CS258231B1 - Method of polymers or copolymers preparation from stabilized vinyl monomers - Google Patents
Method of polymers or copolymers preparation from stabilized vinyl monomers Download PDFInfo
- Publication number
- CS258231B1 CS258231B1 CS865266A CS526686A CS258231B1 CS 258231 B1 CS258231 B1 CS 258231B1 CS 865266 A CS865266 A CS 865266A CS 526686 A CS526686 A CS 526686A CS 258231 B1 CS258231 B1 CS 258231B1
- Authority
- CS
- Czechoslovakia
- Prior art keywords
- polymerization
- monomer
- conversion
- minutes
- monomers
- Prior art date
Links
- 239000000178 monomer Substances 0.000 title claims abstract description 42
- 229920000642 polymer Polymers 0.000 title claims abstract description 17
- 229920001577 copolymer Polymers 0.000 title claims abstract description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 title claims abstract description 4
- 229920002554 vinyl polymer Polymers 0.000 title claims abstract description 4
- 238000000034 method Methods 0.000 title description 15
- 239000003381 stabilizer Substances 0.000 claims abstract description 17
- 238000007720 emulsion polymerization reaction Methods 0.000 claims abstract description 11
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000003999 initiator Substances 0.000 abstract description 14
- 239000000839 emulsion Substances 0.000 abstract description 5
- 239000003505 polymerization initiator Substances 0.000 abstract 1
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 32
- 238000006116 polymerization reaction Methods 0.000 description 30
- 230000005764 inhibitory process Effects 0.000 description 13
- 239000008346 aqueous phase Substances 0.000 description 11
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 6
- 239000003112 inhibitor Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 230000000977 initiatory effect Effects 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 239000000693 micelle Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 239000004141 Sodium laurylsulphate Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000012935 ammoniumperoxodisulfate Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- LRDFRRGEGBBSRN-UHFFFAOYSA-N isobutyronitrile Chemical compound CC(C)C#N LRDFRRGEGBBSRN-UHFFFAOYSA-N 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
Abstract
Rieši sa příprava polymérov alebo kopolymérov emulznou polymerizáciou stabilizovaných vinylových monomérov. Spočívá v tom, že polymerizujúca emulzia obsahuje pri monoméri a iniciátore polymerizácie aj stabilizátor monoméru. Ako stabilizátory monomérov sa používajú deriváty piperidín-l-oxylu obecného vzorca I, kde R je alkyl o počte uhlíkov 7 až 17. Pri tomto spůsobu nie je třeba čistit monoméry, ani používat vysoké koncentrácie iniciátora.The preparation of polymers or copolymers is solved by emulsion polymerization stabilized vinyl monomers. It consists in being polymerizing the emulsion contains a monomer and a polymerization initiator as well as a monomer stabilizer. Monomer stabilizers are used piperidine-1-oxyl derivatives of formula I wherein R is alkyl of 7 to 17. It is not necessary to clean in this way monomers, nor to use high concentrations the initiator.
Description
Vynález sa týká spósobu přípravy polymérov alebo kopolymérov zo stabilizovaných vinylových monomérov.The invention relates to a process for preparing polymers or copolymers from stabilized vinyl monomers.
Emulzná polymerizácia sa používá na přípravu polymérov a kopolymérov a polymérových disperzi! pre rózne odvetvia národného hospodárstva. Ako příklad móže slúžit emulzná polymerizácia butylakrylátu (I. Čapek, J. Bartoň, E. Orolínová, Chem. Zvěsti 38 (6) 803-822 (1984)), alebo kopolymerizácia akrylonitrilu s butylakrylátom (I. Čapek, J. Bartoň, E. Orolínová,Emulsion polymerization is used to prepare polymers and copolymers and polymer dispersions! for different sectors of the national economy. Examples are emulsion polymerization of butyl acrylate (I. Capek, J. Barton, E. Orolinova, Chem. Zvěsti 38 (6) 803-822 (1984)), or copolymerization of acrylonitrile with butyl acrylate (I. Capek, J. Barton, E). Orolínová,
Acta Polymerlca 36, 4, (1985)). Výhodou emulznej polymerizáoie je vysoká rýchlosť polymerizácie, možnosť přípravy polymérov róznorodej chemiokej a fyzikálnej štruktúry (latexy typu jadro/obal) a v porovnaní s polymerizáciou v organickom rozpúšťadle, ekologická nezávadnost disperzného média - vody.Acta Polymer 36, 4, (1985)). The advantage of emulsion polymerization is the high rate of polymerization, the possibility of preparing polymers of diverse chemical and physical structure (core / shell latices) and, compared to polymerization in an organic solvent, the ecological safety of the dispersion medium - water.
Naviac polymerizácia v heterofázovom emulznom systéme umožňuje použiť vhodné stabilizované monoméry bez nutnosti odstrániť stabilizátor před uskutočnením polymerizačnej reakcie (D. C. Blackley, Emulsion Polymerization, Applied Science Publishers, London (1975)); J. W. Vanderhoff,In addition, polymerization in a heterophasic emulsion system makes it possible to use suitable stabilized monomers without having to remove the stabilizer before carrying out the polymerization reaction (D. C. Blackley, Emulsion Polymerization, Applied Science Publishers, London (1975)); J. W. Vanderhoff,
J. Polym. Sci., Polymer Symposium 72, 161 (1981).J. Polym. Sci., Polymer Symposium 72,161 (1981).
Monoméry ako látky náchylné teplom, svetlom alebo za přítomnosti zdroja radikálov spontánně polymerizovať v priebehu skladovania alebo přepravy, je potřebné stabilizovat.Monomers, such as those susceptible to heat, light or in the presence of a radical source spontaneously polymerize during storage or transport, need to be stabilized.
Ako stabilizátory monomérov sa používajú rózne látky, ktoré zabraňujú iniciácii, alebo retardujú rastové reakcie polymerizáoie. Před uskutočnením polymerizáoie je potřebné tieto látky z monomérov odstrániť. Oddělit monomér od stabilizátora možno destiláciou monoméru spravidla za zníženého tlaku, vypieraním zriedeným lúhom s následným prepieraním a destiláciou, alebo prosto použitím stabilizovaného monoméru k polymerizáoii (G. M. Burnett,Various monomers are used as monomer stabilizers to prevent initiation or retard polymerization growth reactions. It is necessary to remove these substances from the monomers before carrying out the polymerization. The monomer can be separated from the stabilizer by distillation of the monomer as a rule under reduced pressure, by washing with dilute liquor followed by washing and distillation, or simply by using the stabilized monomer for polymerization (G. M. Burnett,
Mechanism of Polymer Reactions, Interscience Publishers, London (1954)).Mechanism of Polymer Reactions, Interscience Publishers, London (1954).
V poslednom případe je však potřebné použiť vysoké koncentrácie iniciátora, aby sa znížila inhibičná perioda podmienená prítomnosťou stabilizátora v monoméri. Je zřejmé, že tieto spósoby majú značné nevýhody. Čistenie monoméru je operáciou naviac, energeticky náročnou a ekologicky nepriaznivou, pretože časť monoméru prechádza do prepieraoej vody, resp. sa stráca pri vákuovej destilácii a priamo, či nepriamo sa dostává do životného prostredia Použitie vysokej koncentrácie iniciátora jednak zdražuje výrobný proces, zanáša do produktu vyšší počet produktov rozkladu iniciátora a móže spósobovať i vedlajšiee reakcie pri polymerizácii, alebo neskoršie v hotovom produkte.In the latter case, however, it is necessary to use high concentrations of the initiator in order to reduce the inhibition period due to the presence of the stabilizer in the monomer. Obviously, these methods have considerable disadvantages. The purification of the monomer is an extra, energy-intensive and environmentally unfavorable operation, since part of the monomer passes into the washed water or water. It is lost in vacuum distillation and directly or indirectly enters the environment. The use of a high concentration of initiator both increases the cost of the production process, introduces a higher number of initiator decomposition products into the product and can cause side reactions during polymerization or later in the finished product.
Uvedené nevýhody odstraňuje spósob přípravy polymérov a- kopolymérov zo stabilizovaných monomérov účinkom vodorozpustného iniciátora akým je napr. peroxodisiran amónny alebo olejovorozpustného iniciátora, akým je 2,2-azoizobutyronitril alebo dibenzoylperoxid, ktorého podstata spočívá v tom, že na stabilizáciu monomérov sa použijú deriváty piperidín-l-oxylu obecného vzorce X, kde R je alkylo počte atomov uhlíka 7 až 17, ktorých inhibičné účinky na radikolovú polymerizáciu sú velmi dobré známe a ktorých rozpustnost vo vodnej fáze emulzného polymerizačného systému je nižšia ako 10 3 mol.dm 3.These disadvantages are eliminated by the process of preparing polymers and copolymers from stabilized monomers by the action of a water-soluble initiator such as e.g. ammonium peroxodisulfate or an oil-soluble initiator such as 2,2-azoisobutyronitrile or dibenzoyl peroxide, characterized in that piperidine-1-oxyl derivatives of the general formula (X) in which R is an alkyl number of 7 to 17, the inhibitory effects on radical polymerization are well known and whose solubility in the aqueous phase of the emulsion polymerization system is less than 10 3 mol.dm 3 .
Výhodou navrhovaného spósobu prlpravy polymérov a kopolymérov zo stabilizovaných radikálovo polymerizovatelných monomérov je, že proces emulznej polymerizáoie a kopolymerizáoie prebieha ako v případe čistých, nestabilizovaných monomérov, prakticky bez významnejšej inhibičnej periody. Použitie navrhovaného spósobu je osobitne výhodná v případe použitia iniciátorov rozpustných prevážne v olejovej fáze pretože sa tak blokuje polymerizácia v kvapkách monoméru a v micelách emulgátora obsahujúcich časť monoméru.An advantage of the proposed process for preparing polymers and copolymers from stabilized radically polymerizable monomers is that the process of emulsion polymerization and copolymerization proceeds as in the case of pure, unstabilized monomers, with virtually no significant inhibition period. The use of the proposed method is particularly advantageous in the case of using primarily oil-soluble initiators, as this prevents polymerization in the monomer droplets and in the micelles of the emulsifier containing a portion of the monomer.
Inioiácia polymerizáoie nastáva vo vodnej fáze, v ktorej je čiastočne popři monoméri rozpuštěný aj tzv. olejovorozpustný iniciátor. Rozpustnosť 2,2-azoizobutyronitrilu (AIBN) vo vodnej fáze pri teplote 60 °C je asi 7 % z celkového použitého množstva iniciátora.The polymerization initiation takes place in the aqueous phase, in which the so-called " oil-soluble initiator. The solubility of 2,2-azoisobutyronitrile (AIBN) in the aqueous phase at 60 ° C is about 7% of the total amount of initiator used.
-2 -3-2 -3
Použitím koncentrácie AIBN cca 10 mol.dm monoméru možno teda dosiahnuť vo vodnej fáze takú koncentráciu iniciátora, ktorá zabezpečí přibližné rovnakú rýchlosť polymerizáoie aká sa získá použitím vodorozpustného iniciátora peroxodisíranu draselného o koncentráciiThus, by using an AIBN concentration of about 10 mol.dm of monomer, an initiator concentration can be achieved in the aqueous phase which provides approximately the same polymerization rate as is obtained by using a water-soluble potassium peroxodisulfate initiator at a concentration of
-4 -3 cca 5x10 mol.dm vodnej fázy. Iniciačný mechanizmus polymerizácie je pre oba druhy iniciátorov teda rovnaký, pretože stabilizátor monoméru blokuje iniciáciu v olejovej fáze., zatial čo iniciácia polymerizácie vo vodnej fáze, v ktorej stabilizátor je rozpustný v maximálněj -5 -3 koncentrácii do 1x10 mol.dm nie je významnejšie blokovaná.-4 -3 approx. 5x10 mol.dm of the aqueous phase. Thus, the polymerization initiation mechanism is the same for both types of initiators since the monomer stabilizer blocks the initiation in the oil phase, while the initiation of the polymerization in the aqueous phase in which the stabilizer is soluble at maximum -5 -3 concentrations up to 1x10 mol.dm is not significantly blocked. .
Hlavný podiel rastových reakcii sa uskutočňuje v postupné sa vytvárajúcej novej olejovej fáze, pozostávajúcej z polymérovo-monomérových častíc, a neobsahujúcej původně v monoméry rozpuštěný stabilizátor (inhibitor). Transferom monoméru z kvapiek a z miciel emulgátora dochádza k postupnému zvyšovaniu koncentrácie inhibítora v kvapkách a micelách. V oblasti konverzi! monoméru nad 70 % začína aj difúzia stabilizátore do vodnej fázy.The major part of the growth reactions is carried out in a progressively forming new oil phase, consisting of polymer-monomer particles, and which does not initially contain a stabilizer (inhibitor) dissolved in the monomers. By transferring the monomer from the droplets and from the emulsifier micelles, the inhibitor concentration in the droplets and micelles is gradually increased. In the conversion area! The monomer above 70% also begins the diffusion of the stabilizer into the aqueous phase.
Dezaktivácia stabilizátora vo vodnej fáze radikálmi iniciátora vedie k postupnému zániku stabilizačného (inhibičného) účinku molekúl stabilizátora v reakčnom systéme. Vzhladom k tomu, že v tomto Stádiu polymerizácie, rastové reakcie sa uskutečfiujú v polymérovo-monomérových častlciach tj. v novovytvorenej olejovej fáze, přechod stabilizátora do vodnej fázy sa už nepřejaví kineticky na polymerizačný proces. Z uvedeného plynie, že pre realizovanie záměru predmetu vynálezu nie je rozhodujúci mechanizmus dezaktivačnej reakcie reaktívnych radikálov s molekulami stabilizátora.Inactivation of the stabilizer in the aqueous phase by initiator radicals leads to a gradual disappearance of the stabilizing (inhibitory) effect of the stabilizer molecules in the reaction system. Since at this stage of polymerization, the growth reactions take place in the polymer-monomer particles, i.e. in the polymer. In the newly formed oil phase, the transition of the stabilizer to the aqueous phase is no longer converted kinetic to the polymerization process. Accordingly, the mechanism of the deactivation reaction of reactive radicals with stabilizer molecules is not critical to the practice of the present invention.
Rozhodujúce pri výrobě stabilizátora je, aby bol čo najmenej rozpustný vo vodnej fáze emulzného polymerizačného systému. Horná hranice rozpustnosti stabilizátora pri obvyklých podmienkach emulznej polymerizácie nesmie překročit 10 5 mol.dm 3 vodnej fázy. vlastnosti produktov připravených zo stabilizovaných monomérov sú totožné s vlastnosťami produktov připravených z nestabilizovaných, čištěných monomérov.The decisive factor in the production of the stabilizer is that it be as soluble as possible in the aqueous phase of the emulsion polymerization system. The maximum solubility limit of the stabilizer under normal emulsion polymerization conditions must not exceed 10 5 mol.dm 3 of the aqueous phase. the properties of the products prepared from the stabilized monomers are identical to those of the products prepared from the unstabilized, purified monomers.
Příklad 1Example 1
Do trojhrdlej reakčnej banky objemu 250 ml opatrenej miešadlom, spatným chladičom, prívodom pre dusík a zariadením pre odběr vzoriek sa vnesie 80 ml destilovanej vody, 40 ml metylmetakrylátu, 1x10 2 mol. dm 3 (0,2307 g) laurylsulfátu sodného, 5x10 4 mol.dm 3 (0,00913 g) -4 -3 peroxodisíranu amonného a 1x10 mol.dm (0,00175 g) 4-stearoyloxy-2,2,6,6-tetrametylpiperidín-l-oxylu.A three-necked 250 ml reaction flask equipped with a stirrer, a reflux condenser, a nitrogen inlet and a sampling device was charged with 80 ml of distilled water, 40 ml of methyl methacrylate, 1x10 2 mol. dm 3 (0.2307 g) sodium lauryl sulphate, 5x10 4 mol.dm 3 (0.00913 g) -4 -3 ammonium persulfate and 1x10 mol.dm (0.00175 g) 4-stearoyloxy-2,2.6, 6-tetramethylpiperidine-l-oxyl.
V priebehu polymerizácie sa odoberalo po 1,5 ml emulzie k izolácii polyméru a k stanoveniu stupňa konverzie. Polymerizácia bola robená pri teplote 60 °C v atmosféře dusika. Polymér sa izoloval z emulzie tak, že sa emulzia vysrážala do etanolu. Získaný skoagulovaný polymér sa sušil pri teplote 60 °C a pri tlaku 5 kPa po dobu 8 hodin. Z takto získaných údajov o množstve vznikájúceho polyméru za daný časový úsek sa vypočítá časový priebeh polymerizácie, inhibičná perioda a rýchlosť polymerizácie. Rýchlost polymerizácie v intervale stacionárněj rýchlosti je 0,033 % konverzie s 3; celková doba polymerizácie je 150 minút. Inhibičná perioda je kratšia ako 10 minút. Velkost častíc je 54 nm. Finálna konverzia monoméru: 98 %.During the polymerization, 1.5 ml of an emulsion was taken to isolate the polymer and to determine the degree of conversion. The polymerization was carried out at 60 ° C under a nitrogen atmosphere. The polymer was isolated from the emulsion by precipitating the emulsion into ethanol. The resulting coagulated polymer was dried at 60 ° C and 5 kPa for 8 hours. The polymerization time, the inhibition period and the polymerization rate are calculated from the amount of polymer formed over a given period of time. The polymerization rate at the stationary rate interval is 0.033% conversion with 3 ; the total polymerization time is 150 minutes. The inhibition period is less than 10 minutes. The particle size is 54 nm. Final monomer conversion: 98%.
Příklad 2Example 2
Postupuje sa ako v příklade 1 s tým rozdielom, že sa použije ako monomér butylmetakrylát v množstve 40 ml. Rýchlosť polymerizácie v intervale stacionárnej rýchlosti je 0,012 % konverzie s-3. Finálna konverzia 99 % sa dosiahla za 200 minút. Inhibičná perioda bola kratšia ako 10 minút.The procedure was as in Example 1 except that butyl methacrylate monomer was used in an amount of 40 ml. The polymerization rate at the stationary rate interval is 0.012% conversion with -3 . A final conversion of 99% was achieved in 200 minutes. The inhibition period was less than 10 minutes.
Příklad 3Example 3
Postupuje sa ako v příklade 1 s tým rozdielom, že sa použil ako monomér styrén. Rýchlosť polymerizácie v intervale stacionárnej rýchlosti je 0,004 % konverzie s 3. Finálna konverzia 95 % sa dosiahla za 300 minút, velkost častíc latexu bola 110 nm.The procedure was as in Example 1 except that styrene was used as the monomer. The polymerization rate at the stationary rate interval is 0.004% conversion with 3 . The final conversion of 95% was achieved in 300 minutes, the particle size of the latex was 110 nm.
Příklad 4Example 4
Postupuje sa ako v příklade 1 s tým rozdielom, že sa použili ako monoméry styrén/akrylonitril v mólovom pomere 1:1. Rýchlosť polymerizácie v intervale.stacionárnej rýchlosti je 0,008 % konverzie s . Konverzia 60 % sa dosiahla za 150 minút, inhibičná perioda bola kratšia ako 10 minút.The procedure was as in Example 1 except that styrene / acrylonitrile monomers were used in a molar ratio of 1: 1. The polymerization rate at the stationary rate interval is 0.008% conversion s. Conversion of 60% was achieved in 150 minutes, the inhibition period was less than 10 minutes.
Příklad 5Example 5
Postupuje sa ako v příklade 1 s tým rozdielom, že sa použili ako monoméry butylmetakrylát/akrylonitril v mólovom pomere 55/45. Rýchlosť polymerizácie v intervale stacionárnej rýchlosti je 0,010 % konverzie s-3. konverzia 80 % sa dosiala za 250 minút. Inhibičná perioda bola kratšia ako 5 minút.The procedure was as in Example 1 except that butyl methacrylate / acrylonitrile monomers were used in the 55/45 molar ratio as monomers. The polymerization rate at the stationary rate interval is 0.010% conversion with -3 . a conversion of 80% was achieved in 250 minutes. The inhibition period was less than 5 minutes.
Príklad6Example 6
Postupuje sa ako v příklade 1 s tým rozdielom, že sa ako monomér použil 2-etylhexylmetakrylát v množstve 40 ml. Rýchlosť polymerizácie v intervale stacionárnej rýchlosti je 0,010 % konverzie s-1. Finálna konverzia 98 % sa dosiahla za 230 minút. Inhibičná perioda bola 15 minút.The procedure was as in Example 1 except that 2-ethylhexyl methacrylate was used as monomer in an amount of 40 ml. The polymerization rate at the stationary rate interval is 0.010% conversion s -1 . A final conversion of 98% was achieved in 230 minutes. The inhibition period was 15 minutes.
Příklad 7Example 7
Postupuje sa ako v případe 1 s tým rozdielom, že sa ako inhibitor použil 2,2,6,6-tetrametyl-4-dodekanoyloxypiperidín-l-oxyl lxlO-4 mol.dm-3 (0,00142 g) . Rýchlosť polymerizácie v intervale stacionárnej rýchlosti je 0,009 % konverzie s-3. Konverzia 96 % sa dosiahla za 250 minút. Inhibičná perioda bola 20 minút.The procedure was as in Example 1 except that 2,2,6,6-tetramethyl-4-dodecanoyloxypiperidine-1-oxyl-lx10 -4 mol.dm -3 (0.00142 g) was used as the inhibitor. The polymerization rate at the stationary rate interval is 0.009% conversion s -3 . Conversion of 96% was achieved in 250 minutes. The inhibition period was 20 minutes.
Příklad 8Example 8
Postupuje sa ako v příklade 1 s tým rozdielom, že sa ako inhibitor použil 2,2,6,6-tetra-4 -3 metyl-4-dekanoyloxypiperidín-l-oxyl 1x10 mol.dm (0,0013 g). Rýchlosť polymerizácie v intervale stacionárnej rýchlosti je 0,009 % konverzie s . Finálna konverzia 95 % sa dosiahla za 250 minút. Inhibičná perioda bola 25 minút.The procedure was as in Example 1 except that 2,2,6,6-tetra-4-methyl-4-decanoyloxypiperidine-1-oxyl 1x10 mol.dm (0.0013 g) was used as the inhibitor. The polymerization rate at the stationary rate interval is 0.009% conversion s. The final conversion of 95% was achieved in 250 minutes. The inhibition period was 25 minutes.
Příklad 9Example 9
Postupuje sa ako v příklade 1 s tým rozdielom, že sa ako inhibitor použil 2,2,6,6-tetra-4 -3 mety1-4-oktanoyloxypiperidín-l-oxyl 1x10 mol.dm (0,00119 g,. Rýchlosť polymerizácie v intervale stacionárnej rýchlosti je 0,01 % konverzie s 3. Finálna konverzia 97 % sa dosiahla za 220 minút. Inhibičná perióda 33 minút.The procedure was as in Example 1 except that 2,2,6,6-tetra-4-methyl-4-octanoyloxypiperidine-1-oxyl 1x10 mol.dm (0.00119 g, was used as inhibitor). at a stationary rate interval is 0.01% conversion with 3. Final conversion of 97% was achieved in 220 minutes Inhibition period 33 minutes.
Příklad 10Example 10
Postupuje sa ako v příklade 1 s tým rozdielom, že sa použily: ako iniciátor 2,2-azo-2-3 izobutyronitril 1x10 mol.dm (0,06568 g), ako inhibitor 4-stearoyloxy-2,2,6,6-tetrametyl-. piperidín-1-oxyl 5xl0-4 mol.dm-3 (0,00865 g) . Rýchlosť polymerizácie pri 20 % konverzii bola 0,017 4 konverzie s 3. Finálna konverzia 95 4 sa dosiahla za 120 minút. Inhibičná perióda bola kratšia ako 10 minút. Velkost častíc: 52 nm.The procedure was as in Example 1 except that the initiator was 2,2-azo-2-3 isobutyronitrile 1x10 mol.dm (0.06568 g), as the 4-stearoyloxy-2,2,6,6 inhibitor tetramethyl-. piperidine-1-oxyl 5x10 -4 mol.dm -3 (0.00865 g). The polymerization rate at 20% conversion was 0.017 4 conversions with 3 . The final conversion of 95% was achieved in 120 minutes. The inhibition period was less than 10 minutes. Particle size: 52 nm.
Příklad 11Example 11
Postupuje sa ako v přiklade 1 s tým rozdielom, že sa ako monomér použije 40 ml butylmetakrylátu. Rýchlosť polymerizácie v intervale stacionárnej rýchlosti je 0,010 4 konverzie s 1. Konverzia 70 4 sa dosiahla za 150 minút. Inhibičná perióda je 25 minút. Velkost častíc: 56 nm.The procedure is as in Example 1 except that 40 ml of butyl methacrylate is used as monomer. The polymerization rate at the stationary rate interval is 0.010 4 conversions with 1 . Conversion of 70% was achieved in 150 minutes. The inhibition period is 25 minutes. Particle size: 56 nm.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS865266A CS258231B1 (en) | 1986-07-11 | 1986-07-11 | Method of polymers or copolymers preparation from stabilized vinyl monomers |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS865266A CS258231B1 (en) | 1986-07-11 | 1986-07-11 | Method of polymers or copolymers preparation from stabilized vinyl monomers |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CS526686A1 CS526686A1 (en) | 1987-11-12 |
| CS258231B1 true CS258231B1 (en) | 1988-07-15 |
Family
ID=5397227
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CS865266A CS258231B1 (en) | 1986-07-11 | 1986-07-11 | Method of polymers or copolymers preparation from stabilized vinyl monomers |
Country Status (1)
| Country | Link |
|---|---|
| CS (1) | CS258231B1 (en) |
-
1986
- 1986-07-11 CS CS865266A patent/CS258231B1/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| CS526686A1 (en) | 1987-11-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1322674B1 (en) | Control agents for living-type free radical polymerization, methods of polymerizing, emulsions and polymers with same | |
| EP0103698B1 (en) | Process for the production of homo- and co-polymers of quaternary ammonium monomers | |
| US3336270A (en) | Preparation of acrylamide-type water-soluble polymers | |
| US3832317A (en) | Process for reducing acrylic ester monomer residues in acrylate latices | |
| AU5881501A (en) | Process for producing vinylpyrrolidone polymer | |
| KR100345911B1 (en) | Method of Making Acrylic Polymers | |
| McGrath | Chain reaction polymerization | |
| EP0000419B1 (en) | Process for preparing copolymers, and products fully or partly made of these copolymers. | |
| Zhang et al. | Deactivation effect caused by catalyst-cocatalyst pre-contact in propylene polymerization with MgCl2-supported ziegler-natta catalyst | |
| US3222328A (en) | Process for polymerizing vinyl monomers with a catalyst of peracetic acid and an alkyl mercaptan | |
| US6667376B2 (en) | Control agents for living-type free radical polymerization and methods of polymerizing | |
| KR20010012378A (en) | Polymerisation reactions under miniemulsion conditions | |
| US3249595A (en) | Aqueous emulsion polymerization process employing water-soluble peroxides | |
| US3574177A (en) | Production of acrylonitrile polymers | |
| US3716524A (en) | T-butyl alcohol/water cosolvent emulsion copolymerization of a monomeric system comprising methyl methacrylate and bicyclic methacrylate | |
| CS258231B1 (en) | Method of polymers or copolymers preparation from stabilized vinyl monomers | |
| GB944266A (en) | Process for the production of acrylonitrile copolymers | |
| US6100355A (en) | Process for acrylic suspension polymerization with partially hydrosoluble comonomers | |
| GB1497602A (en) | Process for producing an impact resistant thermoplastic graft copolymer | |
| KR100215515B1 (en) | Method for producing polymer powder by suspension polymerization | |
| JP3869898B2 (en) | Method for producing acrylamide polymer dispersion | |
| Elgood et al. | The emulsion polymerisation of vinyl acetate by redox initiation | |
| US3651035A (en) | Copolymers of alkyl styrenes and nvinyl heterocyclic monomers and inverse suspension polymerization using the same | |
| Bartoň et al. | Partitioned polymerization, 1. Transfer of initiator and/or monomer | |
| Seifert et al. | A Study of Simple RAFT Transfer Agents for the Polymerization of (Meth‐) acrylates and Acrylamides |