CN109679038A - Emulsion polymerisation system, emulsion polymerisation process and application - Google Patents
Emulsion polymerisation system, emulsion polymerisation process and application Download PDFInfo
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- CN109679038A CN109679038A CN201910006609.2A CN201910006609A CN109679038A CN 109679038 A CN109679038 A CN 109679038A CN 201910006609 A CN201910006609 A CN 201910006609A CN 109679038 A CN109679038 A CN 109679038A
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- 239000000839 emulsion Substances 0.000 title claims abstract description 110
- 238000000034 method Methods 0.000 title claims abstract description 28
- 230000008569 process Effects 0.000 title claims description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 131
- 239000003999 initiator Substances 0.000 claims abstract description 63
- 239000000178 monomer Substances 0.000 claims abstract description 54
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 49
- 229920000642 polymer Polymers 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 17
- 239000003995 emulsifying agent Substances 0.000 claims description 15
- 238000004945 emulsification Methods 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 2
- 230000000977 initiatory effect Effects 0.000 claims 1
- 238000009826 distribution Methods 0.000 abstract description 7
- 239000006210 lotion Substances 0.000 abstract description 6
- 230000009257 reactivity Effects 0.000 abstract description 5
- 125000005396 acrylic acid ester group Chemical group 0.000 description 19
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 14
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 12
- 239000007788 liquid Substances 0.000 description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 8
- -1 acrylic ester Chemical class 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000004908 Emulsion polymer Substances 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 230000001804 emulsifying effect Effects 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 3
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 description 3
- 239000006071 cream Substances 0.000 description 3
- 230000005311 nuclear magnetism Effects 0.000 description 3
- 229920000058 polyacrylate Polymers 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- TUZBYYLVVXPEMA-UHFFFAOYSA-N butyl prop-2-enoate;styrene Chemical compound C=CC1=CC=CC=C1.CCCCOC(=O)C=C TUZBYYLVVXPEMA-UHFFFAOYSA-N 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000010556 emulsion polymerization method Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 2
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical group CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- RZYKUPXRYIOEME-UHFFFAOYSA-N CCCCCCCCCCCC[S] Chemical compound CCCCCCCCCCCC[S] RZYKUPXRYIOEME-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 102000004882 Lipase Human genes 0.000 description 1
- 108090001060 Lipase Proteins 0.000 description 1
- 239000004367 Lipase Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BAPJBEWLBFYGME-UHFFFAOYSA-N acrylic acid methyl ester Natural products COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 235000019421 lipase Nutrition 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 208000004396 mastitis Diseases 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000012875 nonionic emulsifier Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 235000019394 potassium persulphate Nutrition 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229940117958 vinyl acetate Drugs 0.000 description 1
Classifications
-
- 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
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
-
- 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
- C08F2/01—Processes of polymerisation characterised by special features of the polymerisation apparatus used
-
- 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
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
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)
Abstract
The present invention provides emulsion polymerisation systems, methods and applications.Wherein, which includes the emulsion tank that reaction kettle, initiator tank and Duo Tai are connected in parallel；Reaction kettle is equipped with reaction solution and mouth and initiator addition mouth is added；The first addition mouth, the second addition mouth and reaction solution outlet are respectively equipped on emulsion tank, reaction solution is exported to be connect with the reaction solution of reaction kettle addition mouth；Initiator tank is equipped with initiator and mouth and initiator outlet is added, and initiator is exported to be connect with the initiator of reaction kettle addition mouth；First flow control valve is respectively equipped on the pipeline that emulsion tank is connect with reaction kettle.The emulsion polymerisation system passes through more emulsion tanks in parallel, different monomers are individually emulsified, reaction kettle polymerization is added in different periods respectively on demand again, it solves the problems, such as the polymer segment random distribution that the reactivity ratio because of different monomers generates, realizes the control to different monomers polymerization quantity and position on lotion polymer segment.
Description
Technical field
The present invention relates to field of chemical engineering, in particular to a kind of emulsion polymerisation system and method are specifically designed including more
The emulsion polymerisation system and method for emulsifying kettle.
Background technique
Acrylic polymer is widely used product in industrial production, can be used for producing coating, adhesive, plastics
Equal products, it is with good performance.Acrylic polymer is usually formed by acrylic ester monomer by emulsion polymerization.
Emulsion polymerization makes monomer be dispersed into emulsion in water, by drawing using water as dispersed phase under the action of emulsifier
Send out agent initiated polymerization.
In the acrylic acid ester emulsion polyplant of the prior art, polymerization reaction is all made of a monomer emulsifying kettle, one
The production system of reaction kettle and an optional post-processing kettle carries out.Several monomeric needed for polymerization reaction is in same emulsion tank
Interior carry out pre-emulsification is added drop-wise to reaction kettle, under the action of initiator, is closed by chain mechanism then by flow control
At high molecular polymer.
Existing acrylic acid ester emulsion synthesis technology process and equipment as shown in Figure 1, in the synthesis process, due to not
The polymerization rate of connatural monomer has differences and (is called reactivity ratio in industry), different monomers structure in macromolecular chain
Random distribution is presented in putting in order for unit.Requirement with market to acrylic acid ester emulsion technical performance is continuously improved, currently,
Acrylic acid ester emulsion manufacturing enterprise is all made of the mode of all kinds of extraordinary monomers of addition to improve the performance of acrylic acid ester emulsion, makes third
The cost of olefin(e) acid ester product emulsion is continuously improved.
Therefore, it is necessary to a kind of device and method that can be effectively improved acrylic acid ester emulsion performance and save production cost.
Summary of the invention
The purpose of the present invention is to provide a kind of emulsion polymerisation systems, pass through more emulsion tanks in parallel of setting and flow control
Valve processed carries out individually emulsification and controllable charging to different monomers, to control different monomers structural unit in polymer segment
Distribution, to realize effective control of block polymerization.
According to an aspect of the present invention, a kind of emulsion polymerisation system is provided, comprising: reaction kettle, initiator tank and Duo Tai
The emulsion tank being connected in parallel；The reaction kettle is equipped with reaction solution and mouth and initiator addition mouth is added；The emulsion tank is respectively equipped with
For the first addition mouth, the second addition mouth for emulsifier to be added and reaction solution outlet of monomer and water, the reaction to be added
Liquid outlet is added mouth with the reaction solution of the reaction kettle respectively and connect；The initiator tank is equipped with initiator and mouth and initiator is added
Outlet, the initiator outlet are added mouth with the initiator of the reaction kettle and connect；The emulsion tank is connect with the reaction kettle
Pipeline on be respectively equipped with first flow control valve.
Preferably, the first flow control valve is successively opened on schedule.
Preferably, the first flow control valve is opened simultaneously.
Preferably, the pipeline that the initiator tank is connect with reaction kettle is equipped with second flow control valve.
Preferably, the top or lower part that the reaction kettle is arranged in mouth is added in the reaction solution.
Another aspect provides a kind of emulsion polymerisation process, are carried out using above-mentioned emulsion paradigmatic system, and
And the following steps are included: the first flow control valve and second flow control valve is made to be in closed state；Described in every
It is separately added into a kind of monomer progress pre-emulsification processing needed for water, emulsifier and emulsion polymerization in emulsion tank, is reacted
Liquid；The initiator is added in the initiator tank；The first part in first flow control valve is opened on demand, so that right
The reaction solution flowed out in emulsion tank is answered to be added in the reaction kettle；Second flow control valve is opened, so that described in initiator addition
Cause the first polymerization reaction in reaction kettle；Optionally, it after first polymerization reaction carries out predetermined amount of time, closes and has turned on
First part's flow control valve opens the second part in first flow control valve, so that the reaction flowed out in corresponding emulsion tank
Liquid is added in the reaction kettle, carries out the second polymerization reaction；Optionally, after second polymerization reaction carries out predetermined amount of time,
The second part flow control valve having turned on is closed, the Part III in first flow control valve is opened, so that corresponding emulsion tank
The reaction solution of middle outflow is added in the reaction kettle, carries out third polymerization reaction.
Preferably, multiple first flow control valves are opened simultaneously, are opened according to each first flow control valve
Size come separately adjustable corresponding reaction solution flow.
Preferably, multiple first flow control valves are successively opened on schedule, while passing through each described first
The size that flow control valve is opened carrys out the flow of separately adjustable corresponding reaction solution.
It preferably, is normal pressure or positive pressure environment in the reaction kettle.
It is yet another aspect of the present invention to provide the applications that above-mentioned emulsion paradigmatic system is used to prepare block polymer.
Emulsion polymer system and method according to the present invention realize independent emulsification and individually charging to various monomers,
It is capable of addition time and the sequence of the various monomers of independent control, to realize the control to monomer distribution and polymer chain segment structure
System.Emulsion polymerisation process of the invention is particularly suitable for block polymer synthesis as a result, can be used for synthesis by kernel to
The core-shell polymer of shell performance gradual change.
Detailed description of the invention
With reference to the attached drawing of accompanying, the more purposes of the present invention, function and advantage are by the as follows of embodiment through the invention
Description is illustrated, in which:
Fig. 1 diagrammatically illustrates the acrylic acid ester emulsion paradigmatic system of the prior art；
Fig. 2 diagrammatically illustrates emulsion polymerisation system of the invention；
Fig. 3 is the polymer that the acrylic ester emulsion polymerization method of comparative example 1 obtains13C nuclear magnetic spectrum；
Fig. 4 is to be individually added into the polymer of butyl acrylate generation the first stage of the embodiment of the present invention 113C core
Magnetic chart spectrum；
Fig. 5 is that the second stage of the embodiment of the present invention 1 continuously adds the polymer for polymerizeing generation after styrene13C nuclear-magnetism
Map；
Fig. 6 is the phase III of the embodiment of the present invention 1 to continuously add the polymer for polymerizeing generation after butyl acrylate13C
Nuclear magnetic spectrum.
Fig. 7 is the DSC map for the acrylic acid ester emulsion polymer that the embodiment of the present invention 1 is prepared.
Fig. 8 is the DSC map for the acrylic acid ester emulsion polymer that comparative example 1 is prepared.
Specific embodiment
As shown in Figure 1, acrylic acid ester emulsion production system 100 includes: the acrylic acid ester emulsion paradigmatic system of the prior art
Monomer emulsifying kettle 101, initiator kettle 102 and reaction kettle 103.
Traditional acrylic ester emulsion polymerization method is as follows: monomer cream is added in several monomeric needed for polymerization reaction together
Change kettle 101 and carry out pre-emulsification, then by flow control, be added drop-wise to reaction kettle 103, in the initiator that initiator kettle 102 is added dropwise
Under the action of, pass through radical reaction mechanism synthesising macromolecule copolymer.In the synthesis process, since all monomers are same
When be added, and the polymerization rate of variety classes monomer has differences (industry in be referred to as reactivity ratio), the height because obtained from
Random distribution is presented in putting in order for different monomers in strand.
The present invention provides a kind of emulsion polymerisation system, by designing more emulsion tanks in parallel, to needed for emulsion polymerization
Different monomers are individually emulsified, according still further to chain length needed for target block polymer and block position respectively when different
Section is added to reaction kettle and is polymerize, and solves asking for the polymer segment random distribution of the reactivity ratio generation because of different monomers
Topic realizes the control to different monomers polymerization quantity and position on lotion polymer segment.
Specifically, emulsion polymerisation system according to the present invention includes the cream that reaction kettle, initiator tank and Duo Tai are connected in parallel
Change tank.Wherein, the reaction kettle is equipped with reaction solution and mouth and initiator addition mouth is added；It is respectively provided on the emulsion tank
The the first addition mouth, the second addition mouth for emulsifier to be added and reaction solution outlet, the reaction solution that monomer and water is added go out
Mouth is added mouth with the reaction solution of the reaction kettle respectively and connect；The initiator tank is equipped with initiator addition mouth and initiator goes out
Mouthful, the initiator outlet is added mouth with the initiator of the reaction kettle and connect.
First flow control valve is respectively equipped on the pipeline that the emulsion tank is connect with the reaction kettle.The be arranged such
Flow control valve can control the reaction solution of more emulsion tanks generation while add or add at times, and various reaction solutions
It can independently be added with identical or different speed.
First flow control valve can be opened successively on schedule.At this point, differential responses liquid is added in different time sections,
It can effectively realize the block polymerization of different monomers component the polymerization quantity and sequence of macromolecular chain.
First flow control valve can also be opened simultaneously.If differential responses liquid adds simultaneously according to different flow, can
Realize emulsion particle by kernel to the hud polymerization of shell performance gradual change.
Further, the pipeline that the initiator tank is connect with reaction kettle is equipped with second flow control valve.
Preferably, it is respectively equipped with agitating device in the emulsion tank, initiator tank and reaction kettle, for accelerating emulsion process
Or in reaction kettle reaction solution reaction.
According to a specific embodiment, in emulsion polymerisation system of the invention, in each emulsion tank be added monomer and
The mouth of water is the same addition mouth, is added by a main pipe rail, two bye-passes are usually added on main pipe rail, are water respectively
Pipe is added and pipe is added in monomer.
According to another embodiment, a kind of emulsion polymerisation process using above-mentioned emulsion paradigmatic system is provided:
The first flow control valve and second flow control valve is set to be in closed state；
It is pre- that a kind of monomer progress needed for water, emulsifier and emulsion polymerization is separately added into every emulsion tank
Emulsification treatment obtains reaction solution；
The initiator is added in the initiator tank；
The first part in first flow control valve is opened on demand, so that institute is added in the reaction solution flowed out in corresponding emulsion tank
It states in reaction kettle；
Second flow control valve is opened, so that initiator, which is added in the reaction kettle, causes the first polymerization reaction；
Optionally, after first polymerization reaction carries out predetermined amount of time, the first part's flow control having turned on is closed
Valve opens the second part in first flow control valve, so that the reaction kettle is added in the reaction solution flowed out in corresponding emulsion tank
In, cause the second polymerization reaction；
Optionally, after second polymerization reaction carries out predetermined amount of time, the second part flow control having turned on is closed
Valve opens the Part III in first flow control valve, so that the reaction kettle is added in the reaction solution flowed out in corresponding emulsion tank
In, carry out third polymerization reaction.
First part, second part and the Part III of above-mentioned first flow control valve may include one or more the respectively
Flow control valve, preferably a respectively first flow control valve.
Monomeric species quantity is determined according to the chain segment number of subject polymer, correspondingly can determine emulsion tank quantity, with
And the stage quantity of polymerization reaction.
Emulsion polymerization is carried out using emulsion polymerisation system provided by the invention, can be reacted under normal pressure, it can also be just
Pressure ring reacts under border.Under synthesis under normal pressure, the settable condenser in reaction kettle top；Under malleation reaction, reaction kettle passes through with emulsion tank
Upper pipeline connection, and and atmospheric isolation.Reaction kettle can be added to by gravity stream in high-order emulsion tank by designing,
Reaction kettle can be added to by fluid pump.
Reaction solution enters the position of reaction kettle, i.e., reaction solution addition mouth can be on reaction kettle top, can also be in reaction kettle
Lower part, it can be added under addition or liquid level on liquid level.
The monomer of above-mentioned acrylic acid ester emulsion polymerization can be alkene and acrylic compounds containing unsaturated double-bond.Its
In, acrylic compounds for example can be selected from (methyl) acrylic acid, (methyl) methyl acrylate, (methyl) ethyl acrylate, (first
Base) propyl acrylate, (methyl) butyl acrylate, (methyl) Isooctyl acrylate monomer etc..Alkene containing unsaturated double-bond is for example
It can be selected from ethylene, propylene, isopropyl alkene, styrene, butadiene, maleic anhydride, vinylacetate, acrylonitrile, acrylamide etc..
Ionic (anionic or cationic) emulsifier, nonionic emulsifier or two can be selected in mentioned emulsifier
The compound emulsion system of person.Above-mentioned suppurative mastitis agent may be, for example, alkyl sulfate, alkylsulfonate, polyoxyethylene ether etc., dosage
Usually the 0.1~5.0% of monomer total amount.
The initiator of emulsion polymerization generally can be by the initiator that generates free radicals of thermal decomposition or organic peroxide and also
Former agent combination, may be, for example, ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate, dibenzoyl peroxide or hydrogen peroxide etc..Initiator
Dosage be usually the 0.2~1.0% of monomer total amount.
Specifically, for tri-block acrylic acid ester emulsion polymerization starting monomer include the first monomer, second comonomer and
Third monomer.
For example, as shown in Fig. 2, emulsion polymerisation system according to the present invention 200 includes 204, one, an initiator tank anti-
Answer kettle 205 and three emulsion tanks (201,202,203) in parallel.
Three emulsion tanks be respectively provided with for monomer and water to be added first be added mouth (206,207,208), for being added
Mouth (209,210,211) and reaction solution outlet (212,213,214), and the reaction solution of three emulsion tanks is added in the second of emulsifier
Outlet is added mouth 222 with the reaction solution of reaction kettle respectively and connect and be correspondingly provided with three first flow control valves therebetween
(215,216,217).There is initiator tank initiator to be added mouth 218 and initiator outlet 219, and initiator outlet 219 with it is anti-
It answers the initiator of kettle that the connection of mouth 220 is added and a second flow control valve 221 is provided therebetween.
Above-mentioned first flow control valve (215,216,217) can independent control, be respectively used to the anti-of three emulsion tanks of control
Liquid stream output is answered, they can be opened simultaneously, can also successively be opened on schedule.
Above-mentioned three emulsion tanks (201,202,203), initiator tank 204 and reaction kettle 205 are equipped with agitating device, are used for
Accelerate emulsion process or polymerization reaction therein.
Specifically, tri-block acrylic acid ester emulsion polymerization procedure is as follows:
Close three first flow control valves (215,216,217)；
Mouth 206 is added by first in first monomer and water, emulsifier is added mouth 209 by second and the first emulsion tank is added
It is emulsified in 201, obtains the first reaction solution；
Mouth 207 is added by first in second comonomer and water, emulsifier is added mouth 210 by second and the second emulsion tank is added
It is emulsified in 202, obtains the second reaction solution；
Mouth 208 is added by first in Third monomer and water, emulsifier is added mouth 211 by second and third emulsion tank is added
It is emulsified in 203, obtains third reaction solution；
Mouth 218 is added by initiator in initiator to be added in initiator tank 204, is stirred evenly；
The first flow control valve 215 of the first emulsion tank 201 is opened, so that the reaction solution of the first monomer is added by reaction solution
Entrance 222 is added in reaction kettle 205；
Second flow control valve 221 is opened, mouth 220 is added by initiator in initiator and is added in reaction kettle 205, is caused
First polymerization reaction forms the first segment；
After first polymerization reaction carries out predetermined amount of time, the first flow control valve 215 of the first emulsion tank 201 is closed, is opened
The first flow control valve 216 of the second emulsion tank is opened, is added instead so that mouth 222 is added by reaction solution in the reaction solution of second comonomer
It answers in kettle 205, causes the second polymerization reaction, form the second segment；
After second polymerization reaction carries out predetermined amount of time, the first flow control valve 216 of the second emulsion tank 202 is closed, is opened
The first flow control valve 217 of third emulsion tank 203 is opened, is added so that mouth 222 is added by reaction solution in the reaction solution of Third monomer
Enter in reaction kettle 205, causes third polymerization reaction, form third segment.
It can be obtained when at least one of the first monomer to Third monomer is acrylic ester monomer by above method
The acrylate polymer emulsion of tri-block.
Hereinafter, the embodiment of the present invention will be described with reference to the drawings.In the accompanying drawings, identical appended drawing reference represents identical
Or similar component or same or like step.
Embodiment 1
The method for carrying out acrylic emulsion polymerization using the embodiment of the present invention 1 is as follows:
Make first flow control valve (215,216,217) and second flow control valve 221 all in closed state；
Butyl acrylate 208.75g, water 52.25g, lauryl sodium sulfate 5.3g are added in emulsion tank 201, under room temperature
Pre-emulsification 0.5h is carried out, the first reaction solution is obtained；
Styrene 130g, water 33g, lauryl sodium sulfate 3.4g are added in emulsion tank 202, carries out pre-emulsification, reaction
Condition is stirring at normal temperature 0.5h, obtains the second reaction solution；
Butyl acrylate 208.75g, water 52.25g, emulsifier (lauryl sodium sulfate) 5.3g are added in emulsion tank 203,
Room temperature carries out pre-emulsification 0.5h, obtains third reaction solution；
Initiator (dibenzoyl peroxide) 3g is added in initiator tank 204；
Flow control valve 215 is opened, the first reaction solution (i.e. butyl acrylate emulsion) is added in reaction kettle 205, stream
Speed control is in 185L/h.Initiator is added into reaction kettle 205 for turn-on flow rate control valve 221, and flow control is in 0.75L/h.Into
The first polymerization reaction of row 1.5h；
Flow control valve 215 is closed, flow control valve 216 is opened, the second reaction solution (i.e. styrene emulsion) is added
In reaction kettle 205, the second polymerization reaction 1h is carried out, flow velocity is identical as the first polymerization reaction；
Flow control valve 216 is closed, flow control valve 217 is opened, makes third reaction solution (i.e. butyl acrylate emulsion)
It is added in reaction kettle 205, carries out third polymerization and react 1.5h, flow velocity is identical as the first polymerization reaction, and tri-block propylene is made
Acid esters lotion.
Above-mentioned polymeric reaction temperature is 82~85 DEG C.
The lotion that each stage of reaction of above-described embodiment 1 obtains is carried out13The detection of C nuclear-magnetism, obtained map such as Fig. 4~6
It is shown.
Fig. 4 is the polymer generated at the end of the present embodiment the first polymerization reaction13C nuclear magnetic spectrum.At this point, only carrying out
The homopolymerization of butyl acrylate forms butyl acrylate segment.Figure 4, it is seen that only showing methyl (0 in polymer
~50ppm), the characteristic peak of methylene (50~100ppm) and carbonyl (150~200ppm).
Fig. 5 is the polymer generated at the end of the present embodiment the second polymerization reaction13C nuclear magnetic spectrum.At this point, being added second
After monomer styrene, on styrene-grafted to butyl acrylate segment, the polymerization of butyl acrylate-styrene di-block is formd
Object.From figure 5 it can be seen that having newly increased the characteristic peak (100~150ppm) of phenyl ring compared to Fig. 4.
Fig. 6 is the polymer generated at the end of the present embodiment third polymerization is reacted13C nuclear magnetic spectrum.At this point, third is added
After monomer butyl acrylate, butyl acrylate is grafted on the segment of butyl acrylate-styrene di-block, forms propylene
Acid butyl ester-Styrene And Butyl-acrylate tri-block polymer.Compared to Fig. 4, after butyl acrylate again is added, methyl, Asia
The characteristic peak peak area of methyl and carbonyl becomes larger.
Comparative example 1
Emulsion polymerization is carried out with condition same as Example 1, difference is the emulsion polymerization system using the prior art,
Reaction kettle is added according to the primary emulsification of identical proportion in three kinds of monomers.
Step 1: by butyl acrylate 417.5g, distilled water 137.5g, styrene 130g and emulsifier (dodecyl sulphur
Sour sodium) 14g be added monomer emulsifying kettle 101 in stirring carry out pre-emulsification, process conditions be room temperature under stir 0.5h, reacted
Liquid；
It polymerize step 2: above-mentioned reaction solution and initiator (dibenzoyl peroxide) are added in reaction kettle, polymerize
Reaction temperature is 82~85 DEG C, reacts 4h, and acrylic acid ester emulsion is made.
The result of comparative example 1 is as shown in figure 3, as can be seen that due to comparison from the nuclear-magnetism test map of the polymer of Fig. 3
Monomer is mixed together addition in method used by example 1, and what is allowed to carry out is random atactic polymerization, therefore the polymerization of its synthesis
The noise signal peak of the nuclear magnetic spectrum of object is relatively more.
To the acrylic acid ester emulsion according to made from above embodiments 1 and comparative example 1 with differential scanning calorimetry (DSC,
NETZSCH DSC 200F3 240-20-1204L) measurement glass transition temperature (Tg) curve, as a result it is shown in Fig. 7 and figure
8。
By Fig. 7 and Fig. 8 it can further be shown that acrylate cream is made with according to the existing emulsion polymerisation process of comparative example 1
Liquid (Tg=-21.8 DEG C) is compared, and according to embodiments of the present invention 1 acrylic acid ester emulsion has well-regulated three block structure, is had
Significantly lower glass transition temperature (- 45.6 DEG C).
It follows that the present invention individually emulsifies different monomers, then press by more emulsion tanks in parallel of design
It is added separately to reaction kettle according to formula time segment to be reacted, the reactivity ratio for solving different monomers is random to polymer segment
Distribution problem realizes the control to different monomers polymerization quantity and position on acrylic emulsion polymer segment.
It is equipped with flow control valve on the pipeline that every emulsion tank is connect with reaction kettle, these flow control valves can control
More emulsion tanks are added dropwise simultaneously or are added dropwise at times.When more emulsion tanks are added dropwise simultaneously, just it is close with traditional reaction process；
But if be added dropwise respectively according to different time sections, so that it may realize to different monomers on acrylic acid and ester lotion polymer segment
Polymerization quantity and the control to put in order, that is, realize the block polymerization of acrylic acid ester emulsion polymer segment, to develop lotion
The new function of product provides condition；If more emulsion tanks are added dropwise simultaneously according to different flow, gradation type nucleocapsid may be implemented
Polymerization technique.
In short, the present invention realizes the industrialization of acrylic acid and ester body emulsion theory, traditional acrylic acid has been overturned
And the design theory of Lipase absobed formula, a new method has been expanded for the raising of the performance of acrylic acid and ester product emulsion.Pass through
Transformation to existing acrylic acid ester emulsion production procedure, may be implemented the combination of a variety of emulsion polymerization processes, and production is more
The product of performance-adjustable.
In conjunction with the explanation and practice of the invention disclosed here, the other embodiment of the present invention is for those skilled in the art
It all will be readily apparent and understand.Illustrate and embodiment is regarded only as being exemplary, true scope of the invention and purport are equal
It is defined in the claims.
Claims (10)
1. a kind of emulsion polymerisation system, comprising:
The emulsion tank that reaction kettle, initiator tank and Duo Tai are connected in parallel；
Wherein, the reaction kettle is equipped with reaction solution and mouth and initiator addition mouth is added；
The emulsion tank is respectively provided with the first addition mouth that monomer and water is added, the second addition mouth for emulsifier to be added
It is exported with reaction solution, the reaction solution outlet is added mouth with the reaction solution of the reaction kettle respectively and connect；
The initiator tank is equipped with initiator and mouth and initiator outlet, the initiation of the initiator outlet and the reaction kettle is added
Mouth connection is added in agent；
First flow control valve is respectively equipped on the pipeline that the emulsion tank is connect with the reaction kettle.
2. emulsion polymerisation system according to claim 1, wherein the first flow control valve is successively opened on schedule
It opens.
3. emulsion polymerisation system according to claim 1, wherein the first flow control valve is opened simultaneously.
4. emulsion polymerisation system according to claim 1, wherein set on the pipeline that the initiator tank is connect with reaction kettle
There is second flow control valve.
5. emulsion polymerisation system according to claim 1, wherein the reaction solution is added mouth and the reaction kettle is arranged in
Top or lower part.
6. a kind of emulsion polymerisation process, which is characterized in that it is used such as emulsion polymerization according to any one of claims 1 to 5
System carries out, and the following steps are included:
The first flow control valve and second flow control valve is set to be in closed state；
A kind of monomer progress pre-emulsification needed for water, emulsifier and emulsion polymerization is separately added into every emulsion tank
Processing, obtains reaction solution；
The initiator is added in the initiator tank；
The first part in first flow control valve is opened on demand, so that the reaction solution addition flowed out in corresponding emulsion tank is described anti-
It answers in kettle；
Second flow control valve is opened, so that initiator, which is added in the reaction kettle, causes the first polymerization reaction；
Optionally, after first polymerization reaction carries out predetermined amount of time, the first part's flow control valve having turned on is closed, is opened
The second part in first flow control valve is opened, so that the reaction solution flowed out in corresponding emulsion tank is added in the reaction kettle, into
The second polymerization reaction of row；
Optionally, after second polymerization reaction carries out predetermined amount of time, the second part flow control valve having turned on is closed, is opened
The Part III in first flow control valve is opened, so that the reaction solution flowed out in corresponding emulsion tank is added in the reaction kettle, into
The reaction of row third polymerization.
7. emulsion polymerisation process according to claim 6, wherein multiple first flow control valves are opened simultaneously, root
Carry out the flow of separately adjustable corresponding reaction solution according to the size that each first flow control valve is opened.
8. emulsion polymerisation process according to claim 6, wherein multiple first flow control valves are first on schedule
After open, while the size opened by each first flow control valve is come the flow of separately adjustable corresponding reaction solution.
9. emulsion polymerisation process according to claim 6, wherein be normal pressure or positive pressure environment in the reaction kettle.
10. the application that emulsion polymerisation system according to any one of claim 1 to 5 is used to prepare block polymer.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111718440A (en) * | 2020-08-01 | 2020-09-29 | 浙江亦龙新材料有限公司 | Production process of acrylate emulsion |
| CN111871243A (en) * | 2020-08-01 | 2020-11-03 | 浙江亦龙新材料有限公司 | Emulsification system of production acrylic ester emulsion |
| CN115414881A (en) * | 2022-08-26 | 2022-12-02 | 昆山石梅新材料科技有限公司 | Acrylic resin processing equipment and processing technology |
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| CN2622181Y (en) * | 2003-05-27 | 2004-06-30 | 东营市圣光高分子化工有限责任公司 | Full sealing and automatic equipment for emulsion polymerization |
| CN205575987U (en) * | 2016-04-22 | 2016-09-14 | 浙江新力化工有限公司 | A ally oneself with and use device for preparing acrylic emulsion |
| CN209383683U (en) * | 2019-01-04 | 2019-09-13 | 北京华腾东光科技发展有限公司 | Emulsion polymerisation system |
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| JP2002293812A (en) * | 2001-04-02 | 2002-10-09 | Nitto Denko Corp | Method for producing aqueous dispersion-type polymer and production device |
| CN2622181Y (en) * | 2003-05-27 | 2004-06-30 | 东营市圣光高分子化工有限责任公司 | Full sealing and automatic equipment for emulsion polymerization |
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| CN111718440A (en) * | 2020-08-01 | 2020-09-29 | 浙江亦龙新材料有限公司 | Production process of acrylate emulsion |
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| CN115414881A (en) * | 2022-08-26 | 2022-12-02 | 昆山石梅新材料科技有限公司 | Acrylic resin processing equipment and processing technology |
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