CN109485784A - A kind of method of microreactor synthesis polyacrylic acid ester soap-free emulsion - Google Patents

A kind of method of microreactor synthesis polyacrylic acid ester soap-free emulsion Download PDF

Info

Publication number
CN109485784A
CN109485784A CN201811424131.7A CN201811424131A CN109485784A CN 109485784 A CN109485784 A CN 109485784A CN 201811424131 A CN201811424131 A CN 201811424131A CN 109485784 A CN109485784 A CN 109485784A
Authority
CN
China
Prior art keywords
microreactor
emulsion
acid ester
polyacrylic acid
free emulsion
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201811424131.7A
Other languages
Chinese (zh)
Inventor
周建华
李红
禹志宏
杨明杰
高敬民
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shaanxi University of Science and Technology
Original Assignee
Shaanxi University of Science and Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shaanxi University of Science and Technology filed Critical Shaanxi University of Science and Technology
Priority to CN201811424131.7A priority Critical patent/CN109485784A/en
Publication of CN109485784A publication Critical patent/CN109485784A/en
Pending legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10Esters
    • C08F220/12Esters of monohydric alcohols or phenols
    • C08F220/16Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00Processes of polymerisation
    • C08F2/01Processes of polymerisation characterised by special features of the polymerisation apparatus used
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00Processes of polymerisation
    • C08F2/12Polymerisation in non-solvents
    • C08F2/16Aqueous medium
    • C08F2/22Emulsion polymerisation
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10Esters
    • C08F220/12Esters of monohydric alcohols or phenols
    • C08F220/14Methyl esters, e.g. methyl (meth)acrylate
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10Esters
    • C08F220/12Esters of monohydric alcohols or phenols
    • C08F220/16Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10Esters
    • C08F220/12Esters of monohydric alcohols or phenols
    • C08F220/16Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1808C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polymerisation Methods In General (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

A kind of method of microreactor synthesis polyacrylic acid ester soap-free emulsion disclosed by the invention, it is synthesized using microreactor, microreactor is made of the micro-mixer and stop reaction tube being connected to, specific steps: using double bond acrylic monomers as oily phase, using alkyl vinyl sulfonic acid saline solution as water phase, the oily micro-mixer for being mutually pumped into microreactor with water phase is emulsified, pre-emulsion is made;Prepare initiator solution;Pre-emulsion and initiator solution are pumped into microreactor and reacted, cold bath discharging is after reaction to get polyacrylic acid ester soap-free emulsion.The present invention realizes controllable multiphase Micro-flows using microreactor, enhances mixing, mass transfer and diabatic process in polymerization process, substantially reduces the reaction time, improve polymerization efficiency;Since microreactor has excellent heat-transfer capability, shed in time so that heat is released in reaction, realize the control of temperature, overcome conventional method because temperature it is excessively high caused by sudden and violent poly- problem.

Description

A kind of method of microreactor synthesis polyacrylic acid ester soap-free emulsion
Technical field
The invention belongs to soap-free emulsion preparation method technical fields, and in particular to a kind of microreactor synthesis polyacrylate The method of soap-free emulsion.
Background technique
Polyacrylate is because it is with good heat-resisting, fast light, weather-proof and film forming, in household, automobile, building, resistance Heat-insulated equal fields are fired to be widely used.Currently, the preparation of polyacrylate dispersion carries out generally in tank reactor, Operating time generally a few hours, reactor size generally in the rice order of magnitude, and there are mass-and heat-transfer low efficiency, stop when Between and temperature not easy-regulating the disadvantages of.Due to the phenomenon that automatically speeds up of free radical polymerization, these disadvantages of stirred-tank reactor It is easy to generate that heat transfer is slow, mixing efficiency is low, the reaction time is long in emulsion polymerization process, easily in reactor the problems such as fouling, These problems can all generate certain influence to the performance of polymer.
As chemical industry is towards the development in the directions such as efficient, easily-controllable, safe and environment-friendly, microreaction technology is gradually answered Use chemical field.Compared to stirred-tank reactor, microreactor short, heat and mass transfer efficiency with the reaction time The features such as high, reaction time and accurate temperature control, in conjunction with these features, it is poly- that microreaction technology can efficiently solve lotion The problem of closing reaction process.In addition, microreactor there are also Highgrade integration, without enlarge-effect, it is green safe the advantages that. Based on these advantages, the advantage of microreactor can be given full play to, is come according to different needs with the characteristics of polymerization reaction system Microreactor is selected, and design reaction route and process the characteristics of further combined with microreactor, have can to prepare Control structure and high performance polyacrylic acid ester soap-free emulsion.
Summary of the invention
The purpose of the present invention is to provide a kind of methods of microreactor synthesis polyacrylic acid ester soap-free emulsion, solve benefit It is existing during preparing polyacrylic acid ester soap-free emulsion with tank reactor that heat transfer efficiency is low, complicated for operation, the reaction time is long, The shortcomings that easily cruelly poly- etc..
The technical scheme adopted by the invention is that: a kind of method of microreactor synthesis polyacrylic acid ester soap-free emulsion, benefit It is synthesized with microreactor, the microreactor is made of the micro-mixer and stop reaction tube being connected to, and is specifically included following Step:
Prepare pre-emulsion: using double bond acrylic monomers as oily phase, using alkyl vinyl sulfonic acid saline solution as Water phase is mutually pumped into after mixing in the micro-mixer of a microreactor respectively with water phase by oily and carries out cream in stopping reaction long tube Change, pre-emulsion is made;
It prepares initiator solution: persulfate is dissolved in deionized water, the initiator is made after mixing evenly Aqueous solution;
It prepares polyacrylic acid ester soap-free emulsion: the pre-emulsion and initiator solution is pumped into another micro- reaction respectively It is reacted in stopping reaction long tube after being mixed in the micro-mixer of device, cold bath discharging is after reaction to get described poly- Soap-Free Acrylate Emulsion.
Further, described to prepare in pre-emulsion step, the double bond acrylic monomers includes double bond acrylic acid soft monomer It is oily phase after being mixed uniformly with two kinds of double bond acrylic acid hard monomer.
Further, the double bond acrylic acid soft monomer and double bond acrylic acid hard monomer are according to (3-6): the quality of (4-9) Than being mixed.
Example, the double bond acrylic acid soft monomer includes methyl acrylate, ethyl acrylate, butyl acrylate or third Olefin(e) acid -2- ethylhexyl, the double bond acrylic acid hard monomer include methyl methacrylate or butyl methacrylate.
Further, described to prepare in pre-emulsion step, by alkyl vinyl sulfonate and deionized water according to 1:(25- 30) it is the water phase in the deionized water that mass ratio, which is completely dissolved in,.
Further, described to prepare in pre-emulsion step, the oil is mutually and the velocity ratio of water phase is (1-1.5): 1.
Preferably, described to prepare microreactor used in pre-emulsion step, the internal diameter of micro-mixer is 20-2000 μ m;The internal diameter for stopping reaction tube is 0.5-3mm, residence time 12-60s, reaction pressure 1-5MPa, and reaction temperature is 20℃-30℃。
Further, described to prepare in initiator solution step, by persulfate and deionized water according to 1:(70- 120) mass ratio is completely dissolved in the deionized water up to the initiator solution, and the persulfate is persulfuric acid Ammonium or potassium peroxydisulfate.
Further, described to prepare in polyacrylic acid ester soap-free emulsion step, the pre-emulsion and initiator solution Velocity ratio is 3:2.
Preferably, described to prepare microreactor used in polyacrylic acid ester soap-free emulsion step, micro-mixer it is interior Diameter is 20-2000 μm;The internal diameter for stopping reaction tube is 0.5-3mm, residence time 50-2000s, reaction pressure 5- 10MPa, reaction temperature are 80 DEG C -90 DEG C.
The beneficial effects of the present invention are: the side disclosed by the invention using microreactor synthesis polyacrylic acid ester soap-free emulsion Method, compared with the traditional handicraft of tank reactor preparation, microreactor realizes controllable multiphase Micro-flows, enhances polymerization Mixing, mass transfer and diabatic process in reaction process, substantially reduce the reaction time, improve polymerization efficiency;In addition, polypropylene Acid esters emulsion polymerization is strong exothermal reaction, since microreactor has excellent heat-transfer capability, so that heat is released in reaction Shed in time, realize the control of temperature, overcome conventional method because temperature it is excessively high caused by sudden and violent poly- problem;And microreactor Using serialization feeding manner, operating efficiency is substantially increased.On the whole, the present invention has reaction speed fast, easy to operate, The advantages that production is flexibly, safely controllable, Highgrade integration, serialization.
Detailed description of the invention
Fig. 1 is the shape appearance figure of polyacrylic acid ester soap-free emulsion prepared by the embodiment of the present invention 1;
Fig. 2 is the grain size distribution of polyacrylic acid ester soap-free emulsion prepared by the embodiment of the present invention 1.
Specific embodiment
A kind of method that the present invention discloses microreactor synthesis polyacrylic acid ester soap-free emulsion, this method utilize microreactor It being synthesized, microreactor is made of the micro-mixer and stop reaction tube being connected to, specifically includes the following steps:
Prepare pre-emulsion: using double bond acrylic monomers as oily phase, using alkyl vinyl sulfonic acid saline solution as Water phase, by oily mutually with water phase according to (1-1.5): 1 velocity ratio is pumped into the micro-mixer of a microreactor respectively after mixing It is emulsified in stopping reaction long tube, pre-emulsion is made;
Preferably, it prepares in pre-emulsion step, double bond acrylic monomers includes double bond acrylic acid soft monomer and double bond propylene Two kinds of sour hard monomer is oily phase after being mixed uniformly.Certainly, single double bond acrylic acid soft monomer or double bond acrylic acid are hard Monomer can be used as oil and be combined to polyacrylic acid ester soap-free emulsion, but will lead to the mechanicalness of polyacrylic acid ester soap-free emulsion Can be bad, therefore preferably double bond acrylic acid soft monomer and the mixing of double bond acrylic acid hard monomer is as oily phase.
And specifically, double bond acrylic acid soft monomer and double bond acrylic acid hard monomer according to mass ratio are (3-6): (4-9's) Ratio mixing.
Example, double bond acrylic acid soft monomer includes methyl acrylate, ethyl acrylate, butyl acrylate or propylene Acid -2- ethylhexyl, the double bond acrylic acid hard monomer include methyl methacrylate or butyl methacrylate.
Further, by alkyl vinyl sulfonate and deionized water according to 1:(25-30) mass ratio be completely dissolved in It is water phase in deionized water.
Preferably, microreactor used in pre-emulsion step is prepared, the internal diameter of micro-mixer is 20-2000 μm;Institute State stop reaction tube internal diameter be 0.5-3mm, residence time 12-60s, reaction pressure 1-5MPa, reaction temperature be 20 DEG C- 30℃。
Prepare initiator solution: by persulfate according to 1:(70-120) mass ratio be dissolved in deionized water, stir Obtained initiator solution after mixing uniformly;
Example, persulfate can be ammonium persulfate or potassium peroxydisulfate.
It prepares polyacrylic acid ester soap-free emulsion: pre-emulsion and initiator solution is pumped into respectively according to the velocity ratio of 3:2 It is reacted in stopping reaction long tube after being mixed in the micro-mixer of another microreactor, cold bath goes out after reaction Material is to get polyacrylic acid ester soap-free emulsion.
Preferably, microreactor used in polyacrylic acid ester soap-free emulsion step is prepared, the internal diameter of micro-mixer is 20-2000μm;It is described stop reaction tube internal diameter be 0.5-3mm, residence time 50-2000s, reaction pressure 5-10MPa, Reaction temperature is 80 DEG C -90 DEG C
The following describes the present invention in detail with reference to the accompanying drawings and specific embodiments.
Embodiment 1
The preparation method of the polyacrylic acid ester soap-free emulsion of the present embodiment, comprising the following steps:
Step 1 prepares pre-emulsion
Mix monomer work is prepared after weighing methyl methacrylate, butyl acrylate mixing respectively in mass ratio for 3:4 For oily phase, using emulsifier alkyl vinyl sulfonate: deionized water according to mass ratio be 1:30 prepare emulsifier aqueous solution as Water phase is mutually pumped into oily in the micro-mixer of microreactor after mixing in stopping reaction tube with water phase with the flow velocity of 1.2:1 Emulsification, the logical internal diameter of micro-mixer are 50 μm;The internal diameter for stopping reaction tube is 3mm, residence time 14.4s, and reaction pressure is 1MPa, reaction temperature are 25 DEG C or so, under the above conditions, pre-emulsion are made.
Step 2 prepares initiator solution
With initiator ammonium persulfate: deionized water is that 1:102 prepares initiator solution according to mass ratio;
Step 3, synthesis polyacrylic acid ester soap-free emulsion
The pre-emulsion and initiator solution that step 1 and step 2 are prepared respectively are led to velocity ratio for 3:2 using constant-flux pump It crosses polyfluortetraethylene pipe to be delivered in microreactor, be reacted.Wherein, the internal diameter of micro-mixer is 50 μm;Stop reaction tube Internal diameter be 2mm, reaction pressure 5MPa, reaction temperature be 82 DEG C, reaction time 480s.After reaction, cold water Bathe the polyacrylic acid ester soap-free emulsion that discharges to obtain.Measure monomer conversion be 95.20%, partial size 75.91nm, PDI 0.131, Fig. 1 and Fig. 2 is respectively the shape appearance figure and grain size distribution for the polyacrylic acid ester soap-free emulsion for utilizing transmission electron microscope to obtain, It can be seen from the figure that the spherical morphology of the emulsion particle of the soap-free emulsion of synthesis is regular, and it is evenly distributed.
Embodiment 2
The preparation method of the polyacrylic acid ester soap-free emulsion of the present embodiment, comprising the following steps:
Step 1 prepares pre-emulsion
Mix monomer work is prepared after weighing methyl methacrylate, methyl acrylate mixing respectively in mass ratio for 2:3 For oily phase, using emulsifier alkyl vinyl sulfonate: deionized water according to mass ratio be 1:25 prepare emulsifier aqueous solution as Water phase is mutually pumped into oily in the micro-mixer of microreactor after mixing in stopping reaction tube with water phase with the flow velocity of 1.5:1 Emulsification, the logical internal diameter of micro-mixer are 100 μm;The internal diameter for stopping reaction tube is 2mm, residence time 20s, and reaction pressure is 1.5MPa, reaction temperature are 20 DEG C, under the above conditions, pre-emulsion are made.
Step 2 prepares initiator solution
With initiator ammonium persulfate: deionized water is that 1:75 prepares initiator solution according to mass ratio;
Step 3, synthesis polyacrylic acid ester soap-free emulsion
The pre-emulsion and initiator solution that step 1 and step 2 are prepared respectively are led to velocity ratio for 3:2 using constant-flux pump It crosses polyfluortetraethylene pipe to be delivered in microreactor, be reacted.Wherein, the internal diameter of micro-mixer is 100 μm;Stop reaction tube Internal diameter be 3mm, reaction pressure 7MPa, reaction temperature be 80 DEG C, reaction time 600s.After reaction, cold water Bathe the polyacrylic acid ester soap-free emulsion that discharges to obtain.Measuring monomer conversion is 96.00%, partial size 86.22nm, PDI 0.151.
Embodiment 3
The preparation method of the polyacrylic acid ester soap-free emulsion of the present embodiment, comprising the following steps:
Step 1 prepares pre-emulsion
Mix monomer work is prepared after weighing butyl methacrylate, ethyl acrylate mixing respectively in mass ratio for 4:7 For oily phase, using emulsifier alkyl vinyl sulfonate: deionized water according to mass ratio be 1:27 prepare emulsifier aqueous solution as Water phase is mutually pumped into oily in the micro-mixer of microreactor after mixing in stopping reaction tube with water phase with the flow velocity of 1.3:1 Emulsification, the logical internal diameter of micro-mixer are 200 μm;The internal diameter for stopping reaction tube is 1.5mm, residence time 25s, and reaction pressure is 2MPa, reaction temperature are 23 DEG C, under the above conditions, pre-emulsion are made.
Step 2 prepares initiator solution
With initiator ammonium persulfate: deionized water is that 1:85 prepares initiator solution according to mass ratio;
Step 3, synthesis polyacrylic acid ester soap-free emulsion
The pre-emulsion and initiator solution that step 1 and step 2 are prepared respectively are led to velocity ratio for 3:2 using constant-flux pump It crosses polyfluortetraethylene pipe to be delivered in microreactor, be reacted.Wherein, the internal diameter of micro-mixer is 150 μm;Stop reaction tube Internal diameter be 0.5mm, reaction pressure 6MPa, reaction temperature be 87 DEG C, reaction time 560s.After reaction, cold Water-bath discharges to obtain polyacrylic acid ester soap-free emulsion.Measuring monomer conversion is 93.00%, and partial size 68.47nm, PDI are 0.173。
Embodiment 4
The preparation method of the polyacrylic acid ester soap-free emulsion of the present embodiment, comprising the following steps:
Step 1 prepares pre-emulsion
Mix monomer work is prepared after weighing butyl methacrylate, butyl acrylate mixing respectively in mass ratio for 3:8 For oily phase, using emulsifier alkyl vinyl sulfonate: deionized water according to mass ratio be 1:24 prepare emulsifier aqueous solution as Water phase is mutually pumped into the micro-mixer of microreactor after mixing the cream in stopping reaction tube with water phase by oily with the flow velocity of 1:1 Change, the logical internal diameter of micro-mixer is 20 μm;The internal diameter for stopping reaction tube is 0.5mm, residence time 60s, and reaction pressure is 4MPa, reaction temperature are 28 DEG C, under the above conditions, pre-emulsion are made.
Step 2 prepares initiator solution
With initiator ammonium persulfate: deionized water is that 1:110 prepares initiator solution according to mass ratio;
Step 3, synthesis polyacrylic acid ester soap-free emulsion
The pre-emulsion and initiator solution that step 1 and step 2 are prepared respectively are led to velocity ratio for 3:2 using constant-flux pump It crosses polyfluortetraethylene pipe to be delivered in microreactor, be reacted.Wherein, the internal diameter of micro-mixer is 20 μm;Stop reaction tube Internal diameter be 0.5mm, reaction pressure 9MPa, reaction temperature be 84 DEG C, reaction time 1600s.After reaction, cold Water-bath discharges to obtain polyacrylic acid ester soap-free emulsion.Measuring monomer conversion is 94.55%, and partial size 73.48nm, PDI are 0.146。
Embodiment 5
The preparation method of the polyacrylic acid ester soap-free emulsion of the present embodiment, comprising the following steps:
Step 1 prepares pre-emulsion
Mixing is prepared after weighing butyl methacrylate, acrylic acid-2-ethyl caproite mixing respectively in mass ratio for 1:3 Monomer is as oily phase, with emulsifier alkyl vinyl sulfonate: deionized water is that 1:30 preparation emulsifier is water-soluble according to mass ratio Liquid is mutually pumped into after mixing in the micro-mixer of microreactor with the flow velocity of 1.1:1 and is being stopped instead with water phase as water phase, by oil Ying Guanzhong emulsification, the logical internal diameter of micro-mixer are 2000 μm;The internal diameter for stopping reaction tube is 3mm, residence time 12s, reaction Pressure is 5MPa, and reaction temperature is 30 DEG C, under the above conditions, pre-emulsion is made.
Step 2 prepares initiator solution
With initiator ammonium persulfate: deionized water is that 1:120 prepares initiator solution according to mass ratio;
Step 3, synthesis polyacrylic acid ester soap-free emulsion
The pre-emulsion and initiator solution that step 1 and step 2 are prepared respectively are led to velocity ratio for 3:2 using constant-flux pump It crosses polyfluortetraethylene pipe to be delivered in microreactor, be reacted.Wherein, the internal diameter of micro-mixer is 1000 μm;Stop reaction The internal diameter of pipe is 2.3mm, and reaction pressure 10MPa, reaction temperature is 90 DEG C, reaction time 1000s.Reaction terminates Afterwards, cold bath discharges to obtain polyacrylic acid ester soap-free emulsion.Measuring monomer conversion is 95.80%, and partial size 84.21nm, PDI are 0.161。

Claims (10)

1. a kind of method of microreactor synthesis polyacrylic acid ester soap-free emulsion, which is characterized in that closed using microreactor At, the microreactor is made of the micro-mixer and stop reaction tube being connected to, specifically includes the following steps:
Prepare pre-emulsion: using double bond acrylic monomers as oily phase, using alkyl vinyl sulfonic acid saline solution as water phase, It is mutually pumped into oily after being mixed in the micro-mixer of a microreactor and is emulsified in stopping reaction long tube respectively with water phase, make Obtain pre-emulsion;
It prepares initiator solution: persulfate is dissolved in deionized water, it is water-soluble that the initiator is made after mixing evenly Liquid;
It prepares polyacrylic acid ester soap-free emulsion: the pre-emulsion and initiator solution is pumped into another microreactor respectively It is reacted in stopping reaction long tube after being mixed in micro-mixer, cold bath discharging is after reaction to get the polypropylene Acid esters soap-free emulsion.
2. the method for microreactor synthesis polyacrylic acid ester soap-free emulsion as described in claim 1, which is characterized in that the system In standby pre-emulsion step, the double bond acrylic monomers includes two kinds of double bond acrylic acid soft monomer and double bond acrylic acid hard monomer, It is oily phase after being mixed uniformly.
3. the method for microreactor synthesis polyacrylic acid ester soap-free emulsion as claimed in claim 2, which is characterized in that described double Key acrylic acid soft monomer and double bond acrylic acid hard monomer are according to (3-6): the mass ratio mixing of (4-9).
4. the method for microreactor synthesis polyacrylic acid ester soap-free emulsion as claimed in claim 2 or claim 3, which is characterized in that institute Stating double bond acrylic acid soft monomer includes methyl acrylate, ethyl acrylate, butyl acrylate or acrylic acid-2-ethyl caproite, institute Stating double bond acrylic acid hard monomer includes methyl methacrylate or butyl methacrylate.
5. the method for microreactor synthesis polyacrylic acid ester soap-free emulsion as described in claim 1, which is characterized in that the system In standby pre-emulsion step, by alkyl vinyl sulfonate and deionized water according to 1:(25-30) mass ratio be completely dissolved in institute Stating is the water phase in deionized water.
6. the method for microreactor synthesis polyacrylic acid ester soap-free emulsion as described in claim 1, which is characterized in that the system In standby pre-emulsion step, the oil is mutually and the velocity ratio of water phase is (1-1.5): 1.
7. the method for microreactor synthesis polyacrylic acid ester soap-free emulsion as described in claim 1, which is characterized in that the system Microreactor used in standby pre-emulsion step, the internal diameter of micro-mixer are 20-2000 μm;The internal diameter for stopping reaction tube For 0.5-3mm, residence time 12-60s, reaction pressure 1-5MPa, reaction temperature is 20 DEG C -30 DEG C.
8. the method for microreactor synthesis polyacrylic acid ester soap-free emulsion as described in claim 1, which is characterized in that the system In standby initiator solution step, by persulfate and deionized water according to 1:(70-120) mass ratio be completely dissolved in it is described Up to the initiator solution in deionized water, the persulfate is ammonium persulfate or potassium peroxydisulfate.
9. the method for microreactor synthesis polyacrylic acid ester soap-free emulsion as described in claim 1, which is characterized in that the system In standby polyacrylic acid ester soap-free emulsion step, the velocity ratio of the pre-emulsion and initiator solution is 3:2.
10. the method for microreactor synthesis polyacrylic acid ester soap-free emulsion as described in claim 1, which is characterized in that described Microreactor used in polyacrylic acid ester soap-free emulsion step is prepared, the internal diameter of micro-mixer is 20-2000 μm;It is described to stop Stay reaction tube internal diameter be 0.5-3mm, residence time 50-2000s, reaction pressure 5-10MPa, reaction temperature be 80 DEG C- 90℃。
CN201811424131.7A 2018-11-27 2018-11-27 A kind of method of microreactor synthesis polyacrylic acid ester soap-free emulsion Pending CN109485784A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811424131.7A CN109485784A (en) 2018-11-27 2018-11-27 A kind of method of microreactor synthesis polyacrylic acid ester soap-free emulsion

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811424131.7A CN109485784A (en) 2018-11-27 2018-11-27 A kind of method of microreactor synthesis polyacrylic acid ester soap-free emulsion

Publications (1)

Publication Number Publication Date
CN109485784A true CN109485784A (en) 2019-03-19

Family

ID=65696695

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811424131.7A Pending CN109485784A (en) 2018-11-27 2018-11-27 A kind of method of microreactor synthesis polyacrylic acid ester soap-free emulsion

Country Status (1)

Country Link
CN (1) CN109485784A (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111440063A (en) * 2020-05-09 2020-07-24 惠生(中国)投资有限公司 Production device and production method of liquid crystal polymer precursor acetylated monomer and application of production device
CN111777700A (en) * 2019-04-03 2020-10-16 中国科学院化学研究所 Method for preparing polyolefin by coordination polymerization in microreactor
CN113024708A (en) * 2021-03-15 2021-06-25 浙江大学衢州研究院 Method for preparing fluorine-propylene polymer nano material by micro-channel continuous flow
CN113150204A (en) * 2021-03-15 2021-07-23 浙江大学衢州研究院 Method for preparing soap-free acrylic polymer material by microchannel continuous flow active polymerization
CN113845617A (en) * 2021-11-30 2021-12-28 江苏富淼科技股份有限公司 Method for continuously preparing polyacrylamide inverse emulsion
CN114044845A (en) * 2021-12-01 2022-02-15 上海东升新材料有限公司 Styrene-acrylic latex for papermaking and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2296013A1 (en) * 1999-01-26 2000-07-26 Rohm And Haas Company The reduction of polymer fouling on reactor surfaces in a continuous process for preparing polymers
WO2016003978A1 (en) * 2014-07-02 2016-01-07 Corning Incorporated Synthesis of an acrylic polymer in flow reactor
CN106893015A (en) * 2017-03-28 2017-06-27 南京工业大学 A kind of method that photoinduction organic catalysis prepare polymer under minute yardstick

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2296013A1 (en) * 1999-01-26 2000-07-26 Rohm And Haas Company The reduction of polymer fouling on reactor surfaces in a continuous process for preparing polymers
WO2016003978A1 (en) * 2014-07-02 2016-01-07 Corning Incorporated Synthesis of an acrylic polymer in flow reactor
CN106893015A (en) * 2017-03-28 2017-06-27 南京工业大学 A kind of method that photoinduction organic catalysis prepare polymer under minute yardstick

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
周建华等: "微反应器制备聚丙烯酸酯无皂乳液", 《水性十年 论文集》 *
安德列-斯坦科维茨等: "《化工装置的再设计 过程强化》", 30 September 2012, 国防工业出版社 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111777700A (en) * 2019-04-03 2020-10-16 中国科学院化学研究所 Method for preparing polyolefin by coordination polymerization in microreactor
CN111777700B (en) * 2019-04-03 2021-10-12 中国科学院化学研究所 Method for preparing polyolefin by coordination polymerization in microreactor
CN111440063A (en) * 2020-05-09 2020-07-24 惠生(中国)投资有限公司 Production device and production method of liquid crystal polymer precursor acetylated monomer and application of production device
CN111440063B (en) * 2020-05-09 2023-08-22 惠生(中国)投资有限公司 Production device and production method of liquid crystal polymer precursor acetylated monomer and application of production device
CN113024708A (en) * 2021-03-15 2021-06-25 浙江大学衢州研究院 Method for preparing fluorine-propylene polymer nano material by micro-channel continuous flow
CN113150204A (en) * 2021-03-15 2021-07-23 浙江大学衢州研究院 Method for preparing soap-free acrylic polymer material by microchannel continuous flow active polymerization
CN113845617A (en) * 2021-11-30 2021-12-28 江苏富淼科技股份有限公司 Method for continuously preparing polyacrylamide inverse emulsion
CN114044845A (en) * 2021-12-01 2022-02-15 上海东升新材料有限公司 Styrene-acrylic latex for papermaking and preparation method thereof

Similar Documents

Publication Publication Date Title
CN109485784A (en) A kind of method of microreactor synthesis polyacrylic acid ester soap-free emulsion
CN106832106B (en) A kind of water polyacrylic acid lotion and preparation method thereof
CN102849978B (en) Sustained-release polycarboxylic high-performance water reducing agent and preparation method thereof
CN104261720A (en) Ether polycarboxylate superplasticizer and preparation method thereof
CN105254819A (en) Room-temperature preparation method of early strength type polycarboxylate superplasticizer
CN104530298B (en) A kind of acrylic ester emulsion, preparation method and application thereof
CN106366985A (en) Water-based sealing compound adhesive emulsion and preparation method thereof
CN104892817A (en) Preparation method of organosilicon styrene-acrylate fine emulsion
CN106146755A (en) A kind of preparation method of high solids content silicone acrylic emulsion
CN106632791B (en) One kind resisting fresh cement accumulation of salt in the surface soil priming paint styrene-acrylic emulsion and preparation method thereof
CN108570132B (en) Hybrid emulsion of epoxy ester resin aqueous dispersion and acrylic resin
CN102942659A (en) Method for producing polycarboxylic water reducer by tubular reactor
CN110054727B (en) Preparation method and device of polyacrylamide nano-microspheres
CN107722882A (en) A kind of acrylate emulsion and preparation method thereof
CN108570131A (en) The preparation method of the hybridisation emulsion of epoxy ester resin aqueous dispersion and acrylic resin
CN104844059B (en) A kind of method utilizing numerator self-assembly technique to prepare cement water reducing agent
CN103408681B (en) A kind of method increasing substantially polyvinyl chloride production capacity
CN103755865B (en) soap-free polymerization acrylic emulsion and preparation method thereof
CN103788311B (en) Epoxy-polyacrylate " core-shell structure copolymer " emulsion and preparation method thereof
CN113150204A (en) Method for preparing soap-free acrylic polymer material by microchannel continuous flow active polymerization
CN102826783A (en) Method for rapidly synthesizing polycarboxylic acid water reducers through microwaves and supersonic waves
CN112724309B (en) Continuous production method of hydroxy acrylic resin aqueous dispersion
CN106749802B (en) A kind of preparation method and preparation system of high polymerization degree narrow ditribution polyvinyl alcohol
CN105754046B (en) A kind of preparation method of initiator microcapsules
CN108676114A (en) A kind of synthetic method of acrylic resin

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20190319