CN103145884A - Experimental instrument for photo-initiated solution polymerization - Google Patents

Abstract

The invention discloses an experimental instrument for photo-initiated solution polymerization. The experimental instrument comprises a cabinet and is characterized in that a plurality of narrow-band ultraviolet lamps and a polymerization reaction vessel are arranged in the cabinet; a sliding bracket is arranged at the bottom of the cabinet, and the narrow-band ultraviolet lamps are vertically arranged on the sliding bracket; the polymerization reaction vessel is arranged in the moving direction of the narrow-band ultraviolet lamps, and a gap is formed between the narrow-band ultraviolet lamps and the polymerization reaction vessel; the polymerization reaction vessel can rotate around the axis of the polymerization reaction vessel, and the rotating speed is adjustable; and a light intensity sensor I and a light intensity sensor II are arranged in the moving direction of the narrow-band ultraviolet lamps and are respectively arranged at the two sides of the polymerization reaction vessel. According to the experimental instrument, the use and combination number of ultraviolet lamp sources can be controlled through adjusting and controlling the rotating angular velocity of a turntable, and the light radiation energy received by a polymerization system can be adjusted through adjusting the distance between light sources and a reaction device, so that a method for controlling primary-activity free radical generation rate by using multiple control manners is realized.

Description

The laboratory apparatus of light-initiated solution polymerization

Technical field

The present invention relates to a kind of laboratory apparatus of light-initiated solution polymerization, belong to the photopolymerization synthesis technical field of superpolymer.

Background technology

(molecular weight is greater than 10 for water-soluble extra high molecular polymer ⁷) mainly refer to polyacrylamide (PAM) base polymer, to form by the acrylamide homopolymerization or with other monomer copolymerization, high molecular weight polyacrylamide is mainly as flocculation agent and thickening material (" water-soluble polymers " tight auspicious Xuan, Chen Zhenxing etc., Chemical Industry Press, 1988).The synthetic of water-soluble extra high molecular polymer is a radical polymerization or free-radical polymerized process, can be divided into thermal-initiated polymerization and light initiation polymerization according to the difference of the providing energy.In the thermal-initiated polymerization reaction process, thermal initiator absorbs heat generation primary activity radical polymerization, in a single day thermal initiator adds polymerization system, along with the heat of polymerization that carries out of polyreaction is understood constantly accumulation, cause thermal initiator to decompose and the autoacceleration phenomenon occurs, in polymerization system, number of free radical is wayward.In polymerization mid-term, the autoacceleration phenomenon is obvious, polymerization system number of free radical and system temperature are high, free radical interacts and the probability increase of termination, this is the major cause that thermal-initiated polymerization is difficult to improve polymericular weight, while number of free radical vary within wide limits, synthetic polymer molecule amount wider distribution.With respect to the thermal-initiated polymerization reaction, light initiating polymerizing reaction is to absorb photon by light trigger to decompose and generation primary activity free radical, initiated polymerization.Therefore, light initiating polymerizing reaction only needs the absorb light quantity of radiant energy at the chain initiating stage with regard to the chain reaction of polymerization process, and, light trigger is insensitive to heat, initiation temperature independent (" the high-molecular optical principles of chemistry and application " Li Shanjun, the ability of recording Gui etc., press of Fudan University, 2003).So, control the optical radiation energy of polymerization system reception and just can realize the generating rate of primary activity free radical in polymerization system or the control of growing amount.

Control for the optical radiation energy realizing polymerization system is received, must select suitable laboratory apparatus: treat that polymeric solution accepts intensity of illumination and can measure, intensity of illumination can be regulated control by one or more modes, it is even that same position treats that polymeric solution is accepted illumination, and the polymerization system part is subject to intensity of illumination and can changes and have certain regularity.At present, the photo-actinic action instrument is divided into photochemistry instrument and photopolymerization instrument, and wherein the photochemistry instrument can be divided into ambient light irradiation chemical apparatus, built-in optical irradiation chemical apparatus and overhead type illumination photochemistry instrument according to the difference of radiation of light source mode.Photopolymerization instrument pooled applications is in synthetic materials, according to treating that polymeric material receives the difference of intensity of illumination regulative mode, can be divided into the photopolymerization instrument of intensity of illumination unadjustable (or intermittent control) and the photopolymerization instrument of capable of regulating illumination intensity continuously.Photopolymerization compound experiment instrument based on the water-soluble extra high molecular polymer molecular weight of free radical effective concentration regulation and control there is not yet report.

Ambient light shines and external light source illumination according to being divided into again the inner chamber light source light, patent application CN102056848A discloses a kind of photochemical reactor, its reaction vessel uses sleeve type structure, light source is placed in the inner chamber of reaction vessel, this has just limited it and has treated the regulation and control that reaction solution receives quantity of radiant energy, in addition, the telescoping reaction vessel is unfavorable for the taking-up of photopolymerization experimental product.Patent application CN101947426A discloses a kind of many test tube stirrings-rotary photochemical reaction device, and in vitro stirring, a plurality of test tubes rotate around light source its test tube by magneton, and light source shines the test tube under rotating state after filtering.This appliance ensure accept the homogeneity of illumination between the homogeneity of reaction soln concentration and each test tube, process the photon that makes question response liquid receive narrower wavelength region by optical filtering, but, this device faces equally and can not by the restriction of distance adjustment intensity of illumination, use the larger test tube of length and internal diameter also to be unfavorable for the taking-up of photopolymerization experimental product as reaction vessel.Patent application CN2675243Y discloses a kind of built-in optical chemical reactor, and it uses optical fiber that light is directly introduced in reaction solution.Although this reactor has been avoided the loss of optical radiation energy, improved light efficiency, but, because optical fiber is got involved in reaction solution, the surrounding layer of optical fiber might have certain chemical action to partial reaction liquid, and certain limitation is arranged, optical fiber is got involved in reaction solution simultaneously, the shift in position of its intervention is large, be difficult for accurately controlling, and this controls the important factor of local number of free radical exactly.Patent application CN10172968A discloses a kind of point light source photo-chemical integrated reactor, is characterized in using overhead light source direct irradiation reaction soln, can reduce the vessel that hold reaction solution to the absorption of optical radiation energy.The overhead type light source design is lower to the requirement of reaction vessel, and the parent who is subject to the laboratory staff of preliminary study photo-actinic action looks at.But, being subject to the impact that solution receives illumination uniformity and sample path length, overhead type illumination is unfavorable for the control to the local number of free radical of solution.

Patent application CN2689411Y discloses a kind of production electric wire ultraviolet light cross-linking apparatus, its ultraviolet lighting case by several Non-polarized lamp modular units along treat that the crosslinked cable central axial direction is arranged in order and on the space circumference of distance central axis certain distance evenly distributed combination form.Although equipment has been realized the evenly crosslinked of the same thickness of cable insulation,, the position of this equipment Non-polarized lamp modular unit is immovable, this has just limited the control of this equipment to optical radiation energy, can not regulate and control continuously optical radiation energy.Patent application EP0933801 discloses a kind of polymerization lamp, and it has for measurement light source and treats the device of the distance between polymeric material and adjust the irradiation power of light source or the lamp control unit of time according to described distance.Although the polymerization lamp shows the advantage of having considered to control with the variation of polymerization parameter light source, it can not guarantee to obtain good polymerization.Measurement light source and treat that distance between polymeric material is not enough to guarantee the accurate control to polymerization is particularly to the control of polymerization system microcosmic part.The light initiation polymerization system comprises light trigger, and the photon numbers of the specified wavelength that receives is depended in the activation of light trigger especially.But, measuring distance can not disclose angle or the shape of the focal plane that is applied to material, and the optical radiation energy that material receives depends on these parameters, so, rely on light source and treat that measuring distance between polymeric material is not enough to the optical radiation energy that represents that material receives.

Summary of the invention

Originally the laboratory apparatus that the purpose of this invention is to provide a kind of light-initiated solution polymerization, make the optical radiation energy that the polymerization system differentiation element receives to measure, can calculate, and control the generating rate of primary activity free radical in the light initiation polymerization system as function, make that in Photopolymer System, number of free radical can remain on a dynamic steady concentration.The present invention can be applicable to the aqueous solution polymerization of ordinary light initiator, can control molecular weight and molecualr weight distribution.

The laboratory apparatus of a kind of light-initiated solution polymerization provided by the present invention, it comprises cabinet; Be provided with several narrow ripple ultraviolet lamp and polymerization containers in described cabinet;

The bottom of described cabinet is provided with slide holder, and described several narrow ripple ultraviolet lamps vertically are arranged on described slide holder, and can move along described slide holder;

On the direction that moves along described several narrow ripple ultraviolet lamps, described polymerization container is set, and is provided with spacing between described several narrow ripple ultraviolet lamps and described polymerization container; Described polymerization container can rotate around its axle center, and the speed of described rotation is adjustable;

Be provided with light intensity sensor I and light intensity sensor II on the direction that described narrow ripple ultraviolet lamp moves, and be separately positioned on the both sides of described polymerization container, described light intensity sensor I is arranged near described narrow ripple ultraviolet lamp end, described light intensity sensor II is arranged on away from described narrow ripple ultraviolet lamp end, and described light intensity sensor I and described light intensity sensor II lay respectively at bottom and the top on the plane of living in, bottom of described polymerization container.

In above-mentioned laboratory apparatus, described slide holder comprises slide bar and the screw rod that is connected, described several narrow ripple ultraviolet lamps are arranged on described slide bar, described screw rod is connected with the electric motor I, drives described screw rod rotation and make described narrow ripple ultraviolet lamp move to control distance between light source and described polymerization container when the work of described electric motor I.

In above-mentioned laboratory apparatus, described several narrow ripple ultraviolet lamps are fixed on light holder support, and described light holder support is fixed on described slide bar.

In above-mentioned laboratory apparatus, described polymerization container is located on a rotating disk, and described rotating disk is connected with the electric motor II, drives the rotation of the described polymerization container on described rotating disk with the rotation of described electric motor II.

In above-mentioned laboratory apparatus, described rotating disk is made by iron, cobalt or nickel, as steel;

The chassis of described polymerization container is made by magneticsubstance, and then by magnetic effect, described polymerization container just can be fixed on described rotating disk firmly.

In above-mentioned laboratory apparatus, described rotating disk is provided with the hole of a truncated cone-shaped, and the big opening end face of described hole is connected with described polymerization container;

The lower surface on the chassis of described polymerization container is provided with one and the corresponding Rotary-table of described hole shape, and described Rotary-table can be positioned in described hole; The height of described Rotary-table is less than the height of described hole.

In above-mentioned laboratory apparatus, be provided with tinted shade between described several narrow ripple ultraviolet lamps and described polymerization container.

In above-mentioned laboratory apparatus, described cabinet is provided with one outward with the measuring apparatus of graduated scale, one end of described graduated scale is fixed on described light holder support, and described graduated scale and described slide bar be arranged in parallel, are used for distance, the Calibrating source that measurement light source moves and detect ultraviolet lamp source attenuation degree.

In above-mentioned laboratory apparatus, the shady face of described light holder support is provided with the fan I, is provided with the fan II on the tank wall of described cabinet, and described fan I and described fan II are positioned on same level;

Also be provided with an exhaust blower in described cabinet, described exhaust blower is arranged on the opposite side of described polymerization container, and is the direction away from described narrow ripple ultraviolet lamp.

In above-mentioned laboratory apparatus, between described several narrow ripple ultraviolet lamps, on the inwall of described cabinet, be equipped with temp probe on the outer wall of the inside of described polymerization container and described polymerization container, the temperature signal that described temp probe is measured can respond on computer, regulate the power of described fan I according to displays temperature, to change the flow of heat-eliminating medium, guarantee that the ultraviolet lamp source temperature is stable; According to the described fan II of temperature regulation of described cabinet inboard and the power of described exhaust blower, control the suitable flow of heat-eliminating medium, guarantee that described temperature in chassis is in suitable allowable temperature scope, heat-eliminating medium enters described cabinet from described fan I, through light source, area of illumination and reaction unit, send into the air channel by exhaust blower and discharge, take away simultaneously the ozone of area of illumination and other volatile matter to purify the cabinet environment; Measure quartz reaction container internal and external temperature, by heat transfer theory, can tentatively judge the degree that polymerization is carried out.

In above-mentioned laboratory apparatus, described cabinet uses has the tinned(sheet)iron of shielding effect to be made to UV-light, and its internal layer scribbles non-smooth light absorbing material, in case because of the impact of reflection of light on the experimental data accuracy.The bottom of described cabinet can be used thicker steel or be used in conjunction with concrete, increases the weight of cabinet, to reduce the vibrations that bring when electric motor and blower fan are worked.The case lid of movable folding can be made in a side of cabinet, so that the picking and placeing and the maintenance of instrument of polymerization sample.All all use the window shutter Model Design at area of illumination with the extraneous part that communicates cabinet, to prevent ultraviolet leakage.

Light-initiated solution polymerization laboratory apparatus provided by the invention can realize controlling generating rate or the growing amount of primary activity free radical in the polymerization system differentiation element, and its control principle is as follows:

Due to the size of the reaction vessel that the uses size much smaller than light source, can think only a branch of directional light that reaction unit receives; Because the light path of refraction effect light in the reaction vessel wall changes, use is made the thinner reaction vessel of wall to the less quartzy material of ultraviolet radiation absorption, just can ignore reaction vessel to ultraviolet absorption, be that under the different irradiating angles of identical intensity of illumination, the intensity of illumination that is transmitted in quartzy wall is identical; In order to simplify calculating, the propagation direction of supposing light does not change with the variation of the concentration gradient of the difference of propagation medium or propagation medium.

As shown in Figure 4, light passes differentiation element 404 and shines the place apart from center of rotation axis r apart from the air between directional light 401 and reaction solution, because energy has additivity, the optical radiation energy that differentiation element 404 receives just equals the optical radiation energy that the radiation of light source energy deducts air and reaction solution absorption.According to Law of Lambert-Beer, the intensity of illumination at differentiation element 404 places is:

$I=I_0\exp [-{\mathrm{\ϵ}}_0{c}_0(R-\sqrt{R^2-r^2{\sin }^2\mathrm{\θ}})]\·\exp [-{\mathrm{\ϵ}}_p{c}_p(\sqrt{R^2-r^2{\sin }^2\mathrm{\θ}}-r\cos \mathrm{\θ})]$ （1）

$=I_0\exp [-{\mathrm{\ϵ}}_0{c}_{0}R+{\mathrm{\ϵ}}_p{c}_{p}r\cos \mathrm{\θ}-({\mathrm{\ϵ}}_p{c}_p-{\mathrm{\ϵ}}_0{c}_0)\sqrt{R^2-r^2{\sin }^2\mathrm{\θ}}]$

In formula (1): I ₀From nearest reaction vessel inwall 402 light intensity of light source, ε ₀The optical extinction coefficient of air, c ₀The concentration of air extinction component, ε _pThe optical extinction coefficient of solution, c _pBe the concentration of solution extinction component, R is the internal diameter of reaction vessel cross section annulus, and θ is line and the direction of illumination angulation of differentiation element 404 and center of rotation.

Differentiation element 404 place's optical radiation powers:

P=I△A

$=I_0\mathrm{h\Δlexp}[-{\mathrm{\ϵ}}_0{c}_{0}R+{\mathrm{\ϵ}}_p{c}_{p}r\cos \mathrm{\θ}-({\mathrm{\ϵ}}_p{c}_p-{\mathrm{\ϵ}}_0{c}_0)\sqrt{R^2-r^2{\sin }^2\mathrm{\θ}}]---\left(2\right)$

$=I_0\mathrm{h\ωr\Δtexp}[-{\mathrm{\ϵ}}_0{c}_{0}R+{\mathrm{\ϵ}}_p{c}_{p}r\cos \left(\mathrm{\ωt}\right)-({\mathrm{\ϵ}}_p{c}_p-{\mathrm{\ϵ}}_0{c}_0)\sqrt{R^2-r^2{\sin }^2\left(\mathrm{\ωt}\right)}]$

In formula (2): I is the intensity of illumination at differentiation element 404 places, and Δ A is the optical radiation area of differentiation element 404,

H is the height of solution; Δ l is the circumference differential length of radius r, and ω is the circular frequency of rotating disk, and t is polymerization reaction time, and ω t is the angle 403 that experiences the 404 rotation t times of differentiation element.

The optical radiation energy that receives apart from the center of rotation axis r any point elapsed time T of place is:

$Q={\∫}_0^T{I}_0\mathrm{h\ωrexp}[-{\mathrm{\ϵ}}_0{c}_{0}R+{\mathrm{\ϵ}}_p{c}_{p}r\cos \left(\mathrm{\ωt}\right)-\left({\mathrm{\ω}}_t\right)-({\mathrm{\ϵ}}_p{c}_p-{\mathrm{\ϵ}}_0{c}_0)\sqrt{R^2-r^2{\sin }^2\left(\mathrm{\ωt}\right)}]\mathrm{\Δt}---\left(3\right)$

For convenience of calculation, the ultraviolet wavelength of simplifying narrow ripple ultraviolet lamp is λ, and corresponding frequency is ν:

Treat that the radiant light subnumber that polymeric solution receives is:

According to the definition of quantum yield, the radiant light subnumber that in φ=polymerization system, the growing amount/polymeric solution of primary activity free radical receives:

The growing amount of primary activity free radical in the polymerization system differentiation element T time

=φ×N

$=\frac{\mathrm{\φ}}{\mathrm{hv}}{\∫}_0^T{I}_0\mathrm{h\ωrexp}[-{\mathrm{\ϵ}}_0{c}_{0}R+{\mathrm{\ϵ}}_p{c}_{p}r\cos \left(\mathrm{\ωt}\right)-({\mathrm{\ϵ}}_p{c}_p-{\mathrm{\ϵ}}_0{c}_0)\sqrt{R^2-r^2{\sin }^2\left(\mathrm{\ωt}\right)}]\mathrm{\Δt}---\left(4\right)$

By formula (4) as can be known, after the internal diameter of initiator, optical source wavelength and reaction vessel was selected, impact had apart from the influence factor of the generating rate of center of rotation axis r place any polymerization system differentiation element primary activity free radical: dial rotation angular velocity omega, from the nearest reaction vessel inwall light intensity I of place of light source ₀, polymerization reaction time t, r place solution extinction component t instantaneous concentration c constantly _p

The concentration of supposing solution extinction component in the Δ t time is constant, and in interior polymerization system of Δ t time, generating rate and the long-pending of reaction times Δ t of primary activity free radical is exactly the growing amount of primary activity free radical in polymerization system.Thus, by the generating rate of primary activity free radical and the integral area of polymerization reaction time t in the calculating polymerization system, obtain total growing amount of primary activity free radical in polymerization reaction time t moment polymerization system, in conjunction with the starting point concentration of known solution extinction component, can characterize the constantly instantaneous concentration c of r place solution extinction component of polymerization system t _p

Regulation and control dial rotation angular velocity omega and from the nearest reaction vessel inwall light intensity I of place of light source ₀Be the characteristics of the light-initiated solution polymerization laboratory apparatus design of the present invention, can control ω or I by the present invention ₀, also just realized the adjusting of the generating rate of primary activity free radical in the polymerization system differentiation element, can effectively control the polymerization system number of free radical.

Laboratory apparatus provided by the invention, rotary optical reaction unit wherein uses the ambient light radiation, according to Law of Lambert-Beer, treat that apart from what light source did not exist together the optical radiation energy that polymeric solution receives is different, in rotary course, the generating rate of primary activity free radical in the polymerization system differentiation element can be effectively regulated in the optical radiation energy generating period variation that each differentiation element receives, and controls number of free radical for intermittent type illumination a new method is provided.The optical source wavelength narrow range of laboratory apparatus of the present invention, optical source wavelength is adjustable, and intensity of illumination can be regulated continuously, and the average generating rate of polymerization system primary activity free radical is controlled, uses computer operation.Compare with existing all kinds of photochemistry instruments and photopolymerization instrument, have following beneficial effect:

1, the present invention uses narrow ripple ultraviolet lamp source as light source, avoid or reduced the destruction of energy upper wavelength section to the C-C key in high voltage mercury lamp equiwavelength a wider range light source, the lower ultrared minimizing of energy has simultaneously suppressed ultraviolet lamp and has lighted the transformation of energy of rear luminous energy thermotropism, greatly reduce the temperature of ultraviolet lamp to the dependence of burning time, light source is more tended towards stability.

2, the present invention uses the ultraviolet lamp source as light source, and dismounting is simple, for needing the replacing optical source wavelength that convenience is provided because the selection of light trigger is different.For using the composite light initiation polymerization experiment of carrying out of multiple light initiator, the present invention can be by selecting the combination in the narrow ripple ultraviolet lamp of different wave length source, for the light initiation polymerization experiment provides a kind of combined light source for the difference between the absorption bands of use light trigger.

The distance adjustment of use number of combinations, light source and reaction unit that 3, the present invention can be by the ultraviolet lamp source by the actual measurement intensity of illumination regulation and control intensity of light source, has realized the interior continuous adjusting of light source intensity of illumination greatest irradiation scope.

4, the present invention has realized the calculated with mathematical model of the optical radiation energy that the polymerization system differentiation element receives, and partly controls for the polymerization system microcosmic and has set up the basis.

5, the present invention can control by the adjusting of dial rotation circular frequency, control the use number of combinations in ultraviolet lamp source, and the mode of the distance adjustment of light source and reaction unit regulates the optical radiation energy that polymerization system receives, and realized that multiple control modes controls the method for primary activity free radical generating rate.

6, dial rotation circular frequency of the present invention has been realized control able to programme, by computer settings rotational angular velocity and corresponding rotation time, provides convenience for controlling number of free radical by dial rotation circular frequency.

7, light intensity sensor, temperature sensor and the controller of the present invention's use all are connected with computer, intuitive display, and it is convenient to control, and has guaranteed the real-time of data monitoring and continuity and the accuracy of data gathering.

Description of drawings

Fig. 1 is the structural representation of light-initiated solution polymerization laboratory apparatus of the present invention.

Fig. 2 is front view and the vertical view of the ultraviolet lamp of light-initiated solution polymerization laboratory apparatus of the present invention, and wherein Fig. 2 (a) is front view, and Fig. 2 (b) is vertical view.

Fig. 3 is sectional view and the vertical view of the reaction vessel of light-initiated solution polymerization laboratory apparatus of the present invention, and wherein Fig. 3 (a) is sectional view, and Fig. 3 (b) is vertical view.

Fig. 4 is the simplification mathematical model schematic diagram that the present invention calculates optical radiation.

in figure, each mark is as follows: 100 cabinets, 101 light holder supports, 102 ultraviolet lamps, 103 slide holders, 104 electric motor II, 113 electric motor I, 105 rotating disks, 106 polymerization containers, 107 fan I, 108 fan II, 109 exhaust blowers, 110 air channels, 111 measuring apparatuss, 112 graduated scales, 114 tinted shades, 115 light intensity sensor I, 116 light intensity sensor II, 201 hardwares, 301 holes, 302 chassis, 303 Rotary-tables, 401 directional lights, the inwall of 402 polymerization containers, 403 angles, 404 differentiation elements.

Embodiment

The experimental technique that uses in following embodiment is ordinary method if no special instructions.

In following embodiment, material used, reagent etc., if no special instructions, all can obtain from commercial channels.

As Fig. 1, Fig. 2 and shown in Figure 3, light-initiated solution polymerization laboratory apparatus provided by the invention comprises a cabinet 100, its use has the tinned(sheet)iron of shielding effect to be made to UV-light, its internal layer scribbles non-smooth, blackwash interior interpolation UV light absorber Octabenzone, can absorb in a large number the UV-light of shining on it, in case because of the impact of reflection of light on the experimental data accuracy; Thicker steel are used in bottom at cabinet 100, to increase its weight.Be fixed with a slide holder 103 on the bottom of cabinet 100, it comprises slide bar (not shown) and the screw rod (not shown) that is connected, and wherein screw rod is connected with electric motor I 113, and the power of rotation is provided for screw rod.Be provided with tube stand 101 and can move along slide bar on slide bar, be fixed with 10 ultraviolet lamps that are evenly arranged 102 on it, and ultraviolet lamp 102 being fixed on tube stand 101 by hardware 201.When screw rod rotated under the drive of electric motor I 113,101 of tube stands can move under the drive of screw rod.In cabinet 100, the direction that moves along ultraviolet lamp 102 is provided with polymerization container 106, and it is cylindrical, and it is supported by quartz, and its chassis 302 is made by magneticsubstance.This polymerization container 106 is arranged on 1 rotating disk 105, and this rotating disk 105 is connected with electric motor II 104, will drive rotating disk 105 and rotate when its work, and then polymerization container 106 also rotates under the drive of rotating disk 105.Its turntable 105 is made by steel, and heart place is provided with the hole 301 of a truncated cone-shaped therein, and the diameter of its big opening end is 10mm, and the diameter of osculum end is 5mm, and its big opening end face is connected with the chassis 302 of polymerization container 106; The center of 302 lower surface is provided with 1 corresponding Rotary-table 303 of the shape with this hole 301 on the chassis simultaneously, this Rotary-table 303 can be positioned in this hole 301, and the height of Rotary-table 303 is slightly less than the height of hole 301, due to magnetic effect, polymerization container 106 just can be fixed on rotating disk 105 firmly like this.On the direction that moves along ultraviolet lamp 102, be provided with light intensity sensor I 115 near polymerization container 106 places, and be fixed on the bottom of cabinet 100 by the support (not shown), and a little less than the height of rotating disk 105; Opposite side at polymerization container 106 is provided with the light intensity sensor II equally, and is fixed on the bottom of cabinet 100 by the support (not shown), and detachable, a little more than rotating disk 105 height; The intensity of illumination signal that light intensity sensor I 115, light intensity sensor II 116 are measured can respond on computer, regulates the rotational angular velocity of rotating disk 105 according to the intensity of illumination that shows.Be provided with a tinted shade 114 between ultraviolet lamp 102 and polymerization container 106.Be provided with 1 with the measuring apparatus 111 of graduated scale 112 outside cabinet 100, one end of this graduated scale 112 is fixed on light holder support 101, and this graduated scale and slide bar be for be arrangeding in parallel, is used for distance, the Calibrating source that measurement light source moves and detects ultraviolet lamp source attenuation degree.In cabinet 100, be provided with fan I 108 in the shady face of light holder support 101, be provided with fan II 107 on the tank wall of cabinet 100, and this fan I 108 is positioned on same level with the fan II; Also be provided with an exhaust blower 109 in cabinet 100, this exhaust blower 109 is arranged on the opposite side of polymerization container 106, and is the direction away from ultraviolet lamp 102, and exhaust blower 109 air channel 110 outer with being arranged on cabinet 100 is connected.Between ultraviolet lamp 102, on the inwall of cabinet 100, be equipped with the temp probe (not shown) on the outer wall of the inside of polymerization container 106 and polymerization container 106, the temperature signal that these temp probes are measured can respond on computer, regulate the power of fan I 108 according to displays temperature, to change the flow of heat-eliminating medium, guarantee that the ultraviolet lamp source temperature is stable; According to the temperature regulation fan 107 of cabinet inboard and the power of exhaust blower 109, control the suitable flow of heat-eliminating medium, guarantee that temperature in chassis is in suitable allowable temperature scope, the dotted arrow direction of heat-eliminating medium in Fig. 1, heat-eliminating medium enters cabinet from fan I 107, through light source, area of illumination and reaction unit, send into air channel 110 by exhaust blower 109 and discharge, take away simultaneously the ozone of area of illumination and other volatile matter to purify the cabinet environment.

Use light-initiated solution polymerization laboratory apparatus of the present invention, when ultraviolet lamp being installed for the first time or changing lamp, all will carry out the demarcation of light source.

At first 10 ultraviolet lamps are fixed on light holder support, (as the center in lamp source) in the same horizontal line, use movably light intensity sensor II 116 to be attached to successively on each ultraviolet lamp source, measure light intensity, each ultraviolet lamp source continuously measured is (computer system arranges 5 seconds and gathers a secondary data) about 30 seconds, namely measures 6 data points.Until the light intensity in 10 lamp sources measure complete after, according to the individual difference in lamp source, the position in the lamp source of again arranging makes light on the propagation direction, light intensity distributes about the centrosymmetry of lamp.

Light intensity sensor movably is placed in the inwall place of polymerization container, select respectively the various combination in ultraviolet lamp source, be combined to by two ultraviolet lamp sources in the middle of using the whole ultraviolet lamps source of using, mobile light source, the relation of measuring nose light intensity, polymerization container inwall light intensity and light source position.And the variation relation function of the light intensity that the combination of different ultraviolet lamps sources is lower and light source position inputs in computer, and as from the nearest reaction vessel inwall light intensity I of place of light source ₀Control basis.

Set the required incident illumination intensity of polymerization, select the appropriate vol journey, namely select to open the number of combinations in ultraviolet lamp source, according to the funtcional relationship of light intensity and light source position, calculating is I from the nearest reaction vessel inwall place light intensity of light source ₀The time corresponding front end light intensity value, intensity of illumination by front end light intensity sensor I115 response, selection control light source travel direction moves forward or moves backward, this is to realize by the sense of current that changes electric motor I 113, then press the beginning movable button, connect circuit, light source moves, select to stop movable button when the intensity of illumination of front end light intensity sensor response reaches calculated value, namely be I from the nearest reaction vessel inwall place light intensity of light source this moment ₀

Each light-initiated solution polymerization laboratory apparatus of the present invention that uses all need be opened instrument preheating ultraviolet lamp source 10min in advance, to guarantee light stability.Come in contact or collide for fear of light source facility and reaction unit facility and cabinet, should control the reading of graduated scale at 15～60cm, i.e. in the light-initiated solution polymerization laboratory apparatus of the present invention, the moving range of light source is 45cm.After light source position is regulated and to be completed, observe the reading of graduated scale, if when with calibration value, relatively large deviation being arranged, illustrate that the ultraviolet lamp source is existing decays significantly, should consider to change the ultraviolet lamp source.

According to the Source calibration result, realized and can regulate and control continuously in light source intensity of illumination greatest irradiation scope, select suitable intensity of illumination I ₀, can be by the effective concentration of disc angle speed regulation and control free radical.

The rotary optical reaction unit is under the ambient light radiation condition, treat that apart from what light source did not exist together the optical radiation energy that polymeric solution receives is different, in the rotary course of rotating disk, treat the optical radiation energy generating period variation that polymeric solution differentiation element 404 receives, the speed that generates the primary activity free radical changes thereupon.When the polymeric solution differentiation element turned to apart from light source the most nearby, intensity of illumination was maximum, and the number of photons that receives is many, and the generating rate of primary activity free radical is large; Along with the increase of distance between this differentiation element and light source, intensity of illumination reduces, and the number of photons that differentiation element receives reduces, and the generating rate of primary activity free radical is little.During greater than the termination speed of free radical, number of free radical increases when the generating rate of elementary living radical, and when the generating rate of the elementary living radical termination speed less than free radical, number of free radical reduces.Select suitable rotational angular velocity, make in the dial rotation process in one week, the average generating rate of primary activity free radical equals the average termination speed of free radical, be that chain causes and chain termination reaches one-period running balance, in polymerization system, number of free radical is relatively stable, and synthetic molecular weight distribution is narrower.So, can effectively regulate number of free radical in the polymerization system differentiation element by disc angle speed.

Along with the carrying out of polyreaction, the density loss of initiator, the generating rate of primary activity free radical reduces, and realizes that chain initiation and the disc angle speed that chain termination reaches one-period running balance become thereupon this moment.By the variation relation research to decomposition of initiator speed and disc angle speed, and with in this relation function input computer, control disc angle speed and rotation time with this function.

Claims (10)

1. the laboratory apparatus of a light-initiated solution polymerization, it comprises cabinet; It is characterized in that: be provided with several narrow ripple ultraviolet lamp and polymerization containers in described cabinet;

The bottom of described cabinet is provided with slide holder, and described several narrow ripple ultraviolet lamps vertically are arranged on described slide holder, and can move along described slide holder;

On the direction that moves along described several narrow ripple ultraviolet lamps, described polymerization container is set, and is provided with spacing between described several narrow ripple ultraviolet lamps and described polymerization container; Described polymerization container can rotate around its axle center, and the speed of described rotation is adjustable;

Be provided with light intensity sensor I and light intensity sensor II on the direction that described narrow ripple ultraviolet lamp moves, and be separately positioned on the both sides of described polymerization container, described light intensity sensor I is arranged near described narrow ripple ultraviolet lamp end, described light intensity sensor II is arranged on away from described narrow ripple ultraviolet lamp end, and described light intensity sensor I and described light intensity sensor II lay respectively at bottom and the top on the plane of living in, bottom of described polymerization container.

2. laboratory apparatus according to claim 1, it is characterized in that: described slide holder comprises slide bar and the screw rod that is connected, and described several narrow ripple ultraviolet lamps are arranged on described slide bar, and described screw rod is connected with the electric motor I.

3. laboratory apparatus according to claim 2, it is characterized in that: described several narrow ripple ultraviolet lamps are fixed on light holder support, and described light holder support is fixed on described slide bar.

4. the described laboratory apparatus of any one according to claim 1-3, it is characterized in that: described polymerization container is located on a rotating disk, and described rotating disk is connected with the electric motor II.

5. laboratory apparatus according to claim 4, it is characterized in that: described rotating disk is made by iron, cobalt or nickel;

The chassis of described polymerization container is made by magneticsubstance.

6. laboratory apparatus according to claim 5, it is characterized in that: described rotating disk is provided with the hole of a truncated cone-shaped, and the big opening end face of described hole is connected with described polymerization container;

The lower surface on the chassis of described polymerization container is provided with one and the corresponding Rotary-table of described hole shape, and described Rotary-table can be positioned in described hole; The height of described Rotary-table is less than the height of described hole.

7. the described laboratory apparatus of any one according to claim 1-6, is characterized in that: be provided with tinted shade between described several narrow ripple ultraviolet lamps and described polymerization container.

8. the described laboratory apparatus of any one according to claim 3-7, it is characterized in that: described cabinet is provided with one outward with the measuring apparatus of graduated scale, one end of described graduated scale is fixed on described light holder support, and described graduated scale and described slide bar be arranged in parallel.

9. the described laboratory apparatus of any one according to claim 3-7, it is characterized in that: the shady face of described light holder support is provided with the fan I, be provided with the fan II on the tank wall of described cabinet, and described fan I and described fan II are positioned on same level;

Also be provided with an exhaust blower in described cabinet, described exhaust blower is arranged on the opposite side of described polymerization container, and is the direction away from described narrow ripple ultraviolet lamp.

10. laboratory apparatus according to claim 9 is characterized in that: between described several narrow ripple ultraviolet lamps, on the inwall of described cabinet, be equipped with temp probe on the outer wall of the inside of described polymerization container and described polymerization container.

Images