CS266148B1

CS266148B1 - Process for the Preparation of Polymer Ethyl Acrylate-Methyl Methacrylate-Acrylonitrile Latex

Info

Publication number: CS266148B1
Application number: CS878418A
Authority: CS
Inventors: Ignac Rndr Csc Capek; Jaroslav Clen Korespond Barton
Original assignee: Capek Ignac; Jaroslav Clen Korespond Barton
Priority date: 1987-11-23
Filing date: 1987-11-23
Publication date: 1989-11-14
Also published as: CS841887A1

Abstract

Očelom spĎsobu pripravy terpolymérovéiio etylakrylát-metylmetakrylát-akrylonitrilového latexu je zlepšenie regulácie rýchlosti reakcie a stability polymérového latexu. Uvedený účel sa dosiahne tak, že sa pri priprave terpolymérového etylakrylát- -metylmetakrylát-akrylonitrilového latexu použije 0,22 až 0,67 hmotnostných dielov polyoxyetylén monopalmitán sorbitolu a 1,3 až 1,8 hmotnostných dielov laurylsulfátu sodného vztiahnutého na 100 hmotnostných dielov vody. Spósob pripravy terpolymérového etylakrylát-metylmetakrylát-akrylonitrilového latexu má použitie v ohémii latexových nátěrových a impregnačných prípravkov.The purpose of the method for preparing a terpolymer ethyl acrylate-methyl methacrylate-acrylonitrile latex is to improve the control of the reaction rate and the stability of the polymer latex. The said purpose is achieved by using 0.22 to 0.67 parts by weight of polyoxyethylene monopalmitate sorbitol and 1.3 to 1.8 parts by weight of sodium lauryl sulfate based on 100 parts by weight of water in the preparation of the terpolymer ethyl acrylate-methyl methacrylate-acrylonitrile latex. The method for preparing the terpolymer ethyl acrylate-methyl methacrylate-acrylonitrile latex has application in the chemistry of latex coating and impregnation preparations.

Description

2 CS 266 148 B12 CS 266 148 B1

Vynález sa týká spósobu přípravy terpolymerového etylakrylát-metylmetakrylát-akrylo--nitrolového latexu emulznou kopolymerizáciou etylakrylátu, metylmetakrylátu a akrylonitrilupůsobením volnoradikálového iniciátora a za přídavku 0,22 až 0,67 hmotnostného dielu umulgá-tora polyoxyetylénmonopalmitansorbitolu, vztiahnuté na 100 hmotnostnýoh dielov vody.BACKGROUND OF THE INVENTION The present invention relates to a process for the preparation of ethyl acrylate-methyl methacrylate-acrylonitrile latex terpolymer by emulsion copolymerization of ethyl acrylate, methyl methacrylate and acrylonitrile by treatment with a free radical initiator and 0.22 to 0.67 parts by weight of polyoxyethylene monopalmitanorbitol umulgator based on 100 parts by weight of water.

Emulzná multikomponentná kopolymerizácia sa využívala k príprave polymérových disperzií,ktoré mali široké priemyselné použitie. Často sa používali polymérové disperzie na bázeakrylátov a metakrylátov. Nevýhodou emulzných kopolymerizácií etylakrylátu a akrylonitriluje, že takto vznikali polymérové disperzie s nízkou stabilitou i pri vyšších koncentráciachaniónového emulgátora (sodná sol kyseliny dodecylfenoxybenzendisulfónovej) I. Čapek, J.The emulsion multicomponent copolymerization has been used to prepare polymer dispersions that have been widely used in the industry. Polymer dispersions of base-acrylates and methacrylates have often been used. The disadvantage of emulsion copolymers of ethyl acrylate and acrylonitrile is that polymer dispersions with low stability were obtained even at higher concentration of the ionic emulsifier (sodium salt of dodecylphenoxybenzene disulfonic acid) I. Čapek, J.

Bartoň, E. Orolinová: Acta Polymerica 36, 187 (1985); I. Čapek, J. Bartoň; Chem. Papers40, 45 (1986) . Emulznou kopolymerizáciou akrylonitrilu s vinylovými monomérmi vznikalivelké polymérové častíce koalescenciou menších častíc s nížšou stabilitou C. Hagiopol, B. Dimonie,M. Georgescu, I. Deaconescu, T. Deleanu, M. Marinescu: Acta Polymerica 32, 390(1981) . I zvýšenie koncentrácie emulgačnej zmesi (neiónový a aniónový emulgátor neviedolk očakávanému zvýšeniu stability latexu ale naopak pozorovalo sa zníženie stability latexua tiež rýchlosti kopolymerizácie I. Čapek, J. Bartoň, V. Svoboda, V. Novotný, L. Q. Taun:Makromol. chem. 188, 1 723) .Barton, E. Orolin: Acta Polymerica 36, 187 (1985); I. Capek, J. Barton; Chem. Papers, 40, 45 (1986). Emulsion copolymerization of acrylonitrile with vinyl monomers resulting in large polymer particles by coalescence of smaller particles with lower stability C. Hagiopol, B. Dimonie, M. Georgescu, I. Deaconescu, T. Deleanu, M. Marinescu: Acta Polymerica 32, 390 (1981). I increase the concentration of the emulsifier mixture (nonionic and anionic emulsifier not expected to increase latex stability but, on the contrary, reduce latex stability and also copolymerization rate I. Capek, J. Barton, V. Svoboda, V. Novotny, LQ Taun: Macromol. Chem. 188, 1 723).

Uvedené nevýhody v podstatnej miere odstraňuje shora uvedený spósob přípravy terpolyméro-vého etylakrylát-metylmetakrylát-akrylonitrilového latexu, ktorého podstata spočívá v tom,že sa naviac přidá 1,3 až 1,8 hmotnostnýoh dielov emulgátora laurylsulfátu sodného vztiahnuténa 100 hmotnostnýoh dielov vody. Výhodou navrhovaného spósobu přípravy terpolymérového etylakrylát-metylmetakrylát--akrylonitrilového latexu oproti doterajším spósobom, je vyššia stabilita emulzie a rýchlosťkopolymerizácie. Ďalšou výhodou je účinná regulácia priebehua vlastntností polymerizačnéhosystému zvýšenou intereakciou zložiek emulz ného systému. PřikladlThe above drawbacks are substantially obviated by the aforementioned process for preparing a terpolymer ethylacrylate-methyl methacrylate-acrylonitrile latex which further comprises adding 1.3 to 1.8 parts by weight of a sodium lauryl sulfate emulsifier based on 100 parts by weight of water. The advantage of the proposed method of preparing the terpolymer ethyl acrylate-methyl methacrylate acrylonitrile latex over the prior art is to improve the stability of the emulsion and the rate of copolymerization. Another advantage is the effective control of the course of the polymerization system properties by the increased interaction of the components of the emulsion system. Přikladl

Do trojhrdlej reakčnej baňky objemu 1 000 ml opatrenej miešadlom, spatným chladičom,prívodom pre dusík a zariadením pre kontinuálny odběr vzorky latexu sa vdavkuje 450 g destilo-vanej vody, 245 g etylakrylátu, 31,6 g metylmetakrylátu, 30,4 g akrylonitrilu, 1,8 hmotnostnýohdielov laurylsulfátu sodného (anónový emulgátor) a 0,22 hmotnostnýoh dielov polyoxyetylénmonopalminát sorbitolu (Tween - neiónový emulgátor 40 - neiónový emulgátor) vztiahnuté na100 hmotnostnýoh dielov vody. Po 25 minutách miešaní pri 400 otáčkách za minútu a teplote60 C sa přidá 0,6 g persulfátu amonného (iniciátor). V priebehu polymerizácie sa odoberiekaždých 10 minút 1 ml latexu (na izoláciu polyméru a stanovenie stupňa konverzie). Polymérsa izoluje z emulzie tak, že sa emulzia skoaguluje v 25 ml metanolu okyselenom kyselinouoctovou na pH 2. Získaný polymér sa premýva 50 ml vody a 50 ml 96 hmot. % etanolu a necháse vysušit pri teplote 20 °C po dobu troch dni a potom sa dosuší pri tlaku 5 kPa pri teplote60 °C po dobu 8 hodin. Z týchto získaných údajov sa zostrojí konverzná křivka a vypočítajúrýchlosti polymerizácie v stacionárnych a nestacionárnych intervaloch polymerizácie D.Mikulášová: Makromolekulová chémia; ES Slovenská vysoká škola technická, Bratislava, str. 108 (1967); I. Čapek, J. Bartoň, E. Orolinová: Chemické Zvěsti 38, 803 (1984) . Po dopoly-merizovani monoméru na 100% konverziu s alatex filtruje a skoagulovaný polymer izoluje. Získaný koagulát sa premyje 100 ml vody a 50 ml 96 hmot. % etanolu, suší po dobu 6 dní priteplote 20 °C a potom sa dosuší pri tlaku 5 kPa pri teplote 60 °C po dobu 12 hodin. Rýchlosťpolymerizácie je 7% konverzie za minútu a získá sa 2,0 g skoagulovaného polyméru. Příklad 2450 g of distilled water, 245 g of ethyl acrylate, 31.6 g of methyl methacrylate, 30.4 g of acrylonitrile, 1% of ethyl acetate, 31.6 g of methyl methacrylate, 30.4 g of acrylonitrile are introduced into a 3 ml 1000 ml reaction flask equipped with a stirrer, a low-temperature condenser, a nitrogen inlet and a continuous latex sampling device. , 8 parts by weight of sodium lauryl sulfate (anionic emulsifier) and 0.22 parts by weight of polyoxyethylene monopalminate sorbitol (Tween - nonionic emulsifier 40 - nonionic emulsifier) based on 100 parts by weight of water. After 25 minutes of stirring at 400 rpm and 60 ° C, 0.6 g of ammonium persulfate (initiator) is added. During the polymerization, 1 ml of latex is removed every 10 minutes (for polymer isolation and conversion rate determination). The polymer is isolated from the emulsion by coagulating the emulsion in 25 ml of methanol acidified with acetic acid to pH 2. The polymer obtained is washed with 50 ml of water and 50 ml of 96 wt. % ethanol and allowed to dry at 20 ° C for three days and then dried at 5 kPa at 60 ° C for 8 hours. From these data, the conversion curve and the polymerization rate at stationary and non-stationary polymerization intervals are constructed. D.Mikulášová: Macromolecular Chemistry; ES Slovak Technical University, Bratislava, page 108 (1967); I. Capek, J. Barton, E. Orolinova: Chemicke Zvěsti 38, 803 (1984). After the polymerization of the monomer for 100% conversion with alatex, the filter is filtered and the coagulated polymer isolated. The coagulum obtained is washed with 100 ml of water and 50 ml of 96 wt. % ethanol, dried at 20 ° C for 6 days and then dried at 5 kPa at 60 ° C for 12 hours. The polymerization rate is 7% conversion per minute to obtain 2.0 g of the coagulated polymer. Example 2

Postupuje sa ako v příklade 1 s tým rozdielom, že sa použije 1,67 hmotnostných dielov laurylsulfátu sodného a 0,33 hmotnostných dielov polyoxyetylén monopalmitán sorbitolu vztia- hnuté na 100 hmotnostných dielov vody. Rýchlosť polymerizácie je 9,06% konverzie za minútu a množstvo koagulátu je 1,5 g.The procedure is as in Example 1 except that 1.67 parts by weight of sodium lauryl sulfate and 0.33 parts by weight of polyoxyethylene monopalmitate sorbitol, based on 100 parts by weight of water, are used. The polymerization rate is 9.06% conversion per minute and the amount of coagulum is 1.5 g.

Claims

EXAMPLE 3 The procedure is as in Example 1 except that 1.3 parts by weight of sodium lauryl sulfate and 0.67 parts by weight of polyoxyethylene monopalmate sorbitol based on 100 parts by weight of water are used as emulsifiers. The polymerization rate was 14.3% conversion from the aminate and no coagulum was obtained. To compare the effect of sodium lauryl sulphate emulsifier in combination with polyoxyethylene monopalmate sorbitol with some of the hitherto used emulsifier, ie octadecan-1-enyl sulphonic acid sodium salt, the following example is given by X. Capek, J. Barton, V. Svoboda, V. Novotny, LQ Tuan: Makromol. CHem. 188, 1723 (1987): Example 4 The procedure is as in Example 1 except that 1.5 parts by weight of octadecan-1-enyl sulfonic acid sodium salt and 0.3 parts by weight of polyoxyethylene mono-palmitate sorbitol and 240 g are used. ethyl acrylate and 60 g methyl methacrylate. The polymerization rate is 4% per minute and the resulting coagulum is 3g. The invention can be used in polymer dispersion chemistry! for formulated latex formulations. OBJECT OF THE INVENTION A process for the preparation of terpolymer ethyl acrylate-methyl methacrylate-acrylonitrile by latex emulsion copolymerization of ethyl acrylate, methyl methacrylate and acrylonitrile by the action of a free radical initiator and with the addition of 0.22 to 0.67 parts by weight of polyoxyethylene monopalmate sorbitol based on 100 parts by weight of water. and adding 1.3 to 1.8 parts by weight of a sodium lauryl sulfate emulsifier based on 100 parts by weight of water.