CN103396501B - Method and device of emulsion polymerization initiated by ultraviolet light - Google Patents
Method and device of emulsion polymerization initiated by ultraviolet light Download PDFInfo
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- CN103396501B CN103396501B CN201310338681.8A CN201310338681A CN103396501B CN 103396501 B CN103396501 B CN 103396501B CN 201310338681 A CN201310338681 A CN 201310338681A CN 103396501 B CN103396501 B CN 103396501B
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Abstract
The invention relates to a method and a device of emulsion polymerization initiated by ultraviolet light, and belongs to the technical field of polymer synthesis. The device of the emulsion polymerization comprises a rotating-disk reactor, one end of the reactor is connected with a nitrogen source, the other end of the reactor is connected with a emulsion circulating device, the emulsion circulating device comprises a liquid storage tank, a pump, a flow meter, the nitrogen source is connected with a gas inlet of the reactor, and the emulsion circulating device is connected with a liquid inlet and a liquid outlet of the reactor. The method of the emulsion polymerization includes two steps of emulsion preparation and light initiated polymerization. Compared with the prior art, the biggest characteristic of the method and the device of the emulsion polymerization initiated by the ultraviolet light is that: an emulsion can form a very thin liquid film on a rotating disk, and contact area is large, heat dissipation is good, illumination is uniform and absorption rate is high. A prepared polymer has the advantages of high purity, high relative molecular mass and the like. The device is simple in structure, small in volume, easy to operate, and low in energy consumption, can realize continuous operation, and is safe and environmentally friendly.
Description
Technical field
The present invention relates to a kind of emulsion polymerization device and the method for letex polymerization thereof, be specifically related to a kind of device and method causing letex polymerization with UV-irradiation, belong to macromolecule synthesising technology field.
Background technology
The monomer such as acrylic amide, styrenic all can adopt light initiation polymerization, light-initiated (referring generally to visible ray or UV-light) although efficiency of initiation is lower, have activation energy low, can room temperature or low temperature carries out, economical and energy saving, environmental friendliness, Polymer Molecular Weight advantages of higher.
Consider the propagation of light and effective utilization of luminous energy, light initiation polymerization is generally used for the microemulsion system of clear solution system or transparent/translucent, current Chinese scholars is to light-initiated aqueous solution polymerization (polymer, Shane A. Seabrook, Robert G. Gilbert, 48,2007), conversed phase micro emulsion copolymerization (polymer material science and engineering, Xie Long, Shao Ziqiang, 28(5), 2012; ZL200310113365.7) research is more, is that the research of milky letex polymerization is less to light-initiated outward appearance.Chinese patent ZL02129377.5 reports reversed-phase emulsion/suspension polymerization that a kind of UV-light causes water-soluble monomer, UV-light initiating device described in this method comprises intermittent type and continous way two kinds, there is the advantages such as low temperature, quick, equipment is simple, but the subject matter that this method exists is: obviously weaken along with emulsion thickness increases UV-light light intensity, have impact on the specific absorption of light, thus treatment capacity little, be difficult to batch production.Chinese patent ZL201220275437.2 reports a kind of light-initiated device produced for polyacrylamide, ultraviolet lamp box fastener forms airtight light-initiated device on polymerization tank to be polymerized, after reaction certain hour, move through transport unit and overturn, being discharged to next workshop section; When this device is polymerized, technical process is short, production efficiency of equipment is high, but does not have whipping appts in polymerization tank, comparatively be applicable to transparent polymerization system, and for opaque emulsion system, because light transmission is poor, light utilization efficiency is low, is thus not suitable for for letex polymerization.
Summary of the invention
In order to overcome above-mentioned deficiency, the present invention aims to provide a kind of UV-light and causes the device and method of letex polymerization, UV-light cause have temperature low, there is not initiator residue, Polymer Molecular Weight advantages of higher.Letex polymerization combines with light-initiated feature by the present invention, devises a kind of UV-light initiation reaction device of applicable letex polymerization, and this device has the advantages such as liquid film is very thin, contact area is large, absorptivity is high, process batch is large, can be continuously produced.
A kind of UV-light provided by the invention causes the device of letex polymerization, is to adopt following scheme to realize:
A kind of UV-light causes the device of letex polymerization, it is characterized in that: comprise rotating disk reactor, reactor one end connects source nitrogen, the other end connects emulsion circulation device, UV-light is provided with in reactor, emulsion circulation device comprises reservoir, pump, under meter, and source nitrogen is connected with the inlet mouth of reactor, and fluid inlet, the liquid outlet of emulsion circulation device and reactor are connected.
Further, the inlet mouth of described rotating disk reactor is positioned at reactor upper left face, air outlet is positioned at reactor lower right face, reactor shell is cylindrical structure, internal diameter is 280mm, inside reactor central authorities are provided with rotating disk, liquid-inlet pipe is provided with directly over rotating disk, disc surfaces is letex polymerization place, ultraviolet lamp is positioned at directly over rotating disk, and ultraviolet lamp is fixed on reactor wall, is provided with rotating shaft below rotating disk, rotating shaft is connected with the motor below housing through Housing Base, and motor passes through Frequency Converter Control.
Further, the distance of described liquid-inlet pipe lower end and rotating disk is 2 ~ 20mm.
Further, described ultraviolet lamp is any one in medium pressure mercury lamp, high voltage mercury lamp, high-pressure mercury lamp, hernia lamp, tungsten lamp, halogen lamp.Described ultraviolet lamp is preferably medium pressure mercury lamp or high voltage mercury lamp.
The wavelength of described ultraviolet lamp is 200 ~ 400nm, and UV Light intensity is 1 ~ 800W/m
2.
Present invention also offers above-mentioned emulsion polymerizing reactor causes letex polymerization method for UV-light, it is characterized in that: comprise the following steps:
(1) preparation of emulsion: conventional emulsions or reversed-phase emulsion;
1. the preparation of reversed-phase emulsion
Preparation monomer concentration is the monomer solution of 5% ~ 30%; By emulsifiers dissolve in oil phase, the concentration of emulsifying agent is 1% ~ 14%, and HLB value (hydrophile-lipophile balance value) is 4 ~ 7; Aqueous phase/oil phase volume ratio is 1/1 ~ 1.5; Aqueous phase is dropwise added in oil phase, stirs and form stable reversed-phase emulsion;
2. the preparation of conventional emulsions
By emulsifiers dissolve in aqueous phase, the concentration of emulsifying agent is 0.1% ~ 6%, and HLB value is 12 ~ 18; Dropwise added in aqueous phase by oil phase (monomer phase), stirring and forming stable, monomer concentration is the conventional emulsions of 10% ~ 60%;
(2) light initiation polymerization
In rotating disk reactor, first logical nitrogen drives oxygen ten minutes, open rotating disk reactor again, previously prepared good emulsion is squeezed into center of turntable through pump, under meter from fluid inlet from reservoir, under centrifugal action, emulsion is distributed as the liquid film of very thin (0.04 ~ 2.15mm) on rotating disk, initiated polymerization under ultra violet lamp, emulsion enters after reservoir through liquid outlet and circulates, and obtains the emulsion containing polymkeric substance, obtains polymkeric substance finally by after precipitation (flocculation), washing, drying.
In such scheme, described letex polymerization is a kind of with in the polymerization process of UV-light direct trigger monomer letex polymerization production high molecular weight polymer, polymerization single polymerization monomer can be water-soluble monomer, as acrylamide, vinylformic acid, methacrylic acid, sodium acrylate, vinyl P-TOLUENE SULFO ACID 99 sodium; The organic solvent that oil phase adopts is the mixture of the naphthenic hydrocarbon of conventional nonpolar or low-pole, fat alkane or isoparaffin, as hexanaphthene, white oil, kerosene, toluene etc.; Emulsifying agent used is nonionic emulsifier, as alkylphenol polyoxyethylene, polyoxyethylene sorbitan fatty acid ester or sorbitan fatty acid ester etc.; The better effects if of composite emulsifier, as conventional Span class and OP class or the composite emulsifying agent of Tween class, suitable low molecule emulsifying agent and macromolecule emulsifier composite etc., the hydrophile-lipophile balance value of emulsifying agent is preferably 4 ~ 8.Polymerization single polymerization monomer also can be oil-soluble monomer (apolar polymeric monomer), as vinylbenzene, divinyl, methyl methacrylate etc., emulsifying agent is generally ionic emulsifying agent or nonionic emulsifier, as ionic emulsifying agent fatty acid soaps, aliphatic sulphate, sulfonate and some quaternary ammonium salt; Nonionic emulsifier is as polyoxyethylene sorbitan fatty acid ester, alkyl phenolic group Aethoxy Sklerol class, and the hydrophile-lipophile balance value of emulsifying agent is preferably 12 ~ 18.
In the method for letex polymerization involved in the present invention, the wavelength of described ultraviolet lamp is different with monomeric species used, is 200 ~ 400nm, and UV Light intensity is 1 ~ 800W/m
2.
The present invention carries out illumination polymerization, for water-soluble monomer under adopting ordinary method the emulsion configured to be placed in UV-light: aqueous phase is the aqueous solution of one or more water-soluble monomers, and oil phase is the organic solvent being dissolved with the nonpolar of oil-soluble emulsifier or low-pole; For oil-soluble monomer: aqueous phase is the aqueous solution of hydrophilic emulsifier, oil phase is one or more oil-soluble monomers.
Of the present invention
beneficial effect:
Compared with the prior art, the maximum feature of the present invention is: emulsion can form very thin liquid film on rotating disk, and thickness is 0.04 ~ 2.15mm, and contact area is large, good heat dissipation, uniform illumination and specific absorption is high; The polymkeric substance prepared has that purity is high, relative molecular mass advantages of higher.Apparatus structure of the present invention is simple, volume is little, easy to operate, energy consumption is low, can realize operate continuously, safety and environmental protection.
Accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention;
Fig. 2 is rotating disk structure of reactor sketch of the present invention;
In figure, 1 is reservoir, and 2 is pump, and 3 is under meter, and 4 is reactor, and 5 is valve, and 6 is source nitrogen;
4.1 is fluid inlet, and 4.2 is ultraviolet lamp, and 4.3 is rotating disk, and 4.4 is air outlet, and 4.5 is liquid outlet, and 4.6 is rotating shaft, and 4.7 is motor, and 4.8 is frequency transformer, and 4.9 is housing, and 4.10 is inlet mouth.
Embodiment
Further illustrate the present invention below by embodiment, but be not limited to following examples.
Fig. 1 shows the device that UV-light causes letex polymerization, it is characterized in that: comprise rotating disk reactor 4, reactor 4 one end connects source nitrogen 6, the other end connects emulsion circulation device, emulsion circulation device comprises emulsion groove 1, pump 2, under meter 3, source nitrogen 6 is connected with the inlet mouth 4.10 of reactor, and fluid inlet 4.1, the liquid outlet 4.5 of emulsion circulation device and reactor are connected.
Fig. 2 shows the structure of rotating disk reactor, the fluid inlet 4.1 of described rotating disk reactor is positioned at centre above reactor, liquid outlet 4.5 is positioned at reactor base plate right flank, reactor shell 4.9 is cylindrical structure (internal diameter 280mm), inside reactor central authorities are provided with rotating disk 4.3, liquid-inlet pipe is provided with directly over rotating disk 4.3, emulsion becomes very thin liquid film in rotating disk 4.3 surface arrangement under centrifugal action, disc surfaces is letex polymerization place, ultraviolet lamp 4.2 is positioned at above rotating disk, ultraviolet lamp 4.2 is fixed on reactor 4 inwall, rotating shaft 4.6 is provided with below rotating disk 4.2, rotating shaft 4.6 is connected with the motor 4.7 below housing 4.9 through the base plate of housing 4.9, motor 4.7 is controlled by frequency transformer 4.8.Further, the distance of described liquid-inlet pipe lower end and rotating disk is adjustable, and regulation range is 2 ~ 20mm.
In above-mentioned reaction unit, described ultraviolet lamp is any one in medium pressure mercury lamp, high voltage mercury lamp, high-pressure mercury lamp, hernia lamp, tungsten lamp, halogen lamp.The preferred medium pressure mercury lamp of described ultraviolet lamp or high voltage mercury lamp.
The principle of reaction unit of the present invention is:
Letex polymerization is caused for UV-light, comprise the following steps: the emulsion prepared is injected reservoir, open nitrogengas cylinder, in rotating disk reactor, first logical nitrogen drives oxygen 10min, open rotating disk reactor again, rotating speed is set, by previously prepared good emulsion from reservoir through pump, under meter squeezes into center of turntable from opening for feed, under centrifugal action, emulsion is distributed as very thin liquid film on rotating disk, initiated polymerization under ultra violet lamp, emulsion enters after reservoir through discharge port and circulates, reaction cycle time is 10 ~ 240min, obtain the emulsion containing polymkeric substance, finally by precipitation, washing, polymkeric substance is obtained after drying.By regulating emulsion flow and rotary speed to control thickness of liquid film in polymerization process, flow control is 5 ~ 60L/h.
Embodiment 1:
conventional emulsion polymerization
Emulsification is filled a prescription:
Vinylbenzene: 300g
Water: 680g
Sodium laurylsulfonate: 16g
Dimethoxybenzoin: 4g
First be dissolved in vinylbenzene by dimethoxybenzoin, emulsifying agent sodium laurylsulfonate is soluble in water, is slowly instilled in aqueous phase by the vinylbenzene being dissolved with dimethoxybenzoin, stirs 45min and is mixed with stable emulsion.
The emulsion prepared is positioned in reservoir, open rotating disk reactor, rotating speed is set, logical nitrogen drives oxygen 10min, previously prepared good emulsion is squeezed into center of turntable through pump, under meter from opening for feed from reservoir, under centrifugal action, emulsion is distributed as very thin liquid film on rotating disk, initiated polymerization under ultra violet lamp, and emulsion enters after reservoir through discharge port and circulates.Reaction solution surface light intensity is 367.8W/m
2, flow is 15L/h, and reaction cycle time is 210min, obtains containing polymer emulsion, obtains polymkeric substance after finally adding electrolyte sodium chloride flocculation, washing, drying.
The transformation efficiency of sampling and measuring monomer in reaction process, it is 210min that transformation efficiency reaches 96.7% the reaction time; The bonded restorations of the product polystyrene (PS) obtained is 6.52 × 10
6.
Embodiment 2:
conventional emulsion polymerization
Methyl methacrylate: 350g
Sodium lauryl sulphate: 0.2g
OP-10：4.8g
Diisopropyl azodicarboxylate: 30g
Water: 615g
Light initiation polymerization process is with embodiment 1, and flow is constant, and it is 180min that transformation efficiency reaches 96.7% the reaction time; The bonded restorations of the product P MMA obtained is 8.47 × 10
5.
Embodiment 3:
inverse emulsion polymerization
After vinylformic acid 80mL sodium hydroxide is neutralized completely, add in 300mL water and dissolve, then load separating funnel;
OP-10 4.8g, Span80 25.2g are dissolved in 500mL hexanaphthene, to be emulsified dose completely dissolve after, aqueous phase is slowly dripped in oil phase, abundant stirring and emulsifying 30min;
Emulsion is positioned in reservoir, open rotating disk reactor, rotating speed is set, logical nitrogen drives oxygen 10min, previously prepared good emulsion is squeezed into center of turntable through pump, under meter from opening for feed from reservoir, under centrifugal action, emulsion is distributed as very thin liquid film on rotating disk, initiated polymerization under ultra violet lamp, and emulsion enters after reservoir through discharge port and circulates.Reaction solution surface light intensity is 478.3W/m
2, flow is 20L/h, and reaction cycle time is 150min, obtains the reversed-phase emulsion containing polymkeric substance, obtains polymkeric substance finally by after precipitation, washing, drying.
It is 100min that transformation efficiency reaches 97.3% the reaction time, and obtaining sodium polyacrylate bonded restorations is 1.59 × 10
7.
Embodiment 4:
inverse emulsion polymerization
Acrylamide (AM) 80g is dissolved in 420g water, then loads dropping funnel;
OP-10 4.8g, Span80 25.2g are dissolved in 470g hexanaphthene, to be emulsified dose completely dissolve after, aqueous phase is slowly dripped in oil phase, abundant stirring and emulsifying 30min;
Light initiation polymerization process is with embodiment 3, and flow 20L/h, changing reaction solution surface light intensity is 319.2W/m
2, the transformation efficiency of sampling and measuring monomer in reaction process, when the reaction times is 120min, transformation efficiency reaches 97.5%; The product polypropylene acid amides (PAM) obtained is energy fast solvent in water, and without insolubles, bonded restorations is 1.72 × 10
7.
Embodiment 5:
inverse emulsion polymerization
Reversed-phase emulsion formula is:
Acrylamide: 80g
Water: 420g
Hexanaphthene: 460g
Span80：33.6g
OP-10：6.4g
Emulsion preparation and light initiation polymerization process are with embodiment 3, and flow 20L/h, reaction solution surface light intensity is 319.2W/m
2, the transformation efficiency of sampling and measuring monomer in reaction process, it is 100min that transformation efficiency reaches 97.5% the reaction time; The product obtained can rapid solution in water, and without insolubles, bonded restorations is 1.53 × 10
7.
Embodiment 6:
inverse emulsion polymerization
Reversed-phase emulsion formula is:
Sodium acrylate: 100g
Water: 450g
OP-10：4.8g
Span80：25.2g
Hexanaphthene: 420g
Emulsion preparation and light initiation polymerization process are with embodiment 3, and it is 110min that transformation efficiency reaches 96.9% the reaction time; The product obtained can rapid solution in water, and without insolubles, bonded restorations is 1.03 × 10
7.
Claims (8)
1. the device of a UV-light initiation letex polymerization, it is characterized in that: comprise rotating disk reactor, reactor one end connects source nitrogen, the other end connects emulsion circulation device, UV-light is provided with in reactor, emulsion circulation device comprises reservoir, pump, under meter, and source nitrogen is connected with the inlet mouth of reactor, and fluid inlet, the liquid outlet of emulsion circulation device and reactor are connected; The inlet mouth of described rotating disk reactor is positioned at reactor upper left face, air outlet is positioned at reactor lower right face, and reactor shell is cylindrical structure, and internal diameter is 280mm, inside reactor central authorities are provided with rotating disk, be provided with liquid-inlet pipe directly over rotating disk, disc surfaces is letex polymerization place, and ultraviolet lamp is positioned at directly over rotating disk, ultraviolet lamp is fixed on reactor wall, be provided with rotating shaft below rotating disk, rotating shaft is connected with the motor below housing through Housing Base, and motor passes through Frequency Converter Control.
2. UV-light according to claim 1 causes the device of letex polymerization, it is characterized in that: the distance of described liquid-inlet pipe lower end and rotating disk is 2 ~ 20mm.
3. UV-light according to claim 1 causes the device of letex polymerization, it is characterized in that: described ultraviolet lamp is any one in mercury lamp, sodium vapor lamp, hernia lamp, tungsten lamp, halogen lamp.
4. UV-light according to claim 3 causes the device of letex polymerization, it is characterized in that: described ultraviolet lamp is preferably medium pressure mercury lamp or high voltage mercury lamp.
5. UV-light according to claim 1 causes the device of letex polymerization, it is characterized in that: the wavelength of described ultraviolet lamp is 200 ~ 400nm, and UV Light intensity is 1 ~ 800W/m
2.
6. the device of the letex polymerization described in any one of claim 1 ~ 5 is used for the method that UV-light causes letex polymerization, it is characterized in that: light initiation polymerization flow process is:
In rotating disk reactor, first logical nitrogen drives oxygen ten minutes, open rotating disk reactor again, previously prepared good emulsion is squeezed into center of turntable through pump, spinner-type flowmeter from opening for feed from reservoir, under centrifugal action, emulsion is distributed as the liquid film of 0.04 ~ 2.15mm on rotating disk, initiated polymerization under ultra violet lamp, emulsion enters after reservoir through liquid outlet and circulates, and obtains the emulsion containing polymkeric substance, obtains polymkeric substance finally by after precipitation or flocculation, washing, drying.
7. UV-light according to claim 6 causes the method for letex polymerization, it is characterized in that: the monomer of described letex polymerization is water-soluble monomer, comprise any one in acrylamide, vinylformic acid, methacrylic acid, sodium acrylate, vinyl P-TOLUENE SULFO ACID 99 sodium; The organic solvent that oil phase adopts is the mixture of the naphthenic hydrocarbon of conventional nonpolar or low-pole, fat alkane or isoparaffin, comprises any one in hexanaphthene, white oil, kerosene, toluene.
8. UV-light according to claim 6 causes the method for letex polymerization, it is characterized in that: the monomer of described letex polymerization is oil-soluble monomer, comprises any one in vinylbenzene, divinyl, methyl methacrylate.
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| CN202643607U (en) * | 2012-06-12 | 2013-01-02 | 东营市华兴化工有限责任公司 | Photo-initiation device for polyacrylamide production |
| CN203440273U (en) * | 2013-08-06 | 2014-02-19 | 中北大学 | Device for initiating emulsion polymerization by ultraviolet |
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| CN202643607U (en) * | 2012-06-12 | 2013-01-02 | 东营市华兴化工有限责任公司 | Photo-initiation device for polyacrylamide production |
| CN203440273U (en) * | 2013-08-06 | 2014-02-19 | 中北大学 | Device for initiating emulsion polymerization by ultraviolet |
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