CS220377B1 - Method of continuously monitoring kinetic processes of monomer polymerization and copolymerization - Google Patents

Description

The invention relates to a method for monitoring the kinetic course of polymerization and copolymerization of monomers in a single experiment independently of the degree of conversion achieved, and provides information on the whole kinetic course of polymerization and copolymerization of monomers.

According to the invention, during the polymerization of the monomer or the copolymerization of the monomers, a representative sample of a homogeneous or heterogeneous reaction mixture is taken over a defined period of time, after which the polymer and other components of the reaction system are separated amount.

The apparatus for carrying out this method consists of a polymerization reactor in which a sampling valve is introduced into which a carrier gas inlet and a carrier gas outlet are connected which are connected to a heat desorber of unreacted monomers which is connected via a carrier gas shift valve and a second resistive member with a gas chromatograph separation column. In the carrier gas path, a first resistive member and an auxiliary pressure carrier gas valve are located upstream of the sampling valve.

The invention relates to a method for following the kinetic course of polymerization and copolymerization of monomers in a single experiment, irrespective of the degree of conversion achieved, and provides information on the whole kinetic course of polymerization and copolymerization of monomers.

The kinetics of polymerization reactions under given conditions is determined by the reaction rate values of the reacting monomers. Single-phase reactions are called homogeneous when the polymer formed is insoluble in monomer or precipitates from solution, etc., and is a heterogeneous system. Measurement of reaction rates. or determination converse curves monomers is still a current issue, because the data obtained allow the ^EH-vhvňovat průb. processes, both on a laboratory and operational scale.

toakíím speed is defrn. ub ^y tkem Počta Mota monomar per unity ^of time, e-respekttv přírůstoem number of moles generated Ymer ^ol p. к postižern koncentračníchi changes ^and realtórn mixture was ^plated in ^U sing polymer chemistry series methods according to the nature of ongoing reakrn monitor ^also tokterou physical or chemical change ^No reaction system, which is a conversion function.

^ME^zi such methods include, for example, dilatometry, gravimetry, calorimetry, viscose^Fra^totome^trie^, spe^totrometry^, Measurement of dielectric toast-measurement of electrical^Odp^steedu. I use physical methods ° why it is cliemic for apparent needs^NYCHA da^t you^h· Odn^Eher^, because the reaction sy^100thhim^thansanitize and rea^toce nec^and be interrupted.

When .Studio het-erogenrá pofymerizace, ^kt er ^s e, ^AL Xperiment them more demanding are the most frequent applied dilatometry and gravimetry. Dilatometry is particularly suitable for bulk polymerization stiadmm in low conversions ^{of manufacture} pop pa e ^d pofymerizace solutions. Grav ^and metry is used for all types of polymerization throughout. range of final conversions. Particularly monitoring of the heterogeneous suspension and emulsion polymerization, or ^the statutes pnslušných onverzníc · ^h knvek been hitherto almost exclusively limited to use gravimetrického- determination of the resulting polymer. In order to construct the conversion curve, one polymerization has to be carried out for each point and the excluded polymer is isolated, which is time consuming. A further disadvantage of this otherwise versatile method is that individual p-polymerizations may differ from one another, for example, by not adhering to exactly the same reaction conditions, which adversely affects the reproducibility of the experimental results. Application of the gravimetric method of the copolymerization reaction, as well as the previously recited m Etot only provides hodnofy summary of reaction speed or sumárrn konverzrn ЫЗДу in ^width all zíteastntoých monomers while already ^p Úsobí according to ^y n ^and that zu is possible to obtain ^T krnettcto data ^for characterized ^d in ^{k -p} o ^ly isomerisation ^and ztáasta & Nu monomer separately.

Among ^{the para} uso ^b stedovárn kinetictóho average ^of b and ^EH at pofymerizace topofymerizace -monomerů ^to esters ^Pr e ^d M. ^et em ^y n and ^l sectional ^area, therefore ^it has ^{the DRI} in the cited methods the following advantages ^y. Desired Hnettcto -data for the rea -definované ^CZK her reward ^alkyl p-CIS ^ z ^ jedrn experiment, independently of the degree of conversion. You can specify not only konverzrn ^bush in ^ky sumánnt but jednothvých monomers of ^p ° C ^and then the ^No. reatórn. r ^ ⁱ r ^s MCST c ^hl axis ^t in toerémtoHv reaction time. It is also possible to determine the copolymerization parameters of the respective comonomers more easily than in the conventional manner. Accuracy of the degree of conversion or reaction rate,. Comparing ^L is N ^and V ^P for the ex erimént Linaria ^{s H} s ^y bs other previously used methods. It ranges from 2 to 5%.

^The ROM ^of previously listed ^d ených Wear ly ^from the use of a ^p · ůsoh according to ^{Y is N,} is climbing ^{TE d} and ^LSI implementation. It can be used for example to test the effectiveness of various initiating systems and ^TX etřov ^á m vhvu rea ^CZK which · ^M o ^d tot ^ki excipients for reaction progress and pofymerizace copolymerization whole. of the monomer range.

The object of the invention. a method for continuously monitoring the kinetics during the polymerization and ^the monomers topofymerizace esters consists in the fact that during polymernace monomer or monomers copolymerizable withdrawn at time intervals -definovaném representative sample of a homogeneous or heterogeneous mixture, whereupon the polymer composition and -dalrn ^alkyl rea ^ mho with a system, the ^p Aruja from the unreacted monomers, which matches · Transfer quantitatively into a gas chromatograph and determining the amounts thereof.

The apparatus for carrying out the method according to the invention consists of a polymerization reactor into which a sampling valve is introduced into the reactor. wherein a carrier gas inlet and a carrier gas outlet connected to the heat deserber of unreacted monomers are connected to a gas chromatograph separation column via a carrier gas shift valve and a second resistive member. A first resistive member and an auxiliary pressure carrier gas valve are disposed in the carrier gas path upstream of the sampling valve.

· Vapor space polymerization reactor may advantageously be connected ^straight ŠL ^ es RTIC shutoff valves and the six-way valve sample valve to which is connected a water seal, which allows to continuously monitor the composition of the gas phase reaction system. ^Z e ^{e f} složern pfynn Aze from TTA ^to ovýc ^h ratio ^of Ru in the reactor. is possible in some. . also obtain additional data on the kinetics of copolymerization.

The thermal desorber The advantage of the unreacted monomers is ^o n ^{e p} res associated with air chtedič Separa ^ em. This arrangement allows the separation of the condensation reaction components

With mixtures - from the gasified monomers before the actual Cernin chromatography.

The invention is further illustrated in the above ^to RESEC ^{h wh} e significance FIG. 1 is a schematic overall arrangement for kontinuálrn ^- sle ^d ovárn HneHckóho 'průbou ^p ol ^y isomerisation and ^to the ^p ol ^y by polymerization of monomers in FIG. 2 REA ^to cm ^p růběh homopotymerizace vinyl FIG. 3 copolymerization reaction progress vin ^y diatoms ^du propene to 10.4% by weight propene in the starting mixture monomeerní, FIG. 4, the copolymerization reaction progress' of vinyl chloride with propene to propene ^24.3% by weight in the starting monomer mixture, giant 5 reaction sequence of vinyl chloride ^- bbutene copolymerization for ^5.4 wt. ^1-butene in the starting monomer mixture, of R ^b. Reaction ^No. 6 M PR ^{ůběh to} opolymerizace vinytahtaridu with bjoentenem to ^15.2% by weight of 1-pentene in the starting monomer mixture, the further and examples.

In the device according to the invention (Fig. 1) is a carrier gas inlet 1 -to gas chromatograph whose inner space is schematically illustrated by the dashed rectangle, connected to šesticestaým vzorkovacta Ventua 2 which is further connected with a shift 'out of ^those m ^{3, -} with No preferably ^Tyr ces ^t Nym ^{and p} res prvrn resistive ^{No. 4} only with ^no tap-ma ⁵ to which is connected auxiliary valve 6 is pressurized carrier gas. The output of branch 5 is connected -with sampling valve 7. Sampling ^{CA T} vzorkovamho Eleventh ⁷ is inserted into ^p NMO 8 polymerizer equipped tempera ^C mm ^tire T ^E M 9 and 0. ¹ mfchadem Sample 7 as well as the six-way - the sampling valve 2 and the shift valve 3 are preferably pneumatically operated. The carrier gas outlet from the sampling valve 7 is introduced into the thermal desorber 11 of unreacted monomers, which is connected via air cooler 12 to a separator 13. The separator 13 is connected to a transfer valve 3, which is connected to a separation column via a second resistive member 14. The vapor space of the polymerization reactor 8 is connected via a choke valves 17, 18 to a solenoid valve 19, the outlet of which is connected to a six-way sampling valve 2. A water seal 20 is connected to the six-way sampling valve 2.

^p olymerační reaklor ⁸ vyMven -a measuring and recording the pressure 21 and temperature 22 of the automatic termostatováním 23rd

Description of the device function

The individual components of the reaction mixture are metered into the polymerization reactor 8 according to the chosen operating procedure and the content of the polymerization reactor 8 is brought to the prescribed operating temperature. From this point on, a gas chromatograph is activated, which controls and manages all the necessary operations in the selected program - including the sampling valve 7 - via the microcontroller.

A sample of the reaction mixture, for example 50 μΐ, is taken by a cylindrical slot in the sampling valve piston 7, which in the sampling position is inserted directly in the reactor 8. After moving the piston to the chromatographic carrier gas, the sample is through valve 6, quantitatively transferred to a heated heat-desor foxtail 11. Here, gasification occurs and fast - desorption of one or more monomers of a polymer or copolymer ^poly mer ^or after evaporation and ^DE-ton denzujfcfch components of the reaction mixture. These components condense in the air cooler 12 and accumulate in the separator 13. The gaseous monomers are transferred by the carrier gas through the transfer valve 3 to the separation column 15 of the gas chromatograph. To prevent transmission of a pressure surge in the circuit carrier gas, the carrier gas to the sample valve 7 - preferably PRIV ^Ade n ^BC EC prvrn by ^dp orový ^Articles en ⁴ and the same ^{hole H} y by ^dp orový ^Article en ¹⁴ is included to route the carrier gas before the separation column 1 ⁵ . Designed ^é -experimentem US ^p ora ^gives it allows by the synchronized ^activity uzavíractao ventita ^19, it Designs esticestn ^é ^ ovamho pfeřazovacl valve ² and valve 3 · him analyze one constant volume of sample taken from the gas space of the polymerization reactor eighth

In the described experimental complex may be The advantage ^o n ^e apltaován ^to Omer ^No. m gas chromatograph that allows programmable control their own gas chromatography ^{f ic} ou operarn and OVTA ^ t periferrn ^d is not ^alkyl in slowly time ^p subroutines I ^'k is described above.

Furthermore, for clarity in Tables I and II contain one of possible programs for continuous ^- s ^l s e ^{d ck} WneH ého ^ r ^p u ^{p ůběh} olymerizace - and copolymerization of monomers. Table I shows the program for self-chromatographic analysis, cyclically repeated, and Table II, the time program for automatic sampling of the gas phase and the heterogeneous reaction mixture in each cycle.

Tab. AND

Chromatographic analysis program

Symbol Controlled variable Meaning of the symbol Requested value Actual (measured) value TEMP I temperature at night 50 (QCJ 50 ° C TIME I time of isothermal analysis 60 ', 0 (min) RATE Line ^and temperature rise RNI 'end TIME I 0.01 pc / min) TEMP II temperature at 2nd isothermal level 52 (° C) TIME II time of 2 isothermal analysis 0.0 · (min) TNJ TEMP injection chamber temperature 150 · (° C) 150 · pC) FID TEMP FID body temperature 150 PC) 150 (* C) TCD TEMP TCD body temperature 0 (° C) 25 (° C) AUX TEMP temperature of the electrically heated block in the periphery of GC 0 (° C) 25 pC) OVEN MAX maximum allowable oven temperature 54 (° C) CHT SPD paper feed speed ^0.20 (cm / min) ATT 2 detector signal attenuation ¹⁵ (attenuation 32,768 times) FID SINGL in ^lb AAZ ^Pooh engagement with ^b FID AND SLP SENS USO of ^{p b} mtegrace ^{pl h} oc peaks 10.00 AREA REJ method of peak integration 1 FLOW A carrier gas flow on route ³⁰ (cm ³ / min) ROW B flow of carrier p ^ly nu ⁰ (cm ^{3 /} min)

(on route B ’

OPTN command for cyclic repetition of the specified program after programmed termination _; . rn analyzes and ^y values in ^the Vytis

Tab. II

Time program ^P ro VZO ^auto-ply OVAM variables phase and hetero ^g Ennio reakčrn ESI ^m s

time from program start (min) Symbol Command ’ Meaning of the symbol 0.1 VLV / EXT 1 valve dispensing position (7) 0.2 VLV / EXT 4 valve opening (6) 0.3 VLV / EXT - 4 closing the valve (6) 0.4. VLV / EXT 2 - valve (3) connected to valve (7) 21.0 VLV / EXT 5 valve opening (19) 21.0 VLV / EXT - 2 unconnected valve (3) with valve (7) 22.0 VLV / EXT - 5 closing the valve (19) 22.0 VLV / EXT 0 SM Ventua ^Yc k (2) for inclusion in a route ^of a carrier gas 30.0 VLV / EXT - 0 the v-eintile loop (2) is put back into the gas phase sampling path 30.6 VLV / EXT - 1 Valve Sampling Position (7) 31.0 VLV / EXT 1 valve dispensing position (7) 31.1 VLV / EXT 4 valve opening (6) 31.2 VLV / EXT - 4 closing the valve (6) 31.3 VLV / EXT 2 valve (3) connected to the valve (7) 59.0 STOP programmed termination

analysis, instruction for listing values and START further analysis

Example 1

Simulated polymerization

Na 'tzv. simulated polymerization was verified by re ^p rodukovate ^l Nost ^b er of ^the samples, especially heterogeneous ^E on ^the APA ^I don phase in terms of solubilizing amount collected ^and sioroní primarily in terms of suspension polymerization of vinyl chloride.

Charged him ^{b 1 d} m ^{3 would be} well to ^be in ^the oTab. III Christmas 8.75 g · ^y solution of hydroxypropylmethylcellulose (3, ^8% solution) ⁵ 1 ^{5 g} distilled water and 216 ^{g of y-vin} chloride without irnciátorů. The heterogeneous liquid and equilibrium gas phase was sampled from a 55 ° C reactor at various stirrer speeds.

The results of the detector response to the sampled solubilizing amount ^{PL hook} oc ^ c ^h jednothvý ^peaks (AREA) are summarized in Tab. III.

Verification of sampling reproducibility in sampling of gaseous and heterogeneous liquid phases

Subscription no. Number of revolutions (min “ ¹ ) Gas phase (AREA). ID ⁵ Liquid phase (AREA). 106 1 300 3859 3173 2 300 3860 3175 3 300 3803 .3201 4 300 3848 3285 5 300 3858 3181 3846 diameter diameter 3203 6 600 3865 3222 7 600 3862 3246 8 ^ H00 - 3879 3255 9 600 3879 3221 10 600 3857 31- (02 3868 diameter diameter 3229

Example 3

Maximálrn relaHvrn c ^Hyb AVO ^db proportions of gaseous samples and heterogeneous liquid phase no ^p řevysuje ^1%.

Example 2

Copoly ^y isomerisation vmytehloridu 10, .4% by weight propene in the starting monomer mixture

Homopolymerization of vinyl chloride

To REA ^the torus volume of ¹ m ^{3 was d} o to ^D and in ^the alkoxylated solution of 8.75 g hydroxypropyimethylcelu ^LO from ^y (% .3,8 ^The organic solution), 515 ^g water and a destiteva 0.20035 g dicetylperoxydikarhonátu. After the reactor was inertized, 216 g of vinyl chloride were added.

The polymerization was carried out for 8 hours at pH 55 + 0.1 ° C; a ^wheelbarrow mkMa ^y was set at ^{5 y} C0 · min ^{'1. In the} ovaries of the heterogeneous reaction mixtures, they were performed automatically at thirty minute intervals according to the selected program.

^N, and Fig. ² is a ^graphite c ^ky Zorn ^of Zn ^and at the time dependence of the quantity of vinyl chloride stanovovaného chromatography (G) in the sample and to achieve it ^{TOWING s} degree ^of onverze ^{to (K),} experimentally determined in the homopolymerization of vinyl chloride. From this figure it is evident a very good correspondence between the chromatographic results with those obtained by the gravimetric method ^for the now obsolete spomvá ^p RERUM ^w ern rea tion ^to zvoteném in time and determination of TEOT and weight polymer. The gravimetric data is indicated by an empty circle in Fig. 2.

To REA ^to him ^b torus about ¹ dm ³ b ^{Y d} to lo ávkováno .13,1'2 solution hydroxypropylmethylcelutezy g ⁽³ 8% solution), ^{515 g of} water, 0.80110 destitovaro '·. g of dicetylperoxydicarbonate. After inertization, propene and vinyl chloride were added in a total amount of 216 g.

Copolymerization proceeded for 18 ^hours at ⁵ s 5 ^ + ^ ⁰ ^ ^{1, and C;} turns ^to s stirred ^yl y b are set to ¹ 500 min ^-1. Time program ^P ro automatic sampling was selected so that the periodic cycle analysis contained four sampling heterogeneous reaction mixture and a gaseous phase collection. Including the printout of the values took 60 minutes. A column diameter of ^2.5 mm ^{, 12} m in length, ²⁰ % by weight was used for chromatographic separation of the monomer mixture (vinyl chloride-1-olefin). ^3,3 '-oxidipropioniirilu to Chromatonu N-AW grains ^{of tup} 6250 - ^{0 31} 5 mm. The isotomeric anatase was carried out at 50 ° C, using a flame ionization detector as nitrogen as the carrier gas.

In Fig. 3, the time dependence of the chromatographically determined amount of monomers (Gj) in the sample and the degree of conversion achieved (Κ,) for vinyl chloride (1) and comonomer (2 ·) are treated.

Example 4 -'- ^p

Copolymerization of vinyl chloride ^- with 243% by weight of propene in the starting monomer mixture

A reactor volume of 1 m ^{3 d} b ^{y d} to lo óvkováno total. 216 g of monomer mixture such that the propene content of the starting monomer mixture was 24.13. % ^h 'mot. DAV ^to ovárn ostatmch rea ^to čmch ^DIMENSION. its quantity. reacting ^p o ^d i Mink program for sampling heterogeneous reaction mixture and the chromatographic operations were the same as in Example 3rd

Realkční copolymerization course is ^p racován similarly as in Example 3> Fig. 4.

Difference ^{R y} zi ^{AI é} the pn compare them stu ^p inversion -stanoveného chromatography gravimetrically vrnytehlortóu not exceed the copolymerization with ^p ro ^{p p} r ene in ^{2% of} mers.

Example - 5

Copolymerization of vinyl chloride with 1-butene

The reactor -o je'mu ^{b 1 d} m ³ byte to ^be alkylated in ^the CELT ^{216 g} monomer ^- a mixture ^anyway. the content of 1-hutenu in the starting monomer -Mixtures amounted to 5.4% mot ^{h. LeVeLs} Community ^ other reactants, reaction conditions and the program for the chromatographic operation were the same as in Example ^3. The selected time schedule for automatic sampling is enabled during N ^{d s h} o ^{d y} in - ^p rov ^E ST ^{D as} analyzing a ^{g h} etero Ennio reatórn mixture and nu ^{d é} --analýzu a gaseous phase.

Reactions ^run posttouje ma. ^p o ^{d b} of them as in the example - the third FIG. 6.

Claims (4)

SUBJECT CLAIMS 1. A process for continuously monitoring the kinetic course of polymerization and copolymerization by monomers indicated by Mm. that during the polymerization of the monomer or monomers copolymerizable -odebírá in a time interval defined by a representative sample of a homogeneous or ^h etero ^g Ennio reaWní ^- a mixture ^of a. whereupon the polymer and other components of the reaction system separate from the unreacted monomers. which are quantitatively transferred to a gas chromatograph and quantified. 2. An apparatus for carrying out the method according to claim 1, characterized by. that it consists of polymer ^C whom you reaMoru (8). ^D o which is ^D EN closes the sampling valve (7). into which the carrier gas inlet and carrier gas outlet open. which is connected to a thermal desorber (11) not Example Copolymerization of vinyl chloride with 1-pentane DO- REALITOR -objemu 1 m ^{3 d} b to ^d of ^yl in ^K s ^and NO ^Cel em Ж ^{g of} monomer mixture and a ^{-t k.} The composition according ^to claim 1, wherein the content of 1-pentene in the starting monomer mixture ^- cinK ¹⁵ . ² wt. No ^M <victories ^s -ostatmto reatónM O ^{L Z} e ^k. -rea ^to project beyond ^D min ^{alkyl and} software pro- chromatography operation was equal ^to I s přtelato ^third The sampling of the heterogeneous reaction mixture was automated according to the time schedule mentioned in Example 5. ^R EAK ^No pr rn ^by BE ^'hk OPO ^ly affected by polymerization. similar to Example 3. FIG. 6. When confronted summary conversion curve topotymerizace zjtetěto cliromatografic ^ S curve obtained using the gravimetric metho ^d y byte ^ZDY zjtéténa Fig very ^{d and} compliance. ^From operates ^dl ev ^y n and ^l can be cut with the above ^h ou ^d used ^for jrné type ^y tomopotymerizací and copolymerization. not only in suspension polymerization, but also in emulsion. solution. and in low conversions and at - Block Poly- merteach method described herein ^of continuously whitebeard The festival ^ y pr ^ůběh isomerisation pol ^{y s and} t kopotymerizací různýto ^ypu monomeríi. For example, the most commonly known monomers such as -styrene and its derivatives are suitable. ^vi nylace ^melt . torw & y ^ky selrny acrylic and methacrylic and others. of the invention of the reacted monomers. which is connected via a shift valve (3) and the path of the gas ^{hole H} y ^d of the pore element (1.4) connected by ELISA ^{d i} Ko ^l sometimes inappropriate ⁽¹⁵⁾ -p ^ly nov ^eh of toroma-Sh. wherein in the path of the carrier ^ply nu ^{d Pr} e sampled release valve (7) is first -odporový en ^{Article (4)} - in L ^ ^ L (6) ^p omocného button ^to AC nosného- gas. 3. Apparatus according to claim 2, characterized by. ^Z e potymeračního vapor space of the reactor (8) is ^straight es škrtím ventdy ^{(17. 18)} and ventral (.19) connected to six-way sampling venti em ^{l (2).} to Seremo pnpojen water is already ^a ver (20). 4. Equipment according to items 2 and 3. -marked by. The thermal desorber - (11) of the unreacted monomers is connected via an air cooler (12) to the separator (13).