix: 300 kg isopropanol alcohol, 2.0 kilograms of benzoyl peroxides (BPO), 32.5 kilograms of MALEIC ANHYDRIDE, 43.1 kilograms of Propylene glycol monoacrylates, 24.4 kilograms of diisobutylene and 2.5 kilograms of S-ethoxycarbonyl-S-ethyl trithiocarbonate are fully mixed;
Polymerization: pre-composition is pressed into 5 liters of stainless steel cauldrons from static mixer ingress, when press-in about 2 kilograms, start stirring and be warming up to 100-102 DEG C, pressure 0 ~ 0.5MPa, be incubated 2 hours, start to pass into premix continuously by 1 kg/hour of speed, polymeric kettle is full of rear spilling material and enters 3 liters of aging stills by aging still bottom, aging still keeps temperature 100-102 DEG C, pressure 0 ~ 0.5MPa.
Neutralization: replace splicing neutralization with still in two 10 liters, with water replacement solvent Virahol (sodium hydroxide is neutralized to pH value 7 ~ 8), spraying dry obtains macromolecule dispersing agent of the present invention, molecular weight Mw=7200, molecular weight distribution index 1.15, tap density 0.42g/l, applies in 10% difenoconazole water dispersible granule, suspensibility reaches 93%, fine properties.
Embodiment 3
Premix: 40 kilograms of vinyl acetic monomers, 0.6 kilogram of methylethyl ketone peroxide, 29.2 kilograms of methacrylic acid macrogol esters (M1200), 30.8 kilograms of methacrylic acids fat alcohol monoesters (carbon 12-14 alcohol) and 0.9 kilogram of dodecylthio thiocarbonyl sulfenyl propionic acid are fully mixed, mixing temperature is lower than 20 degree;
Polymerization: pre-composition is pressed into 5 liters of stainless steel cauldrons from static mixer ingress, when press-in about 2 kilograms, start stirring and be warming up to 70-72 DEG C, pressure 0 ~ 0.3MPa, is incubated 4 hours, starts to pass into premix continuously by 2.5 kgs/hour of speed, polymeric kettle is full of rear spilling material and enters 3 liters of aging stills by aging still bottom, aging still keeps temperature 80-85 DEG C, pressure 0 ~ 0.2MPa, and the residence time is 72 minutes.
Neutralization: replace splicing neutralization with still in two 10 liters, with water replacement solvent vinyl acetic monomer (sodium hydroxide is neutralized to pH value 7 ~ 8), the finished product are the aqueous solution of non-volatile content 40%, molecular weight Mw=20500, molecular weight distribution index 1.21, rotary viscosity (20 degree, No. 2 rotors, 30 revs/min) 5290mpa.s, mix by 2:1 with SP-3060 dispersion agent (Jiangsu Sinvochem S&D Co., Ltd. produces), add 6%, apply in 800 grams per liter diuron suspending agents, formulation viscosity is 450mpa.s, particle diameter D90:4.5 micron, within 2 years, storage is without obvious settling.
Embodiment 4
Premix: by 568 kilograms of toluene, 2 kilograms of di-isopropyl peroxydicarbonates, 41 kilograms of 1-vinyl toluenes, 60 kilograms of allyl alcohol polyethenoxy ethers (M600), 19.6 kilograms of MALEIC ANHYDRIDE and 8 kilograms of S, S-bis-(a-methyl phenyl ketone) trithiocarbonate fully mixes, and mixing temperature is lower than 10 degree;
Polymerization: pre-composition is pressed into 5 liters of stainless steel cauldrons from static mixer ingress, when press-in about 2.5 kilograms, start stirring and be warming up to 110-112 DEG C, pressure 0 ~ 0.3MPa, is incubated 5 hours, starts to pass into premix continuously by 5 kgs/hour of speed, polymeric kettle is full of rear spilling material and enters 10 liters of aging stills by aging still bottom, aging still keeps temperature 120-125 DEG C, pressure 0 ~ 0.2MPa, and the residence time is 120 minutes.
The finished product are the toluene solution of non-volatile content 17.5%, molecular weight Mw=4850, molecular weight distribution index 1.18, rotary viscosity (20 degree, No. 2 rotors, 30 revs/min) 290mpa.s, mix by 1:8 with SP-3462 emulsifying agent (Jiangsu Sinvochem S&D Co., Ltd. produces), add 12%, apply in 40 grams per liter nicosulfuron+280 grams per liter atrazine oil-suspending agents, formulation viscosity is 450mpa.s, particle diameter D90:5.3 micron, and within 2 years, storage is without obvious settling.
Claims (8)
1. an agricultural chemicals polymeric surface active agent continuous production method, is characterized in that, carries out according to the following steps:
1) drop into living chain transfer agent, initiator, solvent and polymerization single polymerization monomer in premix still, mix, and obtain pre-composition with nitrogen replacement;
2) in polymeric kettle, drop into the pre-composition of step 1), with nitrogen replacement, be warming up to 50 ~ 150 degree, pressure-controlling is at-0.05 ~ 1.0MPa, until formation macromonomer chain-transfer agent;
Then in polymeric kettle, pass into the pre-composition of step 1) continuously, control temperature is at 50-150 degree, and pressure is at-0.05 ~ 1.0MPa, until be full of spilling, time controling was at 1 ~ 5 hour;
3) step 2) material that overflows enters aging still, and continue polyreaction, the temperature of aging still controls at 50 ~ 150 degree, pressure-0.05 ~ 1.0MPa, and the residence time remains on 1 ~ 2 hour;
4) material of step 3) alternately enters in follow-up at least two and still, drips alkali aqueous solution neutralization and obtains.
2. an agricultural chemicals polymeric surface active agent continuous production method, is characterized in that, carries out according to the following steps:
1) drop into living chain transfer agent, initiator, solvent and polymerization single polymerization monomer in premix still, mix, and obtain pre-composition with nitrogen replacement, prefabricated pre-composition one and pre-composition two;
2) in polymeric kettle, drop into the pre-composition one of step 1), with nitrogen replacement, be warming up to 50 ~ 150 degree, pressure-controlling is at-0.05 ~ 1.0MPa, until formation macromonomer chain-transfer agent;
Then in polymeric kettle, pass into the pre-composition one of step 1) continuously, control temperature is at 50-150 degree, and pressure is at-0.05 ~ 1.0MPa, until be full of spilling, time controling was at 1 ~ 5 hour;
3) step 2) material that overflows enters aging still, and continue polyreaction, the temperature of aging still controls at 50 ~ 150 degree, pressure-0.05 ~ 1.0MPa, and the residence time remains on 1 ~ 2 hour;
4) block polymerization: aging still material out enters in the second polymeric kettle, is then pressed into pre-composition two in the second polymeric kettle, stirs and is warming up to 50 ~ 150 degree, and pressure-controlling is at-0.05 ~ 1.0MPa, until formation block;
Then in the second polymeric kettle, pass into the pre-composition two of step continuously, control temperature is at 50-150 degree, and pressure is at-0.05 ~ 1.0MPa, until be full of spilling, time controling was at 1 ~ 5 hour;
5) material of step 4) alternately enters in follow-up at least two and still, drips alkali aqueous solution neutralization and obtains.
3. a kind of agricultural chemicals polymeric surface active agent continuous production method according to claim 2, is characterized in that, prefabricated multiple pre-composition also repeats according to described step, obtains many block macromoleculars tensio-active agent.
4. a kind of agricultural chemicals polymeric surface active agent continuous production method according to claim 1 and 2, it is characterized in that, described living chain transfer agent has following structure formation:
In formula:
R comprises alkyl or aryl or alkylaryl or contains heteroatomic group;
Z comprises R or RS or RO or secondary amine R(R1) N, wherein R or R1 is alkyl or aryl or alkylaryl or contains heteroatomic group.
5. a kind of agricultural chemicals polymeric surface active agent continuous production method according to claim 1 and 2, it is characterized in that, described initiator is heat decomposition type peroxide initiator or for azoic compound initiator or for redox decomposition type initiator.
6. a kind of agricultural chemicals polymeric surface active agent continuous production method according to claim 1 and 2, it is characterized in that, described solvent can be one or more combinations in low mass molecule alcohol, ketone or the esters such as water, methyl alcohol, ethanol, Virahol, acetone, butanone, pentanone, vinyl acetic monomer, n-propyl acetate.
7. a kind of agricultural chemicals polymeric surface active agent continuous production method according to claim 1 and 2, it is characterized in that, described monomer comprises hydrophilic monomer and lipophilicity monomer;
Wherein hydrophilic monomer comprises unsaturated carboxylic acid, or the carboxylate of the low son amount alcohol of unsaturated carboxylic acid, or unsaturated Polyoxyalkylene ethers, or unsaturated heterocyclic compound, preferred vinylformic acid, methacrylic acid, MALEIC ANHYDRIDE, the carboxylate of toxilic acid, the carboxylate of fumaric acid, the carboxylate of methyl, the carboxylate of ethyl, the carboxylate of sec.-propyl, the carboxylate of alkyl polyoxyethylene ether (polymerization degree 0-20), allyl polyethenoxy ether (polymerization degree 0-20), polyoxyethylene base Soxylat A 25-7 (polymerization degree 0-20), the combination of any one or any kind in vinyl pyrrolidone,
Described lipophilicity monomer comprises containing the unsaturated compound of terminal double bond or containing double bond heterogeneous ring compound, the combination of any one or any kind in optimization styrene, α-methylstyrene, vinylformic acid Long carbon chain ester, methacrylic acid Long carbon chain ester, vinyl carbinol, vinyl carbinol polyethenoxy ether, 1-butylene, 1-octene, dicyclopentadiene.
8. a kind of agricultural chemicals polymeric surface active agent continuous production method according to claim 2, it is characterized in that, in block polymerization process, in different block order, polymerization single polymerization monomer can be one-component, also can be one or more combinations in hydrophilic, oleophylic monomer.
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| CN106259389A (en) * | 2016-08-08 | 2017-01-04 | 威尔（福建）生物有限公司 | A kind of auxiliary agent for pyraclostrobin water baseization and preparation method thereof |
| CN110358029A (en) * | 2019-07-30 | 2019-10-22 | 江苏擎宇化工科技有限公司 | A kind of anti-high power hard water dispersing agent and the preparation method and application thereof |
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