CN114605599B - Preparation method of high-molecular surfactant containing organic silicon - Google Patents

Preparation method of high-molecular surfactant containing organic silicon Download PDF

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CN114605599B
CN114605599B CN202210340481.5A CN202210340481A CN114605599B CN 114605599 B CN114605599 B CN 114605599B CN 202210340481 A CN202210340481 A CN 202210340481A CN 114605599 B CN114605599 B CN 114605599B
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CN114605599A (en
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申凯华
朱秀婷
乔文清
王红红
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Dalian University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • C08F290/148—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
    • C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C08F299/08—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polysiloxanes

Abstract

The invention provides a preparation method of a high molecular surfactant containing organic silicon, belonging to the field of high molecular compounds. Firstly, hydrophobic and hydrophilic monomers are prepared from a silicon-hydrogen-containing monomer through a hydrosilylation reaction, so that the amphipathy of the hydrogen-containing silicone oil is realized. And then, carrying out graft polymerization reaction with different types of monomers including hydrophilic and hydrophobic monomers through free radical copolymerization reaction of an aqueous phase system to prepare the anionic high molecular surfactant containing the organic silicon functional structure and hydrophilic-hydrophobic functional groups. The invention is characterized in that a two-step method is adopted, and the content of the silicon-containing functional structure is controllable and adjustable. On one hand, the amphipathy of the silicon functional structure is regulated, and meanwhile, the free radical self-crosslinking reaction of the hydrogen-containing silicone oil is controlled. The invention can select different types of polymerization monomers, regulate and control the proportion among the monomers, so that the prepared organosilicon-containing high-molecular surfactant has the characteristics of dispersion, defoaming, emulsification assistance and the like.

Description

Preparation method of high-molecular surfactant containing organic silicon
Technical Field
The invention belongs to the field of high molecular compounds, relates to the field of surfactants, and in particular relates to a preparation method of a high molecular surfactant capable of containing organic silicon.
Background
The high molecular surfactant generally refers to a polymer having surface activity with a relative molecular mass of 1000 or more, and its chemical structure includes hydrophilic and hydrophobic functional groups. The polymer surfactant can be classified into random type, block type, graft type, etc. according to molecular configuration. Compared with the common low-molecular surfactants, the high-molecular surfactants have no outstanding capability of reducing the surface tension, but have better dispersibility, emulsifying property, compatibilizer, thickening property and the like than the low-molecular surfactants. Natural water-soluble polymer compounds such as starch, cellulose and derivatives thereof have certain emulsifying and dispersing ability, but the controllability of structural modification is relatively difficult. The first synthesis of a polymeric surfactant, poly 1-dodecane-4-vinylpyridine bromide, also known as Polysoap (Polysoap) by Stauss in 1950; commercially available high molecular surfactant-poly (oxyethylene oxypropylene) block copolymers were published by Wyandotte corporation in 1954 and reported as nonionic surfactants (trade name Pluronics).
The organic silicon compound has the characteristics of low surface tension, no pollution, quick effect, chemical inertness and the like due to the unique molecular structure. Patent CN 112898507A proposes a silicon block polymer surfactant, which is obtained by uniformly stirring and mixing vinyl silicone oil, polymerizable macromer, polymerizable cationic monomer and water, heating and adding a catalyst to perform polymerization reaction, and has good flexibility and thickening effect. Patent CN 106669539A proposes a compound modified organosilicon surfactant, which is prepared by uniformly mixing hydrogen-containing silicone oil and propenyl polyoxyethylene ether, heating and stirring under the protection of nitrogen, reacting for 4-5 hours at 105-115 ℃, and then removing low-boiling substances in vacuum at 85-95 ℃ and 55-65kpa to obtain the polyether modified organosilicon surfactant. And then the surfactant is compounded with a low-molecular-weight surfactant to obtain the composite modified organic silicon surfactant with excellent defoaming and foam inhibiting properties.
Although silicone oil has excellent defoaming performance, the hydrophobic and oleophobic characteristics of the silicone oil have the problem of poor compatibility with other auxiliary agents when the silicone oil is applied. The main improvement method at present is that the hydrophilic monomer is combined with the hydrophilic monomer through hydrosilylation reaction, for example, the hydrophilicity is enhanced after polyether chain segment is used for modifying the silicone oil, so that the compatibility with other water-soluble auxiliary agents is improved, and the hydrophobic monomer is used for modifying the silicone oil, so that the compatibility with the hydrophobic auxiliary agent is also improved, and the main route of the modified organosilicon surfactant is one. At present, a free radical polymerization mode is mostly adopted in the silicone oil modification process, self-crosslinking of a modified monomer is unavoidable in the monomer grafting modification process, the comprehensive performance of a modified silicone oil polymer is affected, and how to prepare a modified organosilicon surfactant can be controlled is still a hot spot for technical development at present.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides a preparation method of a macromolecular surfactant containing organic silicon, so as to improve the surface characteristics of the macromolecular surfactant, such as dispersion, defoaming, auxiliary emulsification and the like. The invention relates to a two-step process for preparing a polymer surfactant containing organosilicon, wherein the content of a silicon functional structure in the prepared polymer surfactant is controllable and adjustable, and the self-crosslinking problem of organosilicon in the polymerization process can be effectively avoided. Meanwhile, the method can select different types of polymerization monomers, regulate and control the proportion among the monomers to obtain the high-molecular surfactant containing the organic silicon, and is favorable for popularization and application in actual industry.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the preparation method of the organosilicon-containing high molecular surfactant adopts a two-step method to prepare the anionic high molecular surfactant, and comprises the following steps: firstly, preparing an amphiphilic organic silicon monomer through hydrosilylation reaction of hydrophobic and hydrophilic monomers, namely realizing the amphipathy of hydrogen-containing silicone oil. And secondly, carrying out graft polymerization reaction with different types of monomers through free radical copolymerization reaction of an aqueous phase system to prepare the anionic polymer surfactant containing an organosilicon functional structure and hydrophilic and hydrophobic functional groups, wherein the monomers comprise hydrophilic and hydrophobic monomers. The implementation process comprises the following steps:
step one: preparation of silicon-containing intermediates
Adding hydrogen-containing silicone oil, a polymerization monomer, a solvent and a small amount of catalyst into a reactor, heating and stirring to react, wherein the reaction is two stages. Firstly, carrying out low-temperature section reaction, controlling the temperature to be 20-50 ℃ and stirring for 2-8h; after the reaction at the low temperature section is finished, the reaction temperature is raised to 60-85 ℃, the reaction is continued for 2-8h, and the product is obtained after post treatment. Every 80-120g of solvent is correspondingly added with 40-60g of hydrogen-containing silicone oil and 100-150g of polymerized monomer, and the mass of the catalyst accounts for 0.05 per mill of the mass of the total monomer.
The catalyst attacks part of active hydrogen sites of the hydrogen-containing silicone oil by utilizing hydrosilylation reaction, and unsaturated amide, unsaturated carboxylic acid and other monomers are connected on the side chain of the hydrogen-containing silicone oil to obtain a silicon-containing intermediate.
Step two: preparation of organosilicon-containing Polymer surfactant
And (3) respectively adding the product obtained in the step (I), an initiator, a chain transfer agent, a polyether monomer, a polymerization monomer, deionized water and a small amount of organic solvent into a reactor, heating to 30-80 ℃ in a water bath, and reacting for 5-7h. Every 140-150g of deionized water is correspondingly added with 220-330g of silicon-containing intermediate, 1-3g of initiator, 2-5g of chain transfer agent, 15-20g of polyether monomer, 40-50g of polymerized monomer and 60-100g of organic solvent.
The free radical polymerization reaction is utilized to carry out copolymerization reaction in the solution, and the obtained polymer and the silicon-containing intermediate are connected through hydrogen bonds so as to achieve synergistic effect.
Further, the polymerized monomer in the first step includes one or more of hydrophilic monomer, hydrophobic monomer or hydrophobic oleophobic silicon-containing monomer. The hydrophilic monomer comprises unsaturated carboxylic acid compounds (including acrylic acid, methacrylic acid, maleic anhydride, itaconic acid and fumaric acid), unsaturated amide compounds (including acrylamide, N-tertiary butyl acrylamide, N-methyl formamide, N-methyl-N-vinylacetamide and coconut diethanolamide), and polyether compounds (including polyethylene glycol monomethyl ether, allyl polyoxyethylene ether, isopentenyl polyoxyethylene ether, methallyl polyoxyethylene ether and 4-hydroxybutyl polyethylene glycol vinyl ether). The hydrophobic monomer is an unsaturated ester compound and comprises methyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate and hydroxyethyl methacrylate. The hydrophobic oleophobic silicon-containing monomer comprises p-bromophenyl dimethyl hydrogen silane, di-n-octyl methyl silane, hexadecyl dimethyl hydrogen silane, propargyl dimethyl hydrogen silane, propyl methyl monochloro hydrogen silane, polymethyl hydrogen siloxane, triethoxy hydrogen silane, triethyl hydrogen silane and methyl dichloro silane.
Further, the hydrogen content of the silicon-containing monomer in the first step is 0.1-10%.
Further, the catalyst in the first step comprises one or more of metal salt catalysts (such as zinc dichloride, tin dichloride, palladium dichloride, aluminum trichloride and the like), non-metal catalysts (such as boron trifluoride), transition metal catalysts (such as a catalytic system formed by noble metals such as platinum, palladium, rhodium, nickel and the like), and homogeneous catalysts (such as chloroplatinic acid isopropanol solution and tetramethyl divinyl disiloxane platinum complex).
Further, the solvent in the first step includes one or more of isopropanol, tetrahydrofuran, ethanol, toluene, xylene, acetylacetone, carboxylic acid ester, diethyl ether, etc.
Further, the initiator in the second step comprises one or more of a water-soluble initiator and an oil-soluble initiator. The water-soluble initiator comprises hydrogen peroxide, ammonium persulfate, potassium persulfate, sodium persulfate, azo diisobutyl amidine hydrochloride, azo diiso Ding Mi hydrochloride, azo dicyanovaleric acid, azo diisopropyl imidazoline and the like; the oil-soluble initiator comprises azodiisobutyronitrile, azodiisoheptonitrile, dimethyl azodiisobutyrate, benzoyl peroxide, bis (2-ethylhexyl) peroxydicarbonate and the like.
Further, the chain transfer agent in the second step comprises sulfur-containing compounds such as dodecyl mercaptan, thioglycollic acid, mercaptopropionic acid, sodium bisulphite, mercaptoethanol, mercaptopropanol; and is free of one or more of sulfur species such as formic acid, sodium hypophosphite.
Compared with the existing preparation method of the high molecular surfactant, the invention has the following advantages:
(1) The invention is characterized in that the organosilicon-containing high molecular surfactant is prepared by adopting a two-step method, and the content of the silicon-containing functional group structure can be controlled and regulated by selecting different types of polymerization monomers and regulating the proportion among the monomers, wherein the addition condensation of the hydrogen-containing silicone oil can regulate the amphipathy of the silicon functional structure on one hand and can also control the self-crosslinking side reaction of the hydrogen-containing silicone oil.
(2) The siloxane chain containing the organic silicon high molecular surfactant has the characteristics of defoaming, grafting of hydrophilic groups and hydrophobic groups, adjustment of the HLB value, strong compatibility with other auxiliary agents when in use, dispersion and emulsification assistance with defoaming functions, and the like. So that the prepared organosilicon-containing high molecular surfactant has the surface characteristics of dispersion, defoaming, emulsification and the like.
Drawings
FIG. 1 is a MALDI-TOF mass spectrum of the silicone-containing polymer surfactant prepared in example 1.
FIG. 2 shows the surface tension curves of silicone-containing polymeric surfactants of examples 1, 2, 3, 4, and 5.
FIG. 3 is a graph showing the average particle diameter of the silicone-containing polymer surfactant of application example 1 applied to an emulsion reaction.
Detailed Description
Example 1
Step one: preparation of silicon-containing intermediates
40g of polymethylhydrosiloxane (hydrogen content 1%), 20g of methyl acrylate, 55g of maleic anhydride (purity > 99%), 25g of acrylamide, 70g of isopropanol and 10g of tetramethyl divinyl disiloxane platinum complex (1 wt%o) are added into a reaction bottle, and the mixture is heated and stirred; the reaction is two stages. Firstly, carrying out low-temperature section reaction, controlling the temperature at 20 ℃ and stirring for 8 hours; after the reaction at the low temperature section is finished, the reaction temperature is increased to 60 ℃, and the reaction is finished after the reaction is continued for 8 hours, wherein methyl acrylate, acrylamide and isopropanol are refined.
Step two: preparation of organosilicon-containing high-molecular surfactant
220g of the product obtained in the step one, 1g of hydrogen peroxide (28 wt%) and vitamin C0.01g, 2g of dodecyl mercaptan, 15g of isopentenyl alcohol polyethylene glycol ether, 40g of acrylamide, 60g of isopropanol and 140g of water are respectively added into a reaction bottle, the water bath is heated to 30 ℃ and the reaction is finished after 7 hours, wherein the isopentenyl alcohol polyethylene glycol ether, the acrylamide and the isopropanol are refined, and related monomers or solvents in the following examples are subjected to necessary refining.
Example 2
Step one: preparation of silicon-containing intermediates
60g of di-N-octyl methylsilane, 35g of hydroxyethyl acrylate, 70g of methacrylic acid, 45g of N-tertiary butyl acrylamide, 110g of isopropanol and 10g of chloroplatinic acid-isopropanol solution (1 Wt per mill) are added into a reaction bottle, and the mixture is heated and stirred; the reaction is two stages. Firstly, carrying out low-temperature section reaction, controlling the temperature at 50 ℃ and stirring for 2 hours; after the reaction at the low temperature section is finished, the reaction temperature is increased to 85 ℃, and the reaction is finished after the reaction is continued for 2 hours.
Step two: preparation of organosilicon-containing high-molecular surfactant
330g of the product obtained in the step one, 3g of sodium persulfate, 5g of thioglycollic acid, 20g of allyl polyoxyethylene ether, 50g of N-tertiary butyl acrylamide, 100g of isopropanol and 150g of water are respectively added into a reaction bottle, the water bath is heated to 80 ℃ and the reaction is finished after 5 hours.
Example 3
Step one: preparation of silicon-containing intermediates
50g of triethoxysilane, 25g of butyl acrylate, 60g of acrylic acid, 40g of N-methylformamide, 90g of isopropanol and 10g of chloroplatinic acid-isopropanol solution (1 Wt per mill) are added into a reaction bottle, and the mixture is heated and stirred; the reaction is two stages. Firstly, carrying out low-temperature section reaction, controlling the temperature at 35 ℃ and stirring for 5 hours; after the reaction at the low temperature section is finished, the reaction temperature is increased to 72 ℃, and the reaction is finished after the reaction is continued for 5 hours.
Step two: preparation of organosilicon-containing high-molecular surfactant
275g of the product obtained in the step one, 2g of azodiisopropyl imidazoline, 4g of formic acid, 17g of methyl allyl polyoxyethylene ether, 45g of N-methyl formamide, 80g of isopropanol and 145g of water are respectively added into a reaction bottle, the water bath is heated to 50 ℃ and the reaction is finished after 6 h.
Example 4
Step one: preparation of silicon-containing intermediates
Adding 40g of triethylhydrosilane (hydrogen content 1%), 25g of hydroxypropyl acrylate, 60g of itaconic acid, 30g of N-methyl-N-vinylacetamide, 120g of isopropanol and 10g of chloroplatinic acid-isopropanol (1 Wt per mill) into a reaction bottle, heating and stirring; the reaction is two stages. Firstly, carrying out low-temperature section reaction, controlling the temperature at 45 ℃ and stirring for 4 hours; after the reaction at the low temperature section is finished, the reaction temperature is raised to 85 ℃, and the reaction is finished after the reaction is continued for 4 hours.
Step two: preparation of organosilicon-containing high-molecular surfactant
285g of the product obtained in the step one, 1g of potassium persulfate, 2g of dodecyl mercaptan, 15g of methyl allyl polyoxyethylene ether, 40g of acrylamide, 60g of isopropanol and 150g of water are respectively added into a reaction bottle, and the reaction is finished after the water bath is heated to 70 ℃ and the reaction is carried out for 5 hours.
Example 5
Step one: preparation of silicon-containing intermediates
40g of hexadecyldimethylhydrosilane (hydrogen content: 1%) 25g of hydroxyethyl methacrylate, 60g of fumaric acid, 30g of cocodiethanolamide, 120g of isopropanol and 10g of chloroplatinic acid-isopropanol solution (1 Wt per mill) are added into a reaction bottle, and the mixture is heated and stirred; the reaction is two stages. Firstly, carrying out low-temperature section reaction, controlling the temperature at 45 ℃ and stirring for 4 hours; after the reaction at the low temperature section is finished, the reaction temperature is raised to 85 ℃, and the reaction is finished after the reaction is continued for 4 hours.
Step two: preparation of organosilicon-containing high-molecular surfactant
285g of the product obtained in the step one, 1.5g of azodiiso Ding Mi hydrochloride, 3g of sodium hypophosphite, 20g of polyethylene glycol monomethyl ether, 45g of acrylamide, 60g of isopropanol and 140g of water are respectively added into a reaction bottle, the water bath is heated to 70 ℃ and the reaction is finished after 5 hours.
Example 6
Step one: preparation of silicon-containing intermediates
60g of propargyl dimethyl hydrogen silane (hydrogen content: 1%), 20g of acrylic acid, 80g of butyl acrylate, 120g of isopropyl alcohol and 10g of chloroplatinic acid-isopropyl alcohol solution (1 wt%o) are added into a reaction bottle, and the mixture is heated and stirred; the reaction is two stages. Firstly, carrying out low-temperature section reaction, controlling the temperature at 45 ℃ and stirring for 4 hours; after the reaction at the low temperature section is finished, the reaction temperature is raised to 85 ℃, and the reaction is finished after the reaction is continued for 4 hours.
Step two: preparation of organosilicon-containing high-molecular surfactant
290g of the product obtained in the step one, 1.5g of ammonium persulfate, 3g of mercaptoethanol, 85g of methyl allyl polyoxyethylene ether, 70g of isopropanol and 140g of water are respectively added into a reaction bottle, and the water bath is heated to 70 ℃ and the reaction is finished after the reaction is carried out for 5 hours.
Example 7
Step one: preparation of silicon-containing intermediates
40g of polymethylhydrosiloxane (hydrogen content 1%), 20g of acrylic acid, 80g of butyl acrylate, 120g of isopropanol and 10g of chloroplatinic acid-isopropanol solution (1 Wt per mill) are added into a reaction bottle, and the mixture is heated and stirred; the reaction is two stages. Firstly, carrying out low-temperature section reaction, controlling the temperature at 45 ℃ and stirring for 4 hours; after the reaction at the low temperature section is finished, the reaction temperature is raised to 85 ℃, and the reaction is finished after the reaction is continued for 4 hours.
Step two: preparation of organosilicon-containing high-molecular surfactant
270g of the product obtained in the step one, 4.5g of azodicyanovaleric acid, 9g of mercaptopropanol, 255g of methyl allyl polyoxyethylene ether, 90g of isopropanol and 405g of water are respectively added into a reaction bottle, and the reaction is finished after the water bath is heated to 70 ℃ and the reaction is carried out for 5 hours.
Example 8
Step one: preparation of silicon-containing intermediates
40g of polymethylhydrosiloxane (hydrogen content 1%), 25g of methyl acrylate, 60g of methacrylic acid, 30g of N-tertiary butyl acrylamide, 120g of isopropanol and 10g of chloroplatinic acid-isopropanol solution (1 Wt per mill) are added into a reaction bottle, and the mixture is heated and stirred; the reaction is two stages. Firstly, carrying out low-temperature section reaction, controlling the temperature at 45 ℃ and stirring for 4 hours; after the reaction at the low temperature section is finished, the reaction temperature is raised to 85 ℃, and the reaction is finished after the reaction is continued for 4 hours.
Step two: preparation of organosilicon-containing high-molecular surfactant
285g of the product obtained in the step one, 1.5g of azodiisobutyronitrile, 3g of thioglycollic acid, 20g of methyl allyl polyoxyethylene ether, 45g of N-tertiary butyl acrylamide, 70g of isopropanol and 145g of water are respectively added into a reaction bottle, the water bath is heated to 70 ℃ and the reaction is finished after 5 hours of reaction.
MALDI-TOF test was performed on the silicone-containing polymer surfactant obtained in example 1, and analysis of the falling groups in the spectra revealed that monomers such as unsaturated amides had been already attached to the side chains of the silicone, thereby verifying that the experiment was successful in synthesizing the silicone polymer surfactant. The surface tension of the silicone polymer surfactants obtained in examples 1 to 5 was then tested, and it was found that the surface tension of the polymer surfactant could be adjusted by controlling the reaction monomers to suit different application sites, and that the surface tension could be as low as 40mN/m.
Application example 1
In this example, the silicone-containing polymeric surfactant prepared in example 7 was used to control the polymerization of polybutadiene free radical emulsion to prepare a large particle size latex.
The emulsion reaction was operated as follows:
s1, adding deionized water, a compound emulsifier and electrolyte into a reaction kettle (the specific formula is shown in the table below), starting stirring, replacing with nitrogen for three times to remove air in the kettle, then starting a vacuum valve to form negative pressure in the kettle, starting to add butadiene monomer, adding an initiator when the temperature in the kettle reaches a first-stage reaction temperature, and starting a cold bath device to maintain the temperature at 65 ℃;
s2, after polymerization reaches a certain degree, heating to 75 ℃ at the second stage;
s3, after polymerization reaches a certain degree, heating to a three-stage temperature of 85 ℃;
s4, after the high-temperature section reaction is finished, cooling and stopping the reaction to obtain the polybutadiene latex with large particle size, and adjusting the amount of the additive to obtain the polybutadiene latex with large particle size about 300-600 nm.
The emulsion reaction formula is as follows:
Figure BDA0003579000460000081
note that: the autoclave volume was 2000ml.
Application example 2
In the embodiment, the high-stability aqueous carbon black dispersion liquid is prepared by regulating and controlling the organic silicon-containing high-molecular surfactant prepared in the embodiment 6, and the specific process is as follows;
33.4g of carbon black, 0.75g of silicone-containing high-molecular surfactant, 0.33g of silicone oil and 130g of water are added into a 250ml ball milling tank (containing 200g of ball milling beads with diameters of 5, 10 and 15mm respectively) by using a ball mill, the rotating speed during ball milling and dispersing is 300/rpm, a carbon black dispersion system is obtained after ball milling for 5 hours, and the fluidity of the obtained sample is good, and the viscosity is only 1428 mpa.s.
As shown by experimental results of application examples, the organosilicon-containing high-molecular surfactant obtained by the preparation method has the characteristics of good dispersion, emulsification assistance and the like.
The above examples merely represent embodiments of the present invention and are not to be construed as limiting the scope of the patent of the invention, it being noted that variations and modifications can be made by a person skilled in the art without departing from the inventive concept.

Claims (8)

1. The preparation method of the organic silicon-containing high molecular surfactant is characterized in that the preparation method adopts a two-step method to prepare the anionic high molecular surfactant; firstly, preparing an amphiphilic organic silicon monomer through hydrosilylation reaction of hydrophobic and hydrophilic monomers; secondly, carrying out graft polymerization reaction with different types of monomers through free radical copolymerization reaction of an aqueous phase system to prepare the anionic polymer surfactant containing an organosilicon functional structure and hydrophilic and hydrophobic functional groups; the implementation process comprises the following steps:
step one: preparation of silicon-containing intermediates
Adding a hydrophobic oleophobic silicon-containing monomer, a polymerization monomer, a solvent and a small amount of catalyst into a reactor, heating and stirring to react, wherein the reaction is two stages; firstly, carrying out low-temperature section reaction, controlling the temperature to be 20-50 ℃ and stirring for 2-8h; after the reaction at the low temperature section is finished, the reaction temperature is raised to 60-85 ℃, the reaction is continued for 2-8 hours, and the product is obtained after post treatment; every 80-120g of solvent is correspondingly added with 40-60g of hydrophobic oleophobic silicon-containing monomer and 100-150g of polymerized monomer, and the mass of the catalyst accounts for 0.05 per mill of the mass of the total monomer; the polymerization monomer comprises a hydrophilic monomer and a hydrophobic monomer; the content of hydrogen in the silicon-containing monomer is 0.1-10%;
step two: preparation of organosilicon-containing Polymer surfactant
Adding the product obtained in the step one, an initiator, a chain transfer agent, a polyether monomer, a polymerization monomer, deionized water and a small amount of organic solvent into a reactor respectively, heating to 30-80 ℃ in a water bath, and reacting for 5-7h; every 140-150g of deionized water is correspondingly added with 220-330g of silicon-containing intermediate, 1-3g of initiator, 2-5g of chain transfer agent, 15-20g of polyether monomer, 40-50g of polymerized monomer and 60-100g of organic solvent; the free radical polymerization reaction is utilized to carry out copolymerization reaction in the solution, and the obtained polymer and the silicon-containing intermediate are connected through hydrogen bonds so as to achieve synergistic effect;
the hydrophobic oleophobic silicon-containing monomer comprises p-bromophenyl dimethyl hydrogen silane, di-n-octyl methyl silane, hexadecyl dimethyl hydrogen silane, propargyl dimethyl hydrogen silane, propyl methyl monochloro hydrogen silane, polymethyl hydrogen siloxane, triethoxy hydrogen silane, triethyl hydrogen silane and methyl dichloro silane.
2. The method for preparing a surfactant containing organic silicon according to claim 1, wherein the hydrophilic monomer in the first step comprises unsaturated carboxylic acid compounds, unsaturated amide compounds and polyether compounds; the hydrophobic monomer is an unsaturated ester compound.
3. The method for preparing the surfactant containing the organic silicon polymer according to claim 2, wherein the unsaturated carboxylic acid compound in the step one comprises acrylic acid, methacrylic acid, maleic anhydride, itaconic acid and fumaric acid, the unsaturated amide compound comprises acrylamide, N-tert-butyl acrylamide, N-methyl formamide, N-methyl-N-vinylacetamide and coco diethanolamide, and the polyether compound comprises polyethylene glycol monomethyl ether, allyl polyoxyethylene ether, isopentenyl polyoxyethylene ether, methallyl polyoxyethylene ether and 4-hydroxybutyl polyethylene glycol vinyl ether; the unsaturated ester compound comprises methyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate and hydroxyethyl methacrylate.
4. The method of claim 1, wherein the catalyst in the first step comprises one or more of a metal salt catalyst, a non-metal catalyst, a transition metal catalyst, and a homogeneous catalyst.
5. The method for preparing a high molecular surfactant containing organic silicon according to claim 1, wherein the solvent in the first step comprises one or more of isopropanol, tetrahydrofuran, ethanol, toluene, xylene, acetylacetone, carboxylic acid ester and diethyl ether.
6. The method for preparing a surfactant containing a silicone polymer according to claim 1, wherein the initiator in the second step comprises one or more of a water-soluble initiator and an oil-soluble initiator.
7. The method for preparing the organosilicon-containing high molecular surfactant according to claim 6, wherein the water-soluble initiator comprises hydrogen peroxide, ammonium persulfate, potassium persulfate, sodium persulfate, azobisisobutylamidine hydrochloride, azobisiso Ding Mi hydrochloride, azobiscyano valeric acid, azobisisopropylimidazoline; the oil-soluble initiator comprises azodiisobutyronitrile, azodiisoheptonitrile, dimethyl azodiisobutyrate, benzoyl peroxide and bis (2-ethylhexyl) peroxydicarbonate.
8. The method for producing a silicone-containing polymer surfactant according to claim 1, wherein the chain transfer agent in the second step comprises sulfur-containing species: dodecyl mercaptan, thioglycollic acid, mercaptopropionic acid, sodium bisulphite, mercaptoethanol, mercaptopropanol; no sulfur: one or more of formic acid and sodium hypophosphite.
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