CN102954923A - Polymerization-kinetic method for detecting vinyl chloride - Google Patents
Polymerization-kinetic method for detecting vinyl chloride Download PDFInfo
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Abstract
The invention relates to a polymerization-kinetic method for detecting vinyl chloride, belonging to the field of polymerization-kinetic detection methods of vinyl chloride. The method is characterized by comprising the following steps: adding vinyl chloride, water, assistant and tracer accounting for 0.5-10 wt% of vinyl chloride into a polymerization kettle by a conventional method; carrying out polymerization reaction at usual polymerization temperature; recording pressure value and temperature data of the polymerization system in real time; calculating the polymerization conversion rate X at the time point T in a detection system according to a mathematical model of polymer generation conditions; and when the polymerization conversion rate X reaches the technological requirement, adding a terminator, thereby obtaining polymerization-kinetic series data in the whole polymerization reaction process. By using the method provided by the invention, the detection personnel do not contact vinyl chloride, and do not need to invest into large-scale detection equipment; and the method is simple to operate and easy to implement, and implements real-time tracking detection on the whole vinyl chloride polymerization process.
Description
Technical field
A kind of method of chlorine detection ethylene polymerization dynamics belongs to chloroethylene polymerization kinetics detection method field, is specifically related to the conversion ratio in the full conversion ratio scope, the detection technique of polymerization rate in a kind of chloroethylene polymerization process.
Background technology
Chloroethylene polymerization kinetics research can provide necessary basic data for industrial polymer reactor design, device capacity expansion revamping, operating procedure optimization etc., is link indispensable in the process exploitation.In the suspension polymerization of VC process, the Measurement accuracy of polymerisation conversion (quality that namely generates Polyvinylchloride accounts for the percentage of the initial addition of vinyl chloride) and polymerization rate (being the polymerisation conversion of unit interval vinyl chloride) is the core of research polymerization kinetics.The conversion ratio measuring technology of conventional Polymer Synthesizing generally is not suitable for the suspension polymerization of VC system, because in the molecular high pressure mixing system of water, monomer and many Dimension Trees fat granule, sampling can run into very large mechanically actuated trouble, thereby how to avoid in the experimental implementation process being exposed to the minimizing health hazard also is a very large problem in the vinyl chloride atmosphere.
Can be used for the method for measuring of suspension polymerization of VC conversion ratio has " weight method ", " dilatometer method ", " calorimetry " to reach " tracer agent gas vapor-phase chromatography " etc.
" weight method " is to stop polymerization at different polymerization times, and the centrifugal dehydration of gained resin, oven dry are weighed, and the vinyl chloride quality that adds during with polymerization compares asks its conversion ratio.The method has higher degree of accuracy in theory, but needs the test of multiple batches of the same terms, and workload is very large, operates also more loaded down with trivial details.
" dilatometer method " is to utilize the variation of system volume behind the system volume and polymerization before the polymerization, asks for the polymerisation conversion of vinyl chloride.But the method is only applicable to the mensuration of low-conversion, and then error is very large to be used for the mensuration of high conversion.
" calorimetry " is the growing amount that liberated heat calculates Corvic when measuring the chloroethylene polymerization reaction.The method is suitable for the various polymerization techniques such as bulk polymerization of VC, solution polymerization, suspension polymerization, is widely applied at commercial plant.But this technology only has higher degree of accuracy at commercial plant, then can be little because of unit scale on small testing device, polymerization exotherm is few, and uncontrollable thermal loss in the polymerization process and affect measuring accuracy.
" tracer agent gas vapor-phase chromatography " is to add a kind of inert substance (such as normal butane) in polymerization system, variation by this inert substance content in the gas chromatograph trace analysis gas phase, ask for the generation situation of polymkeric substance according to mathematical model, calculate the chloroethylene polymerization conversion ratio.1984, the M.Langsam of Pennsylvania, America Alan town APCI company reported in Polymer Science this method has been applied in the detection of VC polymerization kinetics for the first time; Nineteen ninety, Xie Tuyu, the A.E.Hamielec etc. of Canada McMaster university use tracer agent gas chromatographic technique chlorine detection ethylene polymerization dynamics, and set up the mathematical model that concerns between detailed conversion ratio and tracer agent response peak-Hamielec-Xie model, set up tracer agent chromatogram off-line analysis method; 1996, the professors such as the yellow will of macromolecule engineering research institute of Zhejiang University is bright, Bao Yongzhong set up the dynamic real-time detecting system of the joining polymerization of computing machine on the basis of Hamielec-Xie model.2005, publication number was that the Chinese patent of CN1699992 discloses this chloroethylene polymerization kinetics real time tracing and detecting apparatus and method.In this pick-up unit and the method, need to use the gas chromatography of high measurement degree of accuracy, and set up that pipeline is connected between polymeric kettle and gas chromatography, for guaranteeing that the gas that enters gas chromatography is continuous mobile gas phase, associated line needs complete stroke thermal insulating, holding temperature also will be controlled temperature adjustment according to polymerization, so the method cost of investment is higher, it is quite loaded down with trivial details to operate.
Summary of the invention
The technical problem to be solved in the present invention is: overcome the deficiencies in the prior art, the detection method that provides a kind of testing staff not contact, need not to invest large-scale checkout equipment, the chloroethylene polymerization kinetics that operation is simple with vinyl chloride, thus realize simply and easily the real-time follow-up of chloroethylene polymerization overall process is detected.
The present invention solves the technical scheme that its technical matters takes: a kind of method of chlorine detection ethylene polymerization dynamics, according to a conventional method vinyl chloride, water, auxiliary agent and 0.5～10% the tracer agent that accounts for the vinyl chloride quality are added in the polymeric kettle, polyreaction 3～10h under conventional temperature, real time record polymerization system force value and temperature data, polymerisation conversion X when in detection system, calculating moment t according to mathematical model, treat to add terminator when polymerisation conversion X reaches technological requirement, can obtain the polymerization kinetics series data in the whole polymerization process.
The described mathematical model of asking for the generation of the polymkeric substance under any time situation in the full conversion ratio scope of vinyl chloride is:
In the formula: X is constantly polymerisation conversion (% of unit) of t, m
aBe the addition (unit K g) of tracer agent, M
aBe the molecular weight of tracer agent, m
VcFor vinyl chloride initially adds quality (unit K g), M
VcBe vinyl chloride molecular weight, P
tBe t moment reaction still internal pressure (units MPa), P
aBe the tracer agent saturated vapor pressure (units MPa) under the polymerization temperature, P
VcBe the vinyl chloride saturated vapor pressure (units MPa) under the polymerization temperature.
Preferably, the consumption of described tracer agent is 1～7% of raw material vinyl chloride quality.
Described tracer agent is C
5～C
8Normal alkane or C
5～C
8Isoparaffin in a kind of.
In the described polymerization reaction time, real time record polymerization system force value, the force value degree of accuracy will reach 0.01MPa, preferably can reach 0.001MPa.
Described auxiliary agent comprises dispersed system and initiator system.
The deionized water that adds in the polymerization process need to meet the polymerization technique requirement, in order to avoid affect polyreaction, General Requirements polymerization water conductivity is 1～5 μ S/cm.
The kind of auxiliary agent and consumption all are kind and consumptions of conventional ripening.Be specially: described initiator system for causing any number of free radical type initiating agent of chloroethylene polymerization, such as azo and organic peroxide compounds, can also can be made into compound system with the independent use of certain proportion and use.Azo-initiator in the initiator system, its general structure are (R-N=N-R ', R, R ' are identical or different), such as azoisobutyronitrile (AIBN), ABVN (ABVN), azo two different methylbutyronitriles etc.; Organic peroxide compounds in the initiator system, it is the oil-soluble peroxide initiator, is that 1 or 2 hydrogen atoms are replaced by organic group and the organic peroxide that generates in the hydrogen peroxide molecule.Can be divided into peroxidating two alkane (RO-OR '), peroxidating two acyls (RCO-OCR '), peroxycarboxylic acid esters (RCOO-OR ') and peroxy dicarbonates (ROCOO-OOCOR ') etc. by substituent difference, R or R ' can be identical or different in each class.
Wherein, and peroxidating two alkane in the oil-soluble peroxide initiator (RO-OR ') class, comprise cumyl peroxide, di-tert-butyl peroxide etc.Peroxidating two acyls in the described oil-soluble peroxide initiator (RCO-OCR ') class, comprise diisobutyryl peroxide, peroxidating two different nonanoyls, didecanoyl peroxide, dilauroyl peroxide, dibenzoyl peroxide, peroxidating two (3,5,6-trimethyl acetyl), acetyl peroxide hexamethylene sulphonyl etc.; Peroxycarboxylic acid esters in the described oil-soluble peroxide initiator (RCOO-OR ') class, comprise tert-Butyl peroxypivalate, peroxidating neopentanoic acid tert-pentyl ester, peroxidating neopentanoic acid isopropyl phenyl ester, the new enanthic acid tert-butyl ester of peroxidating, the new enanthic acid of peroxidating-3-hydroxyl-1,1-dimethyl butyl ester, peroxidating is sourer isopropyl phenyl ester newly, zinc peroxide capric acid book butyl ester, peroxidating neodecanoic acid tert-pentyl ester, peroxidating neodecanoic acid isopropyl phenyl ester, peroxidating neodecanoic acid-1,1,3,3-tetramethyl butyl ester, peroxidating neodecanoic acid-2,4,4-trimethyl pentyl ester, peroxidating neodecanoic acid-3-hydroxyl-1,1-dimethyl butyl ester, peroxide-2-ethyl hexanoic acid tert-butyl, peroxidating-2 ethyl hexanoic acid tert-pentyl ester.
Peroxy dicarbonates in the oil-soluble peroxide initiator (ROCOO-OOCOR ') class, comprise the peroxy dicarbonate dibutyl ester, the peroxy dicarbonate dibutyl ester, peroxy dicarbonate and secondary butyl ester, the peroxy dicarbonate di-n-propyl ester, peroxy dicarbonate diisopropyl fat, di-cyclohexylperoxy di-carbonate, peroxy dicarbonate two (2-Octyl Nitrite), peroxy dicarbonate two (4-tert-butyl group cyclohexyl), peroxy dicarbonate two (3-methyl butyl ester), peroxy dicarbonate two-2-ethyl phenoxy, the two cetyl of peroxy dicarbonate, two pairs of myristins of peroxy dicarbonate etc.
Described initiator system compound use comprises that any one arbitrary proportion is compound in azo-initiator and the peroxide initiating agent, comprises that also the arbitrary proportion between various peroxide initiating agents is compound.Initiator system uses with certain proportion, can account for 50～10000ppm of vinyl chloride total amount, generally can select 100～2000ppm.Usually initiator system need to be carried out pre-service, its process is: it is 3～70% homogeneous latex emulsion that initiating agent, emulsifying agent, water are all changed into initiator content, preferred 5～50% homogeneous latex emulsion.Above-mentioned emulsifying agent is polyvinyl alcohol (PVA), comprise the degree of polymerization 800～2000, the polyvinyl alcohol (PVA) of alcoholysis degree between 70%～90%, preferred degree of polymerization 1000～1600, the polyvinyl alcohol (PVA) of alcoholysis degree between 75～80%.
Described polymerization temperature scope can be 0～100 ℃, and polymerization temperature commonly used is generally selected 30～70 ℃.
Described dispersed system is the principal element that affects the polyvinyl chloride resin particle characteristic, joins in the polymerization system with certain proportion, act as the interfacial tension that reduces on the one hand vinyl chloride monomer and water, is conducive to the dispersion of vinyl chloride monomer under beating action; When drop formed, dispersant adsorption played a protective role on the drop surface, prevented from gathering also.The dispersed system kind can be mineral-type or organic, is generally several spreading agent compound uses.The mineral-type spreading agent is non-water-soluble fine inoganic solids powder, such as natural silicate, sulfate, carbonate, phosphate, oxalates, oxyhydroxide, oxide etc.; Described organic dispersing agent is hydrophilic macromolecular compound, such as the polyvinyl alcohol (PVA) of gelatin, cellulose ethers, partial alcoholysis, styrene-maleic anhydride copolymer etc.The dispersed system compound use comprises that any one arbitrary proportion is compound in inorganic dispersant and the organic dispersing agent, comprises that also the arbitrary proportion between various organic dispersing agents is compound.
Dispersed system uses with certain proportion, can account for 50～10000ppm of vinyl chloride total amount, generally can select 300～3000ppm.
Described chain-transferring agent can be adjusted the mean molecular weight of PVC (Polyvinylchloride) effectively.Chain-transferring agent commonly used comprises sulfocompound, comprises mercaptoethanol, thioglycollic acid-2-ethyl hexyl ester, mercaptopropionic acid, ethyl thioglycolate, the different new ester of mercaptoacetic acid etc., and general addition accounts for 100～2000ppm of vinyl chloride total amount.
Described terminator, join and polyreaction is stopped fully or sharply slow down, reach the suitable purpose of control depth of cure, comprise free radical type terminator, quinones, polyatomic phenol, arylamine class, nitro compound, nitroso compound, organic sulfide, mineral compound etc.General 10～the 300ppm that accounts for the vinyl chloride total amount that adds.
The technical conceive that proposes among the present invention and principle are such:
In suspension method chloroethylene polymerization process, with liquid phase, gas phase, and the Polyvinylchloride richness that generates exists in mutually vinyl chloride in polymerization system.Along with the carrying out of reaction, liquid phase vinyl chloride can progressively disappear, and the vinyl chloride of polymkeric substance richness in mutually continues reaction, causes vinyl chloride minute drops in the gas phase, and the gaseous pressure of whole polymerization system reduces, and this is the general process of chloroethylene polymerization reaction.This characteristics according to the chloroethylene polymerization process, in polymerization system, add a kind of inert substance that does not participate in polyreaction do tracer agent (this inert substance vinyl chloride monomer mutually in solubleness higher, solubleness is extremely low in water and polymerization phase, in the polymerization temperature scope that vinyl chloride is commonly used, except having higher solubleness, itself also belongs to volatile substances to this tracer agent in vinyl chloride).When polymerization begins tracer agent is joined in the polymerization system, then tracer agent can be distributed in gas phase, water, monomer phase and the polymerization phase in varing proportions, and forms a kind of mobile equilibrium.Along with the carrying out of polymerization, the free chlorine ethene in the polymerization system liquid phase reduces mutually, the polymerization phase increases, and then be dissolved in the tracer agent of free chlorine ethene in mutually and reduce, and the amount of aqueous phase tracer agent does not change.According to the mass conservation, the amount of tracer agent can increase in the gas phase, and the variation of this gaseous component has caused the variation of polymerization system pressure, can measure the variation of this pressure by precision pressure gauge.If polymerization system is regarded as a system, then this system can regard as by monomer phase, polymerization phase, water, tracer agent and mix mutually, also can explain the pressure changing of polymerization system from multicomponent system thermodynamics.Tracer agent wherein and vinyl chloride are mixed into homogeneous phase solution mutually, it is solvent that mass fraction accounts for most vinyl chloride, the tracer agent that mass fraction accounts for a small amount of part is solute, and the pressure of paradigmatic system is the pressure sum for producing in vinyl chloride, each comfortable gas phase of tracer agent then.
Initial in polymerization, polymerization time t is 0, and conversion ratio X is 0, and system pressure is designated as P
0After polymerization begins, carrying out along with reaction, vinyl chloride monomer more and more aggregates into resin, also namely fewer and feweri as the amount of the solvent of tracer agent (solute), then the solute part proportion in the homogeneous phase solution of vinyl chloride and tracer agent composition is increasing, and namely variation has occured the proportion of composing of solvent and solute in the solution.This variation has caused the variation of the vapour pressure of the solution that both form, and namely precision pressure gauge measures pressure carrying out and change with polymerization.This moment vinyl chloride and tracer agent separately amount of substance, system pressure P
tIn the time of can being designated as polymerization time and being t, the state when conversion ratio is X.Thinking of the present invention then is to extrapolate the situation of chloroethylene polymerization resin in the polymerization system by the variation of observing system pressure P in the polymerization process.Core is as perfect liquid mixture with vinyl chloride and tracer agent, according to perfect liquid mixture vapour-liquid equilibrium characteristics, extrapolate the mathematical model that chloroethylene polymerization conversion ratio X changes with pressure P, the polymkeric substance under any time generates situation in the vinyl chloride conversion ratio scope complete ask for.
The Derivation of Mathematical Model process of asking for the generation of the polymkeric substance under any time situation in the full conversion ratio scope of vinyl chloride is such:
T constantly, when the chloroethylene polymerization conversion ratio is X, the tracer agent amount of substance is
The vinyl chloride amount of substance is
The total amount of substance of tracer agent and vinyl chloride is
M wherein
a, M
aFor tracer agent adds quality and molecular weight, m
VC, M
VCFor vinyl chloride initially adds quality and molecular weight.
The mixed solution that vinyl chloride and tracer agent are formed is as perfect liquid mixture, and then the dividing potential drop in each comfortable gas phase is:
The tracer agent dividing potential drop is
The vinyl chloride dividing potential drop is
Wherein, P
aBe the tracer agent saturated vapor pressure under the polymerization temperature, P
VcBe the vinyl chloride saturated vapor pressure under the polymerization temperature.
According to vapour-liquid equilibrium characteristics in the perfect liquid mixture, the pressure of paradigmatic system is the pressure sum that produces in vinyl chloride, each comfortable gas phase of tracer agent, then
Wherein, P
tBe t moment reaction still internal pressure.
With the following formula mathematics manipulation, can obtain the described mathematical model of asking for lower polymkeric substance generation situation of any time in the full conversion ratio scope of vinyl chloride and be:
Compared with prior art, the beneficial effect that the method for a kind of chlorine detection ethylene polymerization dynamics of the present invention has is: by means of pressure data and mathematical model with calculate the real-time follow-up that can finish the chloroethylene polymerization overall process and detect, the testing staff need not directly to contact vinyl chloride, reduced the harm of vinyl chloride monomer to the staff, testing process need not to use expensive analyzing and testing equipment, can finish in short time, operating process is simple, testing cost is low, higher to the chloroethylene polymerization kinetics accuracy of detection, measuring polymerisation conversion with the weight method of generally acknowledging compares, bounded absolute error is between 0.5～4.3%, average error is approximately 3%, and is higher to the chloroethylene polymerization kinetics accuracy of detection, can be used as the conventional method use that chloroethylene polymerization detects in real time.
Embodiment
Embodiment 1
Polymeric kettle is rinsed well, apply anti-fouling agent and flushing, then vacuumize, 100 parts of vinyl chloride, 130 parts deionized water, 0.08 part dispersed system (are comprised of high alcoholysis degree polyvinyl alcohol (PVA)/polyvinyl alcohol with low alcoholysis level/hydroxypropyl methylcellulose, weight ratio is 3: 1: 2), 0.07 part initiator system (be comprised of peroxy dicarbonate two-(2-ethylhexyl) ester/peroxidating neodecanoic acid isopropyl phenyl ester, weight ratio is 3: 1), 5 parts of C as tracer agent
5The material of normal alkane places polymeric kettle, is evacuated to the vinyl chloride monomer that adds formula ratio behind the 0.098MPa again, and cold stirring 10min is warming up to 57.0 ℃ of beginnings of temperature of reaction timing, carries out polyreaction.
The pressure value P of the real time measure system in the polymerization process
t, P
tValue is accurate to 0.01MPa.By the mathematical model in the detection system:
Embodiment 2～7
Repeat embodiment 1, difference is that embodiment 2 adds terminator when the polymerisation conversion X under the mathematical model reaches 70%, and embodiment 3～7th, adds terminator when polymerisation conversion X reaches respectively 60%, 50%, 40%, 35% and 20%.Polymerisation conversion under the mathematical model and weight method polymerisation conversion result see Table 1 with embodiment 1.
Embodiment 8～9
Embodiment 8 repeats embodiment 1 polymerization and testing process, and difference is tracer agent C among the embodiment 8
5The normal alkane addition is 2.5 parts.Embodiment 9 repeats embodiment 8, and difference is, C among the embodiment 9
5The normal alkane addition is 0.5 part, adds terminator when the polymerisation conversion X under the mathematical model reaches 30%, and polymerisation conversion and the weight method polymerisation conversion result of embodiment 8～9 under mathematical model sees Table 1 together.
Table 1 mathematical model polymerisation conversion and the contrast of weight method conversion ratio
| The embodiment title | Polymerisation conversion under the mathematical model | The weight method polymerisation conversion | Mathematical model-weight method |
| Embodiment 1 | 80％ | 76.5％ | 3.5％ |
| Embodiment 2 | 70％ | 66.4％ | 3.6％ |
| Embodiment 3 | 60％ | 64.3％ | -4.3％ |
| Embodiment 4 | 50％ | 53.9％ | -3.9％ |
| Embodiment 5 | 40％ | 42.0％ | -2.0％ |
| Embodiment 6 | 35％ | 35.5％ | -0.5％ |
| Embodiment 7 | 20％ | 23.1％ | -3.1％ |
| Embodiment 8 | 80％ | 83.0％ | -3.0％ |
| Embodiment 9 | 30％ | 28.5％ | 1.5％ |
Embodiment 10
Polymeric kettle is rinsed well, apply anti-fouling agent and flushing, then vacuumize, 100 parts of vinyl chloride, 150 parts deionized water, 0.10 part dispersed system (are comprised of high alcoholysis degree polyvinyl alcohol (PVA)/hydroxypropyl methylcellulose, the ratio of weight portion is 3: 2), 0.10 part initiator system (be comprised of azoisobutyronitrile/peroxy dicarbonate two-(2-ethylhexyl), weight ratio is 4: 1), 0.01 part chain-transferring agent (mercaptoethanol), 3 parts of C as tracer agent
6The material of normal alkane places polymeric kettle, is evacuated to the vinyl chloride monomer that adds formula ratio behind the 0.098MPa again, and cold stirring 10min is warming up to 61.0 ℃ of beginnings of temperature of reaction timing, carries out polyreaction.
The pressure value P of the real time measure system in the polymerization process
t, be accurate to 0.001MPa.By the mathematical model in the detection system
The polymerisation conversion X that inscribes when calculating difference.When reaching 20%, the polymerisation conversion X under the mathematical model adds 0.02 part of acetone semicarbazone thiocarbamide cessation reaction as terminator, emptying discharging behind the stirring 5min.After centrifugal, drying, obtain sold resin again, weigh and do contrast with the vinyl chloride quality that adds, obtain the polymerisation conversion of weight method.Polymerisation conversion under the described mathematical model and weight method polymerisation conversion the results are shown in Table 2 in the method.
Embodiment 11～15
Repeat embodiment 10, difference is that embodiment 11 adds terminator when the polymerisation conversion X under the mathematical model reaches 30%, and embodiment 12～15th, adds terminator when polymerisation conversion X reaches respectively 40%, 50%, 60% and 80%.Polymerisation conversion under the mathematical model and weight method polymerisation conversion result see Table 2 with embodiment 10.
Embodiment 16～17
Embodiment 16 repeats embodiment 10 polymerizations and testing process, and difference is that tracer agent selects C among the embodiment 16
6The normal alkane addition is 6 parts.Embodiment 17 repeats embodiment 16, and difference is, C among the embodiment 17
6The normal alkane addition is 10 parts, adds terminator when the polymerisation conversion X under the mathematical model reaches 70%.Polymerisation conversion and the weight method polymerisation conversion result of embodiment 16～17 under mathematical model sees Table 2 with embodiment 10.
Table 2 mathematical model polymerisation conversion and the contrast of weight method conversion ratio
| The embodiment title | Polymerisation conversion under the mathematical model | The weight method polymerisation conversion | Mathematical model-weight method |
| Embodiment 10 | 20％ | 21.5％ | -1.5％ |
| Embodiment 11 | 30％ | 33.3％ | -3.3％ |
| Embodiment 12 | 40％ | 38.6％ | 1.4％ |
| Embodiment 13 | 50％ | 51.7％ | -1.7％ |
| Embodiment 14 | 60％ | 62.2％ | -2.2％ |
| Embodiment 15 | 80％ | 79.9％ | 0.1％ |
| Embodiment 16 | 80％ | 81.7％ | -1.7％ |
| Embodiment 17 | 70％ | 66.5％ | 3.5％ |
Embodiment 18
Polymeric kettle is rinsed well, apply anti-fouling agent and flushing, then vacuumize, with 100 parts of vinyl chloride, 180 parts deionized water, 0.07 part dispersed system (be comprised of high alcoholysis degree polyvinyl alcohol (PVA)/hydroxypropyl methylcellulose, the ratio of weight portion is 3: 2), 0.10 part initiator system (peroxidating neodecanoic acid isopropyl phenyl ester), 2 parts of C as tracer agent
7The material of normal alkane places polymeric kettle, is evacuated to the vinyl chloride monomer that adds formula ratio behind the 0.098MPa again, and cold stirring 10min is warming up to 46.0 ℃ of beginnings of temperature of reaction timing, carries out polyreaction.
The pressure value P of the real time measure system in the polymerization process
t, be accurate to 0.001MPa.By the mathematical model in the detection system
The polymerisation conversion X that inscribes when calculating difference.When reaching 75%, the polymerisation conversion X under the mathematical model adds 0.015 part of p-dihydroxy-benzene cessation reaction as terminator, emptying discharging behind the stirring 5min.After centrifugal, drying, obtain sold resin again, weigh and do contrast with the vinyl chloride quality that adds, obtain the polymerisation conversion of weight method.Polymerisation conversion under the described mathematical model and weight method polymerisation conversion the results are shown in Table 3 in the method.
Embodiment 19
Repeat embodiment 18, when the polymerisation conversion X under the mathematical model reaches 45%, add terminator.Polymerisation conversion under the mathematical model and weight method polymerisation conversion the results are shown in Table 3.
Embodiment 20
Repeat embodiment 18, difference is that tracer agent is selected C
8Isoalkane, addition are 1 part, add terminator when the polymerisation conversion X under the mathematical model reaches 85%.Polymerisation conversion under the mathematical model and weight method polymerisation conversion the results are shown in Table 3.
Embodiment 21
Repeat embodiment 20, difference is that the tracer agent addition is 7.0 parts, adds terminator when the polymerisation conversion X under the mathematical model reaches 75%.Polymerisation conversion under the mathematical model and weight method polymerisation conversion the results are shown in Table 3.
Embodiment 22
Repeat embodiment 21, difference is to add terminator when the polymerisation conversion X under the mathematical model reaches 60%.Polymerisation conversion under the mathematical model and weight method polymerisation conversion the results are shown in Table 3.
Embodiment 23
Repeat embodiment 18, difference is that tracer agent is C
6Naphthenic hydrocarbon.Polymerisation conversion under the mathematical model and weight method polymerisation conversion the results are shown in Table 3.
Embodiment 24～26
Repeat embodiment 23, difference is to add terminator among the embodiment 24 when the polymerisation conversion X under the mathematical model reaches 60%, and embodiment 25 and embodiment 26 add terminator, cessation reaction when polymerisation conversion X reaches respectively 40% and 30%.Polymerisation conversion and the weight method polymerisation conversion result of embodiment 24～26 under mathematical model sees Table 3 with embodiment 18～23.
Table 3 mathematical model polymerisation conversion and the contrast of weight method conversion ratio
| The embodiment title | Polymerisation conversion under the mathematical model | The weight method polymerisation conversion | Mathematical model-weight method |
| Embodiment 18 | 75％ | 71.5％ | 3.5％ |
| Embodiment 19 | 45％ | 47.8％ | -2.8％ |
| Embodiment 20 | 85％ | 83.3％ | 1.7％ |
| Embodiment 21 | 75％ | 73.0％ | 2.0％ |
| Embodiment 22 | 60％ | 63.7％ | -3.7％ |
| Embodiment 23 | 75％ | 73.6％ | 1.4％ |
| Embodiment 24 | 60％ | 63.9％ | -3.9％ |
| Embodiment 25 | 40％ | 38.0％ | 2.0％ |
| Embodiment 26 | 30％ | 32.9％ | -2.9％ |
The above only is preferred embodiment of the present invention, is not to be the restriction of invention being made other form, and any those skilled in the art may utilize the technology contents of above-mentioned announcement to be changed or be modified as the equivalent embodiment of equivalent variations.But every technical solution of the present invention content that do not break away to any simple modification, equivalent variations and remodeling that above embodiment does, still belongs to the protection domain of technical solution of the present invention according to technical spirit of the present invention.
Claims (7)
1. the method for a chlorine detection ethylene polymerization dynamics, it is characterized in that: according to a conventional method vinyl chloride, water, auxiliary agent and 0.5～10% the tracer agent that accounts for the vinyl chloride quality are added in the polymeric kettle, usually carrying out polyreaction under the polymerization temperature, real time record polymerization system force value and temperature data, polymerisation conversion X when the mathematical model that generates situation according to polymkeric substance calculates t constantly in detection system, treat to add terminator when polymerisation conversion X reaches technological requirement, can obtain the polymerization kinetics series data in the whole polymerization process.
2. the method for a kind of chlorine detection ethylene polymerization dynamics according to claim 1 is characterized in that: the mathematical model that described polymkeric substance generates situation is:
In the formula: X is constantly polymerisation conversion (% of unit) of t, m
aBe the addition (unit K g) of tracer agent, M
aBe the molecular weight of tracer agent, m
VcFor vinyl chloride initially adds quality (unit K g), M
VcBe vinyl chloride molecular weight, P
tBe t moment reaction still internal pressure (units MPa), P
aBe the tracer agent saturated vapor pressure (units MPa) under the polymerization temperature, P
VcBe the vinyl chloride saturated vapor pressure (units MPa) under the polymerization temperature.
3. the method for a kind of chlorine detection ethylene polymerization dynamics according to claim 1, it is characterized in that: the consumption of described tracer agent is 1～7% of raw material vinyl chloride quality.
4. according to claim 1 or the method for 3 described a kind of chlorine detection ethylene polymerization dynamics, it is characterized in that: described tracer agent is C
5～C
8Normal alkane or C
5～C
8Isoparaffin or C
6A kind of in the naphthenic hydrocarbon.
5. the method for a kind of chlorine detection ethylene polymerization dynamics according to claim 1 is characterized in that: in the polymerization reaction time, and real time record polymerization system force value, the force value degree of accuracy will reach 0.01Mpa.
6. a kind of method of chlorine detection ethylene polymerization dynamics according to claim 1 or 5 is characterized in that: measure polymerization system force value degree of accuracy and reach 0.001MPa.
7. the method for a kind of chlorine detection ethylene polymerization dynamics according to claim 1, it is characterized in that: described auxiliary agent comprises initiator system and dispersed system.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112010998A (en) * | 2020-10-30 | 2020-12-01 | 江西业力医疗器械有限公司 | Preparation process of modified carboxylic styrene-butadiene latex |
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| DE10233179A1 (en) * | 2002-07-22 | 2004-02-12 | Heinz Prof. Dr. Langhals | New N-vinylorganyl-perylene-3,4:9,10-tetracarbobisimide dyes and (co)polymers are used e.g. as dye or fluorescent dye, for bulk coloration of polymer or coloring natural material or in coating, ink, material test or semiconductor device |
| CN1657546A (en) * | 2005-02-05 | 2005-08-24 | 锦化化工（集团）有限责任公司 | Process for preparing polyvinyl chloride in 70.5 mcube polymeri reactor |
| CN1699992A (en) * | 2005-05-11 | 2005-11-23 | 上海氯碱化工股份有限公司 | Chloroethylene polymerization kinetics real time tracing and detecting apparatus and method |
| WO2009083044A1 (en) * | 2007-12-21 | 2009-07-09 | Basf Se | Method for producing a polymer |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE10233179A1 (en) * | 2002-07-22 | 2004-02-12 | Heinz Prof. Dr. Langhals | New N-vinylorganyl-perylene-3,4:9,10-tetracarbobisimide dyes and (co)polymers are used e.g. as dye or fluorescent dye, for bulk coloration of polymer or coloring natural material or in coating, ink, material test or semiconductor device |
| CN1657546A (en) * | 2005-02-05 | 2005-08-24 | 锦化化工（集团）有限责任公司 | Process for preparing polyvinyl chloride in 70.5 mcube polymeri reactor |
| CN1699992A (en) * | 2005-05-11 | 2005-11-23 | 上海氯碱化工股份有限公司 | Chloroethylene polymerization kinetics real time tracing and detecting apparatus and method |
| WO2009083044A1 (en) * | 2007-12-21 | 2009-07-09 | Basf Se | Method for producing a polymer |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112010998A (en) * | 2020-10-30 | 2020-12-01 | 江西业力医疗器械有限公司 | Preparation process of modified carboxylic styrene-butadiene latex |
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