CN104877048B - A kind of bulk polymerization of monomer constant speed dropping - Google Patents

Abstract

The bulk polymerization of a kind of monomer constant speed dropping, after being stirred by reactant, drops to carry out in reactor polyreaction with constant rate of speed constant speed, the maximum rate f of constant rate of speed_maxSelect according to following steps: test polymerization enthalpy and the reaction rate curve of described reactant with dynamic DSC；Use Kamal Sourour kinetic model to carry out optimization matching the reaction rate curve obtained, obtain the parameter value of model；Parameter value and polymerization enthalpy are substituted in heat release model, and combines Fourier's heat transfer model and jointly calculate, it is thus achieved that under different drop rate, during assigned temperature, the monomer conversion of reaction system is schemed over time；When drop rate is more than f_maxTime, described variation diagram represents reaction system generation implode.The present invention is not only restricted to prepare the size of product, it is possible to well solve heat radiation difficulty and " implode " problem in polymerisation in bulk；Prepared material is uniform, it is to avoid introduce new impurity, has the dielectric properties of excellence.

Description

A kind of bulk polymerization of monomer constant speed dropping

Technical field

The present invention relates to a kind of bulk polymerization, especially, the body that the present invention relates to the dropping of a kind of monomer constant speed gathers Conjunction method.

Background technology

In recent years, the frequency involved by electronic equipment and communication has reached the wave band of GHz, and this trend adds By force.However as the rising of frequency, the device temperature that dielectric material loss is caused raises and also can become to be more serious, thus shadow Ring equipment life or even normally work.Meanwhile, the frequency that communication apparatus such as communications satellite and radar is involved at present is the most not It is limited only to single frequency band, due to dielectric loss, decay or distortion can occur when signal is through dielectric material.Therefore, have Necessity prepares the structural material still under a kind of wideband with relatively low-k and dielectric loss.It addition, at large-scale vacuum, Gao Gong Insulating element on rate pulser, also mechanical property and dimensional stability to material have higher requirement.In order to obtain Excellent dielectric properties, should avoid introducing other impurity as far as possible, and its preparation generally uses the method for polymerisation in bulk, because body Polymerization be monomer under conditions of not solubilizer and other dispersant, initiator or heat, light, radiation effect under, be not added with The polymerization process that other media are carried out.Be characterized in that product purity is high, it is to avoid introduce other impurity, be not required to complexity separation, Purifying, operation is relatively simple, produces utilization rate of equipment and installations high.

But, polymerisation in bulk itself there is also the defect of many: such as process heat effect is relatively large, due to system viscosity It is continuously increased with polymerization, system mixing and heat transfer difficult；In the case of radical polymerization, often due to the heat release of reaction itself And rate of polymerization autoacceleration effect occurs, thus material is caused to have bubble, variable color；Molecular weight of product distribution width, unreacted list Body is difficult to eliminate, products machinery degradation etc.；If it is improper to control, easily causes implode, even cause engineering accident.

In some bulk polymerisation process, by taking effective monitoring temperature and cooling provision, still it is capable of big The polymerisation in bulk of scale.Such as, during producing General Purpose Polystyrenre by polymerisation in bulk, reduce reaction system autoacceleration Phenomenon thus avoid the method for " implode " to include: (1) use multi-floating bodies, be responsible for different phase polyreaction；(2) in reaction System adds a small amount of solvent viscosity with reduction reaction system, thus improves the heat-transfer effect of system；(3) reactor with And stirring paddle is equipped cooling water pipe.

But, when preparing crosslinked polystyrene by polymerisation in bulk, crosslinking can make implode problem in bulk polymerisation process More serious, and because product is thermosetting, also will not melt under high temperature, it is impossible to help heat radiation by existing measure, thus Make automatically speeding up of reaction become apparent from, and then cause " implode ".Therefore, for the synthesis of heat cured crosslinked polystyrene, Above-mentioned measure will be the most applicable, instead be analogous to segmented program intensification polymerization used during PMMA sheet material produces, Concrete operations are that monomer is polymerized moulding at a higher temperature to certain viscosity, and are polymerized at a lower temperature to reacting several Complete, carry out high temperature post polymerization the most again.But, when product reaches certain size or requirement has the higher degree of cross linking, Even if under relatively low reaction temperature, it is difficult to the reaction heat distributed runs up to the most easily cause internal temperature mistake High and runaway reaction.Additionally, whole technique seems the most loaded down with trivial details, and during moulding, serious monomer volatilizees not only Polluting environment, healthy to operator also has great harm.

Another kind of measure is to use ultraviolet light supplemental polymeric method.So-called uv photopolymerization refers to the irradiation at ultraviolet light Under, light trigger produces active center by photochemical reaction, thus causes the course of reaction of polymerization.Polymerization methods with other Comparing, uv photopolymerization technology has the feature such as energy-saving and environmental protection, safety.But single uv photopolymerization can not obtain relatively High monomer conversion, needs carry out collaborative with thermal polymerization, seems more complicated in technique.Secondly, except thermal initiator it Outward, also need to add special photoinitiator, thus introduced more impurity, affect the dielectric properties of material.Prior It is that, under the irradiation of ultraviolet light, material can be aging because of molecular chain rupture, thus significantly compromises the mechanical property of material.Cause This, a kind of method being badly in need of crosslinked polystyrene being obtained in that large-size.

Summary of the invention

For solving above-mentioned technical problem, the invention provides the bulk polymerization of a kind of monomer constant speed dropping, the method It is not only restricted to prepare the size of product, it is possible to well solve heat radiation difficulty and " implode " problem in polymerisation in bulk, prepared Material avoid introducing new impurity, have excellence dielectric properties.

The purpose of the present invention is realized by following technical proposal:

The bulk polymerization of a kind of monomer constant speed dropping, including step: after being stirred by reactant, with constant rate of speed Drop to continuously in reactor, carry out polyreaction；The maximum rate f of described constant rate of speed_maxSelect according to following steps:

1) polymerization enthalpy and the reaction rate song of described reactant is tested with dynamic DSC (DSC) Line.In order to improve accuracy, DSC test can use multiple heating rate test reaction rate curve, such as can use 1 DEG C/ Min, 2 DEG C/min and the heating rate of 5 DEG C/min.

2) to step 1) the middle reaction rate curve employing Kamal-Sourour kinetic model obtainedCarry out optimization matching, obtain parameter A₁、A₂、E₁、E₂, m, n Value；

In this model, d α/dt represents that reaction rate, α represent the monomer conversion i.e. extent of reaction, and R is ideal gas constant, R=8.314J/mol/K.

Can be from step 1) DSC result obtain different temperatures T and (also correspond to time t, because temperature is with constant speed Rate rises) corresponding α and reaction rate d α/dt.Optimization matching herein refers to give Model Parameter (A₁、A₂、E₁、 E₂, m, n) different values, until the d α/dt drawn by this model is than the curve of upper temperature and the song in DSC experimental result Line is closest.After obtaining parameter value, it is possible to describe reaction rate d under arbitrary temp with this Kamal-Sourour model α/dt, thus obtain rate of heat release (d α/dt) the * △ H of reaction.

3) owing to, in the present processes, monomer is constant speed dropping, as it is shown in figure 1, can be by sample to be prepared on thickness Approximation is divided into n elementary layer, and the monomer dripped at first is designated as the 1st layer, and its temperature is T₁(can change in time), Rear dropping for n-th layer.Therefore, the transverse axis (thickness) in scattergram, is exactly express time in fact, because thickness is the most not Disconnected increase.And each layer of meeting absorbs heat from extraneous heating source and heat up (being described by Fourier heat transfer model), and reaction itself is also Can generate heat (being described by Newton relation), this Newton relation is Kamal-Sourour model both sides and is multiplied by △ H: $\frac{\mathrm{d\α}}{\mathrm{dt}}\·\mathrm{\ΔH}=(A_1\exp \left(\frac{-E_1}{\mathrm{RT}}\right)+A_2\exp \left(\frac{-E_1}{\mathrm{RT}}\right){\mathrm{\α}}^m){(1-\mathrm{\α})}^n\·\mathrm{\ΔH},$ The temperature of reaction is together decided on by two models.Institute With to the different time, each layer can be combined with the two model and solved, and when just having started only one layer, the most only asks one layer Solve, when last n-th layer, this n-layer is solved simultaneously.

So, by described parameter A₁、A₂、E₁、E₂, m, n substitute into heat release model $\frac{\mathrm{d\α}}{\mathrm{dt}}\·\mathrm{\ΔH}=(A_1\exp \left(\frac{-E_1}{\mathrm{RT}}\right)+A_2\exp \left(\frac{-E_1}{\mathrm{RT}}\right){\mathrm{\α}}^m){(1-\mathrm{\α})}^n\·\mathrm{\ΔH}$ In, and combine Fourier's heat transfer model:

$\left\{\begin{array}{c}\frac{{\∂}^{2}T}{\∂x^2}+\frac{\stackrel{\·}{q}}{k}-\frac{h_{\mathrm{side}}P}{\mathrm{Ak}}(T-T_{\mathrm{oil}})=\frac{1}{\mathrm{\β}(x,T)}\frac{\∂T}{\∂t}\\ k\frac{\∂T}{\∂x}{|}_{x=0}=h_{\mathrm{oil}}(T_{\mathrm{oil}}-T)\\ k\frac{\∂T}{\∂x}{|}_{x=\mathrm{\δ}\left(t\right)}=h_{\mathrm{air}}(T_{\mathrm{air}}-T)\\ T(x,0)=T_i\end{array}\right.$

Wherein:

The temperature of any elementary layer in T-reaction system

T_oil-outside oil bath heating-up temperature

T_air-protection temperature

The rate of heat release of-reaction

A-reactor cross-sectional area

P-reactor circumferential length

The thermal conductivity of k-reactant

The thermal diffusion coefficient of β-reactant

The temperature of any elementary layer of x-distance bottom

The thickness of material in δ-a certain moment reaction still

h_side-reaction system is by the heat transfer coefficient between side and external heat source

h_oil-reaction system is by the heat transfer coefficient between bottom and external heat source

h_airConvective heat-transfer coefficient between-conversion zone and protective atmosphere,

Calculate and obtain assigned temperature T under different drop rate_oilTime reaction system monomer conversion over time Figure；

4) when drop rate is more than f_maxTime, described variation diagram represents reaction system generation implode.

In polymerization process, first it is added drop-wise to the monomer in reactor and is first heated and is polymerized, there is higher list Transformation rate, the rear monomer added has relatively low temperature, can cool down the autoacceleration stage that is in, temperature rising the most instead Answering layer, thus prevent overheated and " implode " occurs, the heat that polyreaction is discharged simultaneously also can farthest be utilized, Save the energy.Owing to the dropping of monomer is constant speed, the monomer conversion of the most whole reaction system present from bottom to Liquid level continuous distribution from high to low.When substrate material heated time long enough, polyreaction is complete, it is believed that monomer conversion Reach 100%, referred to as " reacting complete layer ", and for monomer conversion between the upper strata of 0-100%, due to polyreaction also To continue, therefore be defined as " conversion zone ".The thickness of conversion zone depends on drop rate and the temperature of monomer, and temperature is more Low, drop rate is the fastest, then reaction layer thickness is the biggest, and the heat radiation of conversion zone is the most difficult, is more susceptible to implode.Suitably dripping Under rate of acceleration, " conversion zone " keeps constant thickness constantly to rise, and the thickness of " reacting complete layer " then constantly stably increases, when Reaction i.e. obtains large-sized crosslinked polystyrene bulk material after terminating.The thickness of product is unrestricted technically in theory System, therefore this technique has the biggest advantage on preparation large scale crosslinked polystyrene material.

Further, described reactant includes styrene, cross-linking agent and initiator.

Further, described polyreaction comprises the following steps: that reactant, 50-110 DEG C of polymerization, obtains head product；Just Product, 100-150 DEG C of post polymerization 8-24 hour, obtains end-product.

Further, described styrene is 9:1-999:1 with the mol ratio of cross-linking agent.

Further, described styrene is 24:1-199:1 with the mol ratio of cross-linking agent.

Further, described cross-linking agent includes divinylbenzene, Ethylene glycol dimethacrylate, dimethacrylate fourth Diol ester, divinyl naphthalene or divinyl phenyl alkane.

Further, described initiator molar concentration in reactant is 0.0025-0.05mol/L.

Further, described initiator includes benzoyl peroxide, dilauroyl peroxide, peroxy dicarbonate diisopropyl Ester, di-cyclohexylperoxy di-carbonate, peroxidized t-butyl perbenzoate, cumyl peroxide, di-t-butyl peroxide, azo Bis-isobutyronitrile or 2,2'-Azobis(2,4-dimethylvaleronitrile).

Further, described method is filled with noble gas during being included in polyreaction.

Further, described noble gas includes argon.

Compared with prior art, the beneficial effects of the present invention is:

1) present invention firstly provides Kamal-Sourour model is combined with Fourier's heat transfer model, be applied to calculate single The Temperature Distribution of reaction system, monomer conversion etc. under body constant speed dropping bulk technique, accurately control polymerization process, It is not only restricted to prepare the size of product, it is possible to well solve heat radiation difficulty and " implode " problem in polymerisation in bulk；

2) material prepared by the method is uniform, inside do not exist one macroscopically discontinuous fuzzy in performance continuously It is significantly improved relative to uncrosslinked polystyrene on interface, and intensity；

3) reaction unit of the present invention is simple, it is possible to improved realizing by traditional bulk polymerization device, technique letter Single, under suitable technological parameter, whole building-up process need not the most complicated monitoring feedback procedure；

4) applied widely, for selecting different cross-linking agent and the reaction system of initiator, only need according to kinetics Equation adjusts feed rate；

5) whole reaction is avoided introducing new impurity, and the product prepared by this reaction has the dielectric properties of excellence.

Accompanying drawing explanation

The simulation heat transfer model of Fig. 1 constant speed charging polymerisation in bulk.

In Fig. 2 embodiment 1, Kamal-Sourour model mates figure with the optimization matching of DSC curve.

In Fig. 3 (a) and (b) embodiment 1, drop rate is temperature of reaction system scattergram during 4ml/h and monomer conversion Variation diagram with thickness.

In Fig. 4 (a) and (b) embodiment 1, drop rate is temperature of reaction system scattergram during 6ml/h and monomer conversion Variation diagram with thickness.

In Fig. 5 (a) and (b) embodiment 1, drop rate is temperature of reaction system scattergram during 7.7ml/h and monomer conversion Rate is with the variation diagram of thickness.

The infrared spectrogram of crosslinked polystyrene in Fig. 6 embodiment 1.

The Young's modulus of crosslinked polystyrene in Fig. 7 embodiment 1.

The mechanical strength of crosslinked polystyrene in Fig. 8 embodiment 1.

The TGA figure of crosslinked polystyrene in Fig. 9 embodiment 1.

The dielectric properties of crosslinked polystyrene in Figure 10 embodiment 1.

Detailed description of the invention

The application is theoretically adapted to all polymerization systems with implode problem, and such as polystyrene, PMMA etc., at this The present invention it is described in further detail as a example by crosslinked polystyrene.

Embodiment 1

(1) 2.88mol styrene and 0.12mol divinylbenzene are sufficiently mixed, add 4.233g benzoyl peroxide (BPO) (its molar concentration in total reactant is 0.05mol/L) as initiator and is sufficiently stirred for, and treats that it is completely dissolved it Rear applying argon gas drives away the oxygen of dissolving in monomer with abundant in 30 minutes.All of reactant is stored in syringe and is arranged on On trace propeller, and keep at a lower temperature.

(2) DSC (dynamic DSC) test heating rate is used to be respectively 1 DEG C/min, 2 DEG C/min and 5 DEG C/min under the reaction rate curve of reactant.Further, also testing out polymerization enthalpy △ H with DSC is 600J/g.

(3) curve that step (2) obtained in a figure, and use Kamal-Sourour model:

$\frac{\mathrm{d\α}}{\mathrm{dt}}=(A_1\exp \left(\frac{-E_1}{\mathrm{RT}}\right)+A_2\exp \left(\frac{-E_1}{\mathrm{RT}}\right){\mathrm{\α}}^m){(1-\mathrm{\α})}^n$

Carrying out optimization matching, Fig. 2 is the coupling figure of this optimization matching.

Parameter is obtained as follows after optimization matching:

A1(s-1)	A2(s-1)	E1(kJ/mol)	E2(kJ/mol)	m	n
						9.14×108	4.30×10-1	88.6	9.62	3.38	1.24

Table 1

By the parameter in table 1 and Δ H substitution heat release model:

$\frac{\mathrm{d\α}}{\mathrm{dt}}\·\mathrm{\ΔH}=(A_1\exp \left(\frac{-E_1}{\mathrm{RT}}\right)+A_2\exp \left(\frac{-E_1}{\mathrm{RT}}\right){\mathrm{\α}}^m){(1-\mathrm{\α})}^n\·\mathrm{\ΔH}$

In, and with Fourier's heat transfer model:

$\left\{\begin{array}{c}\frac{{\∂}^{2}T}{\∂x^2}+\frac{\stackrel{\·}{q}}{k}-\frac{h_{\mathrm{side}}P}{\mathrm{Ak}}(T-T_{\mathrm{oil}})=\frac{1}{\mathrm{\β}(x,T)}\frac{\∂T}{\∂t}\\ k\frac{\∂T}{\∂x}{|}_{x=0}=h_{\mathrm{oil}}(T_{\mathrm{oil}}-T)\\ k\frac{\∂T}{\∂x}{|}_{x=\mathrm{\δ}\left(t\right)}=h_{\mathrm{air}}(T_{\mathrm{air}}-T)\\ T(x,0)=T_i\end{array}\right.$

Combined calculation, obtain under 70 DEG C of different drop rate temperature of reaction system scattergram and monomer conversion with The variation diagram (by the reactor of a diameter of 6.4cm) of thickness.Because wherein thickness is uniformly to increase, so monomer conversion is with thickness The variation diagram of degree is exactly that monomer conversion is schemed over time in fact.Fig. 3 (a) be drop rate be reactant during 4ml/h Being temperature profile, Fig. 3 (b) is drop rate variation diagram of monomer conversion (thickness) in time when being 4ml/h.Fig. 4 (a) is Drop rate is temperature of reaction system scattergram during 6ml/h, and Fig. 4 (b) is that monomer conversion is at any time when being 6ml/h for drop rate Between the variation diagram of (thickness).Fig. 5 (a) be drop rate be temperature of reaction system scattergram during 7.7ml/h, Fig. 5 (b) for dropping The variation diagram of monomer conversion (thickness) in time when speed is 7.7ml/h.See Fig. 3, it can be seen that when drop rate is During 4ml/h, the change that thickness rate of rise is 0.125cm/h, temperature profile and monomer conversion of whole reaction system Scheming the most regular, the curve presented shows that reaction system produces without implode phenomenon.When rate of addition increases to 6ml/h, Many that corresponding thickness rate of rise has become big, for 0.187cm/h, at this moment the regular of temperature of reaction system scattergram is deteriorated, There is the trend close to implode.When rate of addition becomes 7.7ml/h, thickness rate of rise reaches 0.240cm/h, in reaction system Have occurred and that implode.With justifying the oval part marked in the part i.e. corresponding diagram 5 (b) that collimation mark goes out in Fig. 5 (a), permissible from Fig. 5 Finding out, the temperature of reaction system all occurs in that out of control with reaction rate.Thus, it will be seen that when drop rate is more than 6ml/h Time, reaction system will occur implode, f is described_max≈6ml/h.To be on the safe side, the present embodiment selects safe rate of addition 4ml/h for slightly smaller than fmax.

(4) argon will be filled with after the reactor evacuation of a diameter of 6.4cm, control temperature at 70 DEG C and with the perseverance of 4ml/h Constant speed rate dropping monomer, and react under argon shield, stop dropping after material thickness reaches 10cm in question response still Monomer, and the monomer polymerization that continuous heating makes newly to drip for 12 hours is completely.

(5) head product obtained is taken out, under argon shield, be polymerized 12 hours at 150 DEG C, obtain full-thickness and reach The large scale crosslinked polystyrene material of 10cm.The infrared spectrum of products therefrom is shown in Fig. 6, as seen from Figure 6 697cm^-1With 759cm^-1For the characteristic peak of phenyl ring monosubstituted in styrene monomer, and 800cm^-1Spy for phenyl ring disubstituted in divinylbenzene Levy peak, illustrate that products therefrom is crosslinked polystyrene.

Fig. 7 illustrates the thermomechanical property of product, and crosslinked polystyrene is relative to uncrosslinked polyphenyl second as can be seen from Figure Alkene, Young's modulus has had and has improved significantly, and after crosslinking is described, mechanical property and the dimensional stability of material have obtained substantially Ground improves.

Fig. 8 illustrates the mechanical strength of product.In prior art, such as " crosslinked polystyrene and fiberglass reinforced composite wood The preparation of material and performance study " the crosslinked polystyrene mechanics disclosed in (Wu Fei, 2010, Wuhan University of Technology: Hubei, Wuhan) Intensity data is as DVB=1.8wt.% (about 1.45mol%), and hot strength and bending strength all reach maximum, point Not Yue Wei 53MPa and 92MPa, and along with the increase of DVB is decreased obviously.And the result of the application Fig. 8 shows, stretch and bend Maximum intensity can respectively reach 55MPa and 118MPa, it is often more important that along with the increase of crosslinking degree, mechanical property there is no substantially Decline.The product that the method prepares is described, even if under higher crosslinking degree, also has more excellent uniformity, because of This mechanical strength is more preferable.

Fig. 9 illustrates the thermostability of product.

Figure 10 is the products therefrom dielectric properties at radio frequency (more than GHz).It is seen that material is more than radio frequency Dielectric constant is stable between 2.5-2.6, and its dielectric loss constant tan δ is only 0.72-0.98 × 10^-3.And prior art In, the dielectric loss of crosslinked polystyrene is primarily retained in the scope of 0.001-0.0249 and already belongs to extraordinary low-dielectric Can, and dielectric loss Changshu of the application is significantly lower than prior art.

Embodiment 2

2.94mol styrene and 0.06mol divinylbenzene being sufficiently mixed, (it is at overall reaction to add 4.209g BPO Molar concentration in thing is 0.05mol/L) as initiator and be sufficiently stirred for, treat its be completely dissolved after applying argon gas 30 minutes with Fully drive away the oxygen dissolved in monomer.All of reactant is stored in syringe and is arranged on trace propeller, and Keep at a lower temperature.

Use DSC (dynamic DSC) test reaction thing polymerization enthalpy and 1 DEG C/min, 2 DEG C/ Reaction rate curve under min and 5 DEG C/min difference heating rate.

Use Kamal-Sourour model to carry out optimization matching rate curve, parameter and the Δ H of acquisition are substituted into and put In thermal model, and with Fourier's heat transfer model combined calculation, determine that the drop rate at 70 DEG C is 5.5ml/h, at thickness direction Upper corresponding rate of rise is 0.171cm/h (reactor of a diameter of 6.4cm).

To be filled with argon after the reactor evacuation of a diameter of 6.4cm, control temperature at 70 DEG C and constant with 5.5ml/h Speed dropping monomer, and react under argon shield, stop dropping after material thickness reaches 10cm in question response still single Body, and the monomer polymerization that continuous heating makes newly to drip for 12 hours is completely.

The head product obtained is taken out, under argon shield, is polymerized 12 hours at 150 DEG C, obtains full-thickness and reach The large scale crosslinked polystyrene material of 10cm.

Embodiment 3

2.97mol styrene and 0.03mol divinylbenzene being mixed, (it is in total reactant for the BPO of addition 4.197g Molar concentration be 0.05mol/L) as initiator and be sufficiently stirred for, treat its be completely dissolved after applying argon gas 30 minutes with fully Drive away the oxygen dissolved in monomer.All of reactant it is stored in syringe and is arranged on trace propeller, and keeping At a lower temperature.

Use DSC (dynamic DSC) test reaction thing polymerization enthalpy and 1 DEG C/min, 2 DEG C/ Reaction rate curve under min and 5 DEG C/min difference heating rate.

Use Kamal-Sourour model to carry out optimization matching rate curve, parameter and the Δ H of acquisition are substituted into and put In thermal model, and with Fourier's heat transfer model combined calculation, determine that the drop rate at 70 DEG C is 7ml/h, in a thickness direction Corresponding rate of rise is 0.218cm/h (reactor of a diameter of 6.4cm).

To be filled with argon after the reactor evacuation of a diameter of 6.4cm, control temperature at 70 DEG C and with the constant speed of 7ml/h Rate dropping monomer, and react under argon shield, stop dropping monomer after material thickness reaches 10cm in question response still, And continuous heating makes the monomer polymerization newly dripped complete for 12 hours.

The head product obtained is taken out, under argon shield, is polymerized 12 hours at 150 DEG C, obtains full-thickness and reach The large scale crosslinked polystyrene material of 10cm.

Embodiment 4

2.88mol styrene and 0.12mol divinylbenzene being mixed, (it is in total reactant for the BPO of addition 4.233g Molar concentration be 0.05mol/L) as initiator and be sufficiently stirred for, treat its be completely dissolved after applying argon gas 30 minutes with fully Drive away the oxygen dissolved in monomer.All of reactant it is stored in syringe and is arranged on trace propeller, and keeping At a lower temperature.

Use DSC (dynamic DSC) test reaction thing polymerization enthalpy and 1 DEG C/min, 2 DEG C/ Reaction rate curve under min and 5 DEG C/min difference heating rate.

Use Kamal-Sourour model to carry out optimization matching rate curve, parameter and the Δ H of acquisition are substituted into and put In thermal model, and with Fourier's heat transfer model combined calculation, determine that the drop rate at 90 DEG C is 6.5ml/h, at thickness direction Upper corresponding rate of rise is 0.202cm/h (reactor of a diameter of 6.4cm).

To be filled with argon after the reactor evacuation of a diameter of 6.4cm, control temperature at 90 DEG C and constant with 6.5ml/h Speed dropping monomer, and react under argon shield, stop dropping after material thickness reaches 10cm in question response still single Body, and the monomer polymerization that continuous heating makes newly to drip for 12 hours is completely.

The head product obtained is taken out, under argon shield, is polymerized 12 hours at 150 DEG C, obtains full-thickness and reach The large scale crosslinked polystyrene material of 10cm.

Embodiment 5

2.88mol styrene and 0.12mol divinyl phenyl ethane being mixed, (it is total anti-for the BPO of addition 4.233g Answering the molar concentration in thing is 0.05mol/L) as initiator and be sufficiently stirred for, treat its be completely dissolved after applying argon gas 30 minutes Fully to drive away the oxygen dissolved in monomer.All of reactant is stored in syringe and is arranged on trace propeller, And keep at a lower temperature.

Use DSC (dynamic DSC) test reaction thing polymerization enthalpy and 1 DEG C/min, 2 DEG C/ Reaction rate curve under min and 5 DEG C/min difference heating rate.

Use Kamal-Sourour model to carry out optimization matching rate curve, parameter and the Δ H of acquisition are substituted into and put In thermal model, and with Fourier's heat transfer model combined calculation, determine that the drop rate at 70 DEG C is 5ml/h, in a thickness direction Corresponding rate of rise is 0.156cm/h (reactor of a diameter of 6.4cm).

To be filled with argon after the reactor evacuation of a diameter of 6.4cm, control temperature at 70 DEG C and with the constant speed of 5ml/h Rate dropping monomer, and react under argon shield, stop dropping monomer after material thickness reaches 10cm in question response still, And continuous heating makes the monomer polymerization newly dripped complete for 12 hours.

The head product obtained is taken out, under argon shield, is polymerized 12 hours at 150 DEG C, obtains full-thickness and reach The large scale crosslinked polystyrene material of 10cm.

Embodiment 6

11.94mol styrene and 0.06mol divinylbenzene being mixed, adding molar concentration is 0.05mol/L's BPO is as initiator and is sufficiently stirred for, treat its be completely dissolved after applying argon gas 30 minutes fully to drive away the oxygen dissolved in monomer Gas.All of reactant it is stored in syringe and is arranged on trace propeller, and keeping at a lower temperature.

Use DSC (dynamic DSC) test reaction thing polymerization enthalpy and 1 DEG C/min, 2 DEG C/ Reaction rate curve under min and 5 DEG C/min difference heating rate.

Use Kamal-Sourour model to carry out optimization matching rate curve, parameter and the Δ H of acquisition are substituted into and put In thermal model, and with Fourier's heat transfer model combined calculation, determine drop rate f at 70 DEG C_max。

Argon will be filled with after the reactor evacuation of a diameter of 6.4cm, control temperature at 70 DEG C and with f_maxConstant rate of speed Dropping monomer, and react under argon shield, stop dropping monomer after material thickness reaches 10cm in question response still, and Continuous heating makes the monomer polymerization newly dripped complete for 12 hours.

The crosslinked polystyrene obtained is taken out, under argon shield, is polymerized 12 hours at 150 DEG C, obtains full-thickness Reach the large scale crosslinked polystyrene material of 10cm.

Embodiment 7

Being mixed with 0.32mol tetramethylene dimethacrylate by 2.88mol styrene monomer, adding molar concentration is The dilauroyl peroxide of 0.0025mol/L is also sufficiently stirred for, treat its be completely dissolved after applying argon gas 30 minutes fully to drive away list The oxygen dissolved in body.All of reactant it is stored in syringe and is arranged on trace propeller, and being maintained at relatively low At a temperature of.

Use DSC (dynamic DSC) test reaction thing polymerization enthalpy and 1 DEG C/min, 2 DEG C/ Reaction rate curve under min and 5 DEG C/min difference heating rate.

Use Kamal-Sourour model to carry out optimization matching rate curve, parameter and the Δ H of acquisition are substituted into and put In thermal model, and with Fourier's heat transfer model combined calculation, determine the f at 70 DEG C_max。

Argon will be filled with after the reactor evacuation of a diameter of 6.4cm, control temperature at 70 DEG C and with f_maxConstant rate of speed Dropping monomer, and react under argon shield, stop dropping monomer after material thickness reaches 10cm in question response still, and Continuous heating makes the monomer polymerization newly dripped complete for 12 hours.

The crosslinked polystyrene obtained is taken out, under argon shield, is polymerized 24 hours at 100 DEG C, obtains full-thickness Reach the large scale crosslinked polystyrene material of 10cm.

Embodiment 8

19.98mol styrene monomer is mixed with 0.02mol Ethylene glycol dimethacrylate, adds molar concentration For the di-isopropyl peroxydicarbonate of 0.02mol/L and be sufficiently stirred for, treat its be completely dissolved after applying argon gas 30 minutes to fill Divide and drive away the oxygen dissolved in monomer.All of reactant it is stored in syringe and is arranged on trace propeller, and protecting Hold at a lower temperature.

Use DSC (dynamic DSC) test reaction thing polymerization enthalpy and 1 DEG C/min, 2 DEG C/ Reaction rate curve under min and 5 DEG C/min difference heating rate.

Use Kamal-Sourour model to carry out optimization matching rate curve, parameter and the Δ H of acquisition are substituted into and put In thermal model, and with Fourier's heat transfer model combined calculation, determine the f at 50 DEG C_max。

Argon will be filled with after the reactor evacuation of a diameter of 6.4cm, control temperature at 50 DEG C and with f_maxConstant rate of speed Dropping monomer, and react under argon shield, stop dropping monomer after material thickness reaches 10cm in question response still, and Continuous heating makes the monomer polymerization newly dripped complete for 12 hours.

The crosslinked polystyrene obtained is taken out, under argon shield, is polymerized 8 hours at 150 DEG C, obtains full-thickness and reach Large scale crosslinked polystyrene material to 10cm.

Embodiment 9

Being mixed with 0.12mol divinyl naphthalene by 2.88mol styrene monomer, adding molar concentration is 0.01mol/L Di-cyclohexylperoxy di-carbonate and be sufficiently stirred for, treat its be completely dissolved after applying argon gas 30 minutes fully to drive away in monomer The oxygen dissolved.All of reactant it is stored in syringe and is arranged on trace propeller, and being maintained at relatively low temperature Under degree.

Use DSC (dynamic DSC) test reaction thing polymerization enthalpy and 1 DEG C/min, 2 DEG C/ Reaction rate curve under min and 5 DEG C/min difference heating rate.

Use Kamal-Sourour model to carry out optimization matching rate curve, parameter and the Δ H of acquisition are substituted into and put In thermal model, and with Fourier's heat transfer model combined calculation, determine the f at 50 DEG C_max。

Argon will be filled with after the reactor evacuation of a diameter of 6.4cm, control temperature at 50 DEG C and with f_maxConstant rate of speed Dropping monomer, and react under argon shield, stop dropping monomer after material thickness reaches 10cm in question response still, and Continuous heating makes the monomer polymerization newly dripped complete for 12 hours.

The crosslinked polystyrene obtained is taken out, under argon shield, is polymerized 16 hours at 120 DEG C, obtains full-thickness Reach the large scale crosslinked polystyrene material of 10cm.

Embodiment 11

Being mixed with 0.12mol divinyl phenylmethane by 2.88mol styrene monomer, adding molar concentration is The peroxidized t-butyl perbenzoate of 0.04mol/L is also sufficiently stirred for, treat its be completely dissolved after applying argon gas 30 minutes fully to drive The oxygen dissolved in demonomerization.All of reactant it is stored in syringe and is arranged on trace propeller, and being maintained at At a temperature of relatively low.

Use DSC (dynamic DSC) test reaction thing polymerization enthalpy and 1 DEG C/min, 2 DEG C/ Reaction rate curve under min and 5 DEG C/min difference heating rate.

Use Kamal-Sourour model to carry out optimization matching rate curve, parameter and the Δ H of acquisition are substituted into and put In thermal model, and with Fourier's heat transfer model combined calculation, determine the f at 90 DEG C_max。

Argon will be filled with after the reactor evacuation of a diameter of 6.4cm, control temperature at 90 DEG C and with f_maxConstant rate of speed Dropping monomer, and react under argon shield, stop dropping monomer after material thickness reaches 10cm in question response still, and Continuous heating makes the monomer polymerization newly dripped complete for 12 hours.

The crosslinked polystyrene obtained is taken out, under argon shield, is polymerized 22 hours at 140 DEG C, obtains full-thickness Reach the large scale crosslinked polystyrene material of 10cm.

Embodiment 12

Being mixed with 0.12mol divinyl phenyl ethane by 2.88mol styrene monomer, adding molar concentration is The cumyl peroxide of 0.0075mol/L is also sufficiently stirred for, treat its be completely dissolved after applying argon gas 30 minutes fully to drive away The oxygen dissolved in monomer.All of reactant it is stored in syringe and is arranged on trace propeller, and being maintained at relatively At a temperature of low.

Use DSC (dynamic DSC) test reaction thing polymerization enthalpy and 1 DEG C/min, 2 DEG C/ Reaction rate curve under min and 5 DEG C/min difference heating rate.

Use Kamal-Sourour model to carry out optimization matching rate curve, parameter and the Δ H of acquisition are substituted into and put In thermal model, and with Fourier's heat transfer model combined calculation, determine the f at 100 DEG C_max。

Argon will be filled with after the reactor evacuation of a diameter of 6.4cm, control temperature at 100 DEG C and with f_maxConstant speed Rate dropping monomer, and react under argon shield, stop dropping monomer after material thickness reaches 10cm in question response still, And continuous heating makes the monomer polymerization newly dripped complete for 12 hours.

The crosslinked polystyrene obtained is taken out, under argon shield, is polymerized 12 hours at 150 DEG C, obtains full-thickness Reach the large scale crosslinked polystyrene material of 10cm.

Embodiment 13

5mol styrene monomer is mixed with 0.01mol divinylbenzene, adds the mistake that molar concentration is 0.01mol/L Oxidation di-t-butyl is also sufficiently stirred for, treat its be completely dissolved after applying argon gas 30 minutes fully to drive away the oxygen dissolved in monomer Gas.All of reactant it is stored in syringe and is arranged on trace propeller, and keeping at a lower temperature.

Use DSC (dynamic DSC) test reaction thing polymerization enthalpy and 1 DEG C/min, 2 DEG C/ Reaction rate curve under min and 5 DEG C/min difference heating rate.

Use Kamal-Sourour model to carry out optimization matching rate curve, parameter and the Δ H of acquisition are substituted into and put In thermal model, and with Fourier's heat transfer model combined calculation, determine the f at 110 DEG C_max。

Argon will be filled with after the reactor evacuation of a diameter of 6.4cm, control temperature at 110 DEG C and with f_maxConstant speed Rate dropping monomer, and react under argon shield, stop dropping monomer after material thickness reaches 10cm in question response still, And continuous heating makes the monomer polymerization newly dripped complete for 12 hours.

The crosslinked polystyrene obtained is taken out, under argon shield, is polymerized 12 hours at 150 DEG C, obtains full-thickness Reach the large scale crosslinked polystyrene material of 10cm.

Embodiment 14

8mol styrene monomer is mixed with 0.01mol divinylbenzene, adds the idol that molar concentration is 0.05mol/L Nitrogen two isobutyl cyanogen is also sufficiently stirred for, treat its be completely dissolved after applying argon gas 30 minutes fully to drive away the oxygen dissolved in monomer. All of reactant it is stored in syringe and is arranged on trace propeller, and keeping at a lower temperature.

Use DSC (dynamic DSC) test reaction thing polymerization enthalpy and 1 DEG C/min, 2 DEG C/ Reaction rate curve under min and 5 DEG C/min difference heating rate.

Use Kamal-Sourour model to carry out optimization matching rate curve, parameter and the Δ H of acquisition are substituted into and put In thermal model, and with Fourier's heat transfer model combined calculation, determine the f at 70 DEG C_max。

Argon will be filled with after the reactor evacuation of a diameter of 6.4cm, control temperature at 70 DEG C and with f_maxConstant rate of speed Dropping monomer, and react under argon shield, stop dropping monomer after material thickness reaches 10cm in question response still, and Continuous heating makes the monomer polymerization newly dripped complete for 12 hours.

The crosslinked polystyrene obtained is taken out, under argon shield, is polymerized 12 hours at 150 DEG C, obtains full-thickness Reach the large scale crosslinked polystyrene material of 10cm.

Embodiment 15

3mol styrene monomer is mixed with 0.3mol divinylbenzene, adds the idol that molar concentration is 0.05mol/L Nitrogen two cyanogen in different heptan is also sufficiently stirred for, treat its be completely dissolved after applying argon gas 30 minutes fully to drive away the oxygen dissolved in monomer. All of reactant it is stored in syringe and is arranged on trace propeller, and keeping at a lower temperature.

Use DSC (dynamic DSC) test reaction thing polymerization enthalpy and 1 DEG C/min, 2 DEG C/ Reaction rate curve under min and 5 DEG C/min difference heating rate.

Use Kamal-Sourour model to carry out optimization matching rate curve, parameter and the Δ H of acquisition are substituted into and put In thermal model, and with Fourier's heat transfer model combined calculation, determine the f at 50 DEG C_max。

Argon will be filled with after the reactor evacuation of a diameter of 6.4cm, control temperature at 50 DEG C and with f_maxConstant rate of speed Dropping monomer, and react under argon shield, stop dropping monomer after material thickness reaches 10cm in question response still, and Continuous heating makes the monomer polymerization newly dripped complete for 12 hours.

The crosslinked polystyrene obtained is taken out, under argon shield, is polymerized 12 hours at 150 DEG C, obtains full-thickness Reach the large scale crosslinked polystyrene material of 10cm.

Should be appreciated that above-described embodiment is only for example for clearly demonstrating the present invention, and be not to the present invention The restriction of embodiment.For the person of ordinary skill of the art, can also be made it on the basis of the above description The change of its multi-form or variation.Here cannot all of embodiment be given exhaustive.Every technology belonging to the present invention What scheme was amplified out obviously changes or changes the row still in protection scope of the present invention.

Claims (10)

1. the bulk polymerization of monomer constant speed dropping, it is characterised in that described method includes step:

After reactant is stirred, drop to continuously in reactor with constant rate of speed, carry out polyreaction；Wherein said constant The maximum rate f of speed_maxSelect according to the following step:

1) polymerization enthalpy and the reaction rate curve of described reactant is tested with dynamic DSC；

2) to step 1) in obtain reaction rate curve use Kamal-Sourour kinetic model carry out optimization matching, Obtaining the parameter value of Kamal-Sourour kinetic model, described Kamal-Sourour kinetic model is:

3) parameter value and polymerization enthalpy are substituted in heat release model, and combine Fourier's heat transfer model and jointly calculate, it is thus achieved that no With under drop rate during assigned temperature the monomer conversion of reaction system scheme over time；Described heat release model is Kamal- △ H is multiplied by Sourour kinetic model both sides simultaneously；

4) when drop rate is more than f_maxTime, described variation diagram represents reaction system generation implode.

Method the most according to claim 1, it is characterised in that described reactant includes styrene, cross-linking agent and initiator.

Method the most according to claim 2, it is characterised in that described polyreaction comprises the following steps: that reactant is at 50- 110 DEG C of polymerizations, obtain head product；Head product, 100-150 DEG C of post polymerization 8-24 hour, obtains end-product.

Method the most according to claim 2, it is characterised in that described styrene is 9:1-999 with the mol ratio of cross-linking agent: 1。

Method the most according to claim 4, it is characterised in that described styrene is 24:1-with the mol ratio of cross-linking agent 199:1。

Method the most according to claim 2, it is characterised in that described cross-linking agent includes divinylbenzene, dimethyl allene Acid glycol ester, tetramethylene dimethacrylate, divinyl naphthalene or divinyl phenyl alkane.

Method the most according to claim 2, it is characterised in that described initiator molar concentration in reactant is 0.0025-0.05mol/L。

Method the most according to claim 2, it is characterised in that described initiator includes benzoyl peroxide, peroxidating ten Two acyls, di-isopropyl peroxydicarbonate, di-cyclohexylperoxy di-carbonate, peroxidized t-butyl perbenzoate, peroxidating two are different Propyl benzene, di-t-butyl peroxide, azodiisobutyronitrile or 2,2'-Azobis(2,4-dimethylvaleronitrile).

Method the most according to claim 1, it is characterised in that described method is filled with lazy during being included in polyreaction Property gas.

Method the most according to claim 9, it is characterised in that described noble gas includes argon.