DK147160B - PROCEDURE FOR PREPARING VINYL CHLORIDE POLYMERS - Google Patents
PROCEDURE FOR PREPARING VINYL CHLORIDE POLYMERS Download PDFInfo
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- DK147160B DK147160B DK403273A DK403273A DK147160B DK 147160 B DK147160 B DK 147160B DK 403273 A DK403273 A DK 403273A DK 403273 A DK403273 A DK 403273A DK 147160 B DK147160 B DK 147160B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F14/02—Monomers containing chlorine
- C08F14/04—Monomers containing two carbon atoms
- C08F14/06—Vinyl chloride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F259/00—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00
- C08F259/02—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00 on to polymers containing chlorine
- C08F259/04—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00 on to polymers containing chlorine on to polymers of vinyl chloride
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Description
147160147160
Den foreliggende opfindelse angår en fremgangsmåde til fremstilling af vinylchloridpolymere ved polymerisation af vinylchlorid i en vandig dispersion af en på forhånd fremstillet vinylchloridpolymer.The present invention relates to a process for preparing vinyl chloride polymers by polymerizing vinyl chloride in an aqueous dispersion of a pre-made vinyl chloride polymer.
Polymerisation af vinylchlorid i vandig dispersion er en velkendt operation. Når dispersionen af den monomere og det dannede polymere materiale foreligger i form af store dråber eller partikler, der er overtrukket med beskyttelsesmiddel, idet polymerisationsreaktionen i reglen initieres af en polymeri-sationsinitiator, der er opløselig i olie, og dispergeringen af disse dråber eller partikler i vand fremkaldes ved mekanisk omrøring, kaldes polymerisationsprocessen for en suspensionspolymerisation, og man opnår polymerpartikler med en middeldiameter på i reglen 10-500 pm, fortrinsvis 50-300 pm.Polymerization of vinyl chloride in aqueous dispersion is a well-known operation. When the dispersion of the monomer and the polymeric material formed is in the form of large droplets or particles coated with a protective agent, the polymerization reaction is usually initiated by a polymerisation soluble in oil and the dispersion of these droplets or particles in the water is induced by mechanical stirring, the polymerization process is called a suspension polymerization, and polymer particles having a mean diameter of usually 10-500 µm, preferably 50-300 µm, are obtained.
Når dispersionen af monomer og det dannede polymere materiale foreligger i form af fine dråber eller partikler, der i reglen anvendes i en sådan mængde, at den vandige dispersion er stabil i en vis tid efter, at omrøringen er indstillet, og polymerisationsreaktionen initieres af en vandopløselig polymerisationsinitiator, benævnes polymerisationsprocessen en emulsionspolymerisation, og den fører til meget små polymerpartikler, hvis diameter i reglen er 0,02-2 jum.When the dispersion of monomer and the polymeric material formed is in the form of fine droplets or particles, which are usually used in such an amount that the aqueous dispersion is stable for a certain time after the stirring is stopped and the polymerization reaction is initiated by a water-soluble polymerization initiator, the polymerization process is referred to as an emulsion polymerization and it results in very small polymer particles whose diameter is generally 0.02-2 microns.
Fremgangsmåden ifølge opfindelsen består i under en emulsionspolymerisation af vinylchlorid at afsætte de dannede partikler med en partikelstørrelse på ca. 0,02 - 2 ^um på partikler af vinylchloridpolymere, der på forhånd er fremstillet ved masseeller suspensionspolymerisation. Metoden består af to trin, der kan skematiseres således: 1) Man fremstiller vinylchloridpolymere ved masse- eller suspensionspolymerisation i vandig dispersion og opnår partikler A.The process of the invention consists in depositing, during an emulsion polymerization of vinyl chloride, the particles formed with a particle size of approx. 0.02 to 2 µm on particles of vinyl chloride polymers prepared in advance by mass or suspension polymerization. The method consists of two steps which can be schematized as follows: 1) Vinyl chloride polymers are prepared by mass or suspension polymerization in aqueous dispersion to obtain particles A.
2) I den foregående dispersion foretager man en polymerisation i nærværelse af de nødvendige additiver til emulsionspolymeri- \ 2 147160 sationen, nemlig en emulgator og en vandopløselig polymerisa-tionsinitiator. Man konstaterer herved, at de dannede fine partikler indhyller partiklerne A.2) In the preceding dispersion, a polymerization is carried out in the presence of the necessary additives for the emulsion polymerization, namely an emulsifier and a water-soluble polymerization initiator. Hereby it is found that the fine particles formed cover the particles A.
Under det første trin er det afgørende, at polymer A er fremstillet ved masse- eller suspensionspolymerisation, og at den befinder sig i dispersion i mediet forud for det andet polymerisationstrin i nærværelse af additiver til emulsionspolymerisation. Fremgangsmåden ifølge opfindelsen omfatter følgende tre tilfælde: a) Polymer A kan være et tidligere fremstillet slutprodukt, som man har redispergeret; b) Polymer A kan være fremstillet i en umiddelbart foregående suspensionspolymerisation i overskud af monomer før tilsætningen af additiver til emulsionspolymerisationen og tilsætning af yderligere monomer, eller c) Polymer A kan være fremstillet umiddelbart forinden ved suspensionspolymerisation i overskud af monomer før tilsætningen af additiver til emulsionspolymerisationen, hvor denne tilsætning udgør starten på andet trin. Denne sidste metode er den mest interessante variant af fremgangsmåden ifølge opfindelsen, eftersom denne variant muliggør en opnåelse af den største porøsitet af de færdige partikler. Det viser sig nemlig, at overskydende monomer, der er mere eller mindre indesluttet i partiklerne A, som er dannet under det første trin, i det andet emulsionspolymerisationstrin vil migrere og polymeriseres som fine partikler på overfladen af partiklerne A.During the first step, it is essential that polymer A is prepared by mass or suspension polymerization and that it is in dispersion in the medium prior to the second polymerization step in the presence of additives for emulsion polymerization. The process of the invention comprises the following three cases: a) Polymer A may be a previously prepared final product which has been redispersed; b) Polymer A may be prepared in an immediately preceding suspension polymerization in excess of monomer prior to the addition of additives to the emulsion polymerization and addition of additional monomer, or c) Polymer A may be prepared immediately by suspension polymerization in excess of monomer before the addition of additives to the emulsion polymer. , where this addition marks the start of the second step. This latter method is the most interesting variant of the process according to the invention, since this variant enables the greatest porosity of the finished particles to be obtained. Namely, it is found that excess monomer more or less enclosed in particles A formed during the first step in the second emulsion polymerization step will migrate and polymerize as fine particles on the surface of particles A.
Formålet med den foreliggende opfindelse er, idet man går ud fra partikler, der har en partikelstørrelse på 10-500 yum, at ændre strukturen af disse partikler for derved at forøge porøsiteten og eksempelvis modificere massefylden og smeltningstiden. Derimod er formålet ikke at forøge partikelstørrelsen, og der sker ikke nogen væsentlig ændring af de oprindelige partikler i henseende til deres dimensioner.The object of the present invention is, based on particles having a particle size of 10-500 µm, to change the structure of these particles, thereby increasing the porosity and, for example, modifying the density and melting time. By contrast, the purpose is not to increase the particle size, and there is no significant change in the original particles in terms of their dimensions.
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Fra svensk fremlæggelsessksrift nr. 330 057 kendes en klassisk fremgangsmåde til polymerisation af vinylchlorid i vandig emulsion i nærværelse af en podningslatex (kimlatex), som bringes til at vokse i større eller mindre udstrækning.From Swedish Patent Specification No. 330,057 a classic method for polymerizing vinyl chloride in aqueous emulsion is known in the presence of a graft latex (germ latex) which is grown to a greater or lesser extent.
Ifølge ovennævnte svenske fremlæggelsesskrift startes emulsionspolymerisationen med en podningslatex, hvis partikel-størrelse ifølge eksemplerne er 0,3-0,4 pm. En sådan latex kan under hensyn til den nævnte partikelstørrelse kun være fremstillet ved emulsionspolymerisation. Der er således tale om en emulsionspolymerisation efterfulgt af en anden .emulsionspolymerisation og ikke en suspensions- eller massepolymerisation efterfulgt af en emulsionspolymerisation som ved fremgangsmåden ifølge opfindelsen.According to the above Swedish presentation specification, the emulsion polymerization is started with a graft latex whose particle size according to the examples is 0.3-0.4 µm. Such a latex, having regard to the particle size mentioned, can only be made by emulsion polymerization. Thus, it is an emulsion polymerization followed by another emulsion polymerization and not a suspension or mass polymerization followed by an emulsion polymerization as in the process of the invention.
Fransk patentskrift nr. 1 485 547 beskriver en fremgangsmåde til kontinuerlig suspensionspolymerisation, hvorved den monomere sammen med et på forhånd fremstillet podet produkt, der omslutter en katalysator, anbringes i en vandig reaktionszone.French Patent Specification No. 1,485,547 discloses a process for continuous suspension polymerization whereby the monomer, together with a pre-prepared grafted product enclosing a catalyst, is placed in an aqueous reaction zone.
Der er således ikke tale om en suspensions- eller massepolymerisation efterfulgt af en emulsionspolymerisation som ved fremgangsmåden ifølge opfindelsen, men derimod om en suspensionspolymerisation, hvilket understreges af, at katalysatoren er en forbindelse, der er uopløselig i vand, men opløselig i monomeren.Thus, it is not a suspension or mass polymerization followed by an emulsion polymerization as in the process of the invention, but a suspension polymerization, which is emphasized that the catalyst is a water-insoluble compound but soluble in the monomer.
Tysk offentliggørelsesskrift nr. 2 023 970 angår en fremgangsmåde ved hvilken man forøger størrelsen af findelte partikler på en sådan måde, at man opnår større kompakte korn ved podning. Ved en sådan podningsteknik går man ud fra en lille partikel, hvis størrelse man derefter forøger under opretholdelse af en homogen morfologi. Man går ud fra en latex, hvis partikelstørrelse er maksimalt 4 μ (fortrinsvis 0,1-2 μ), og som indeholder et overskud af en polymerisa-tionsinitiator. Denne initiator er valgt blandt forbindelser, der ikke er opløselige i vand, men kun i monomeren. Ved polymerisationen opnår man et pulver og ikke, som ved fremgangsmåden ifølge opfindelsen, en vandig dispersion.German Publication No. 2,023,970 relates to a method of increasing the size of finely divided particles in such a way that larger compact grains are obtained by grafting. Such an inoculation technique assumes a small particle whose size is then increased while maintaining a homogeneous morphology. A latex whose particle size is a maximum of 4 µm (preferably 0.1-2 µm) and which contains an excess of a polymerization initiator is assumed. This initiator is selected from compounds which are not soluble in water but only in the monomer. In the polymerization, a powder is obtained and not, as in the process according to the invention, an aqueous dispersion.
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Den foreliggende opfindelse angår som nævnt en fremgangsmåde til fremstilling af vinylchloridpolymere ved polymerisation af vinylchlorid i en vandig dispersion af en forud fremstillet vinylchloridpolymer, hvilken fremgangsmåde er ejendommelig ved, at man til den vandige dispersion af en vinylchlorid-massepolymer eller vinylchloridsuspensionspolymer med en partikeldiameter på 10-500 y.um, eventuelt indeholdende vinylchloridmonomer, sætter en vandopløselig fri-radikal-dannende initiator og de øvrige nødvendige additiver til emulsionspolymerisationen, hvorefter man foretager polymerisationen af den vinylchlorid-monomer, der eventuelt er til stede i reaktoren før indføringen af emulsionspolymerisations-additiverne, og/eller den vinylchlorid-monomer, der er tilsat efter indføringen af additiverne, som en emulsionspolymerisation.The present invention relates, as mentioned, to a process for preparing vinyl chloride polymers by polymerizing vinyl chloride in an aqueous dispersion of a pre-prepared vinyl chloride polymer, characterized in that the aqueous dispersion of a vinyl chloride pulp polymer or vinyl chloride suspension polymer has a -500 µm, optionally containing vinyl chloride monomer, sets a water-soluble free radical-forming initiator and the other necessary additives to the emulsion polymerization, after which the polymerization of the vinyl chloride monomer optionally present in the reactor prior to introduction of the emulsion polymerization is carried out. , and / or the vinyl chloride monomer added after the introduction of the additives, as an emulsion polymerization.
En udførelsesform for fremgangsmåden ifølge opfindelsen består i, at man først fremstiller en vinylchlorid-massepolymer eller -suspensionspolymer under en forudgående masse- eller suspensionspolymerisation på kendt måde, hvorpå man bringer vinyl-chlorid-polymeren i en vandig dispersion; tilsætter emulgeringsmiddel, initiatorsystem for emulsionspolymerisationen og monomer, og foretager polymerisationen.An embodiment of the process of the invention consists in first preparing a vinyl chloride pulp polymer or suspension polymer under a prior pulp or suspension polymerization in a known manner, whereby the vinyl chloride polymer is introduced into an aqueous dispersion; add emulsifier, emulsion polymerization initiator system and monomer, and conduct the polymerization.
Når polymerisationen foretages i nærværelse af en vinylchloridsuspensionspolymer fremstillet under en forudgående polymerisationsproces, kan denne polymer enten frafiltreres og tørres eller simpelthen frafiltreres, før den overføres i en vandig dispersion. Ud fra et økonomisk synspunkt er det en fordel at foretage polymerisationen i nærværelse af en vinylchloridsuspensionspolymer dispergeret i den vandige fase, hvori den er fremstillet.When the polymerization is carried out in the presence of a vinyl chloride suspension polymer prepared during a prior polymerization process, this polymer can either be filtered and dried or simply filtered off before being transferred into an aqueous dispersion. From an economic point of view, it is advantageous to conduct the polymerization in the presence of a vinyl chloride suspension polymer dispersed in the aqueous phase in which it is made.
Det er en fordel at gå frem efter den første udførelsesform i tilfælde, hvor det er nyttigt at kende vægtforholdet mellem monomeren, der deltager i polymerisationen efter indføringen af emulsionspolymerisations-additiver, og den tilstedeværende mængde masse- eller suspensionspolymer på det tidspunkt, hvor additiverne tilsættes, meget nøje.It is an advantage to proceed with the first embodiment in cases where it is useful to know the weight ratio of the monomer participating in the polymerization after the introduction of emulsion polymerization additives and the amount of mass or suspension polymer present at the time the additives are added. , very carefully.
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Ved en anden særlig fordelagtig udførelsesform kan den totale mængde polymer opnået ved afslutningen af den omhandlede polymerisationsproces opnås i løhet af en eneste polymerisationsoperation, idet suspensionspolymerisationen, der udgør den første fase i nro-cessen, og polymerisationen af den monomere efter tilsætningen af emulsionspolymerisationsadditiver udgør den anden fase.In another particularly advantageous embodiment, the total amount of polymer obtained at the end of the present polymerization process can be obtained in a single polymerization operation, the suspension polymerization constituting the first phase of the process and the polymerization of the monomer after the addition of emulsion polymerization additives. second phase.
Den vinylchlorid-monomere, der forbruges i løbet af polymerisationen, kan indføres i reaktoren på én gang. Fremgangsmåden ifølge opfindelsen består derfor i, at man polymeriserer en del af den vinylchlorid-monomere under suspensionspolymerisationsbetingelser, og derpå tilsætter de konventionelle additiver til emulsionspolymerisationssystemer, hvorefter man fortsætter polymerisationen til den ønskede omdannelsesgrad.The vinyl chloride monomer consumed during the polymerization can be introduced into the reactor at once. The process of the invention therefore consists in polymerizing a portion of the vinyl chloride monomer under suspension polymerization conditions, and then adding the conventional additives to emulsion polymerization systems, after which the polymerization is continued to the desired degree of conversion.
Ved en variant af den anden udførelsesform for fremgangsmåden ifølge opfindelsen tilsættes den vinylchlorid-monomere til reaktoren i flere trin, isser i to trin, idet det er en fordel at indføre den anden fraktion af den monomere, efter at emulsionspolymerisa-tionsadditiverne er tilsat.In a variant of the second embodiment of the process of the invention, the vinyl chloride monomer is added to the reactor in several steps, two-step ice, it being advantageous to introduce the second fraction of the monomer after the emulsion polymerization additives have been added.
Anvendelsen af vinylchlorid-masse- eller suspensions-polymer og/eller blandinger af vinylchlorid med andre copolymeriserbare monomere til udøvelse af fremgangsmåden ifølge opfindelsen gør det muligt at opnå interessante blandede produkter.The use of vinyl chloride pulp or suspension polymer and / or mixtures of vinyl chloride with other copolymerizable monomers for practicing the process of the invention makes it possible to obtain interesting mixed products.
For eksempel, kan vinylestere, såsom vinylacetat, estere af acryl-og methacrylsyre, maleinsyre- og fumarsyreestere, samt vinyliden-chlorid virke som passende comonomere til opnåelse af copolymere ved fremgangsmåden ifølge opfindelsen.For example, vinyl esters such as vinyl acetate, esters of acrylic and methacrylic acid, maleic and fumaric acid esters, as well as vinylidene chloride can act as suitable comonomers to obtain copolymers in the process of the invention.
Når der ved fremgangsmåden ifølge opfindelsen anvendes en vinyl-chlorid-suspensionspolymer, kan man anvende de sædvanlige suspensionsmidler, initiatorer og additiver.When a vinyl chloride suspension polymer is used in the process of the invention, the usual suspending agents, initiators and additives can be used.
Blandt de anvendelige suspensionsmidler kan man nævne carboxy-methylcellulose, hydroxypropylcellulose, hydroxypropylmethylcel-lulose, hydroxyethylcellulose, methylcellulose, delvis hydrolyse 6 147160 ret vinyl]?olyaeetat, gelatine og lignende stoffer samt blandinger heraf, i mængder på 0,001 -‘5 vægtprocent, fortrinsvis 0,005 - 2 vægtprocent, beregnet på den anvendte monomer i suspensionspolymerisationsfasen.Among the suspending agents useful are carboxymethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, hydroxyethylcellulose, methylcellulose, partial hydrolysis, vinyl] olyetate, gelatin and similar substances, and mixtures thereof 0.00% by weight - 2% by weight, calculated on the monomer used in the suspension polymerization phase.
Den olieopløselige polymerisationsinitiator kan vælges blandt organiske perestere og peroxider eller forbindelser af azo-bis-isobu-tyronitril-typen. Således kan man for eksempel anvende lauroyl-peroxid, benzoylperoxid, tert.-butylperpivalat, ac.etylcyclohexan-sulfonylperoxid, diisopropylperoxypercarbonat, azo-bis-isobutyro-nitril og også kombinationer af mindst to af disse initiatorer. Initiatoreme anvendes i mængder på 0,0002 - 1 vægtprocent, fortrinsvis 0,001 - 0,1 vægtprocent, beregnet på den anvendte monomer i suspensionspolymerisationsfasen.The oil-soluble polymerization initiator may be selected from organic peresters and peroxides or azo-isobutyronitrile-type compounds. Thus, for example, one can use lauroyl peroxide, benzoyl peroxide, tert.-butyl perpivalate, acetylcyclohexane sulfonyl peroxide, diisopropyl peroxypercarbonate, azo-isobutyro nitrile and also combinations of at least two of these initiators. The initiators are used in amounts of 0.0002 - 1% by weight, preferably 0.001 - 0.1% by weight, calculated on the monomer used in the suspension polymerization phase.
De sædvanligvis anvendte produkter ved suspensionspolymerisationer, f.eks. puffere, såsom natriumbicarbonat og kædeoverføringsmidler, såsom trichlorethylen, kan også anvendes.The products commonly used in suspension polymerizations, e.g. buffers such as sodium bicarbonate and chain transfer agents such as trichlorethylene may also be used.
De sædvanlige emulsionspolymerisationskomponenter anvendt ved fremgangsmåden ifølge opfindelsen er emulgeringsmidler og emulsions-polymerisationsinitiatorer.The usual emulsion polymerization components used in the process of the invention are emulsifiers and emulsion polymerization initiators.
Blandt anvendelige emulgeringsmidler kan nævnes ammonium- eller alkalimetalsalte af fedtsyrer, såsom natriumlaurat eller -myristat, alkylsulfonater, alkylarylsulfonater og alkylsulfater, i mængder på 0,005 - 10 vægtprocent, fortrinsvis 0,05 - 5 vægtprocent, beregnet på den monomere, der tager del i polymerisationen efter tilsætningen af emulgeringsmidlet. Blandt de anvendelige polymerisations-initiatorer kan nævnes kalium- og ammoniumpersulfat og redox-par, i mængder på 0,0001 - 5 vægtprocent, fortrinsvis 0,001 - 2 vægtprocent, beregnet på den monomere, der deltager i polymerisationsreaktionen efter tilsætningen af initiatoren.Useful emulsifiers include ammonium or alkali metal salts of fatty acids, such as sodium laurate or myristate, alkyl sulfonates, alkylarylsulfonates and alkyl sulfates, in amounts of 0.005 - 10% by weight, preferably 0.05-5% by weight, based on the monomer taking part in the polymer. after the addition of the emulsifier. Among the useful polymerization initiators are potassium and ammonium persulfate and redox pairs, in amounts of 0.0001 - 5% by weight, preferably 0.001 - 2% by weight, calculated on the monomer participating in the polymerization reaction after the addition of the initiator.
Initiatoreme, suspenderingsmidleme, emulgeringsmidleme, pufferne, kædeoverføringsmidleme og de andre midler, der anvendes ved emulsionspolymerisationen, er velkendte, og opfindelsen er ikke begrænset til de ovenfor nævnte midler.The initiators, suspending agents, emulsifiers, buffers, chain transfer agents and other agents used in the emulsion polymerization are well known and the invention is not limited to the above mentioned agents.
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Ved den omhandlede vinylchlorid-polymerisationsproces udgør vægten af den tilstedeværende polymer i reaktionsmediet på tilsætningstidspunktet for emulsionspolymerisationskomponenterne mellem 5 og 99 %, fortrinsvis 10 - 95 % af den samlede vægt af denne polymer og de monomere og dermed af vægten af den totale mængde polymer opnået ved afslutningen af polymerisationen. De opnåede vinylchlo-rid-polymere består af partikler af vinylchlorid-suspensionspolymer eller -massepolymer, på hvis overflade der er agglutineret granulater af vinylchlorid-polymer, der har samme dimensioner som de vinylchlorid-polymerpartikler, der sædvanlig opnås ved emulsionspolymerisation. De kan isoleres fra den vandige fase og tørres ved de fremgangsmåder, der sædvanligvis anvendes til tørring af vinyl-chlorid-suspensionspolymere. Disse produkter har et viskositetsin-dex på 50 - 200 målt efter fransk norm NF T 51 013.In the present vinyl chloride polymerization process, the weight of the polymer present in the reaction medium at the time of addition of the emulsion polymerization components is between 5 and 99%, preferably 10 - 95%, of the total weight of this polymer and the monomers and thus the weight of the total amount of polymer obtained at the end of the polymerization. The obtained vinyl chloride polymers consist of particles of vinyl chloride suspension polymer or pulp polymer on whose surface there are agglutinated vinyl chloride polymer granules having the same dimensions as the vinyl chloride polymer particles usually obtained by emulsion polymerization. They can be isolated from the aqueous phase and dried by the methods usually used to dry vinyl chloride suspension polymers. These products have a viscosity index of 50 - 200 measured according to French standard NF T 51 013.
Vinylchlorid-polymere fremstillet ved fremgangsmåden ifølge opfindelsen har forbedrede egenskaber i forhold til vinylchlorid-suspensionspolymere fremstillet på kendt måde.Vinyl chloride polymers prepared by the process of the invention have improved properties over vinyl chloride suspension polymers prepared in known manner.
Efter tørring er en vinylchlorid-suspensionspolymer i stand til at absorbere en vis mængde plastificering middel og/el-ler forskellige additiver ved simpel blanding i en hurtigblander af Henschel eller Papenmeier-typen, således at der dannes et tørt pulver, også benævnt "dry-blend", der kan anvendes direkte til fød-ning af forarbejdningsmaskiner. Denne blandeoperation ledsages af en forøgelse af produktets tilsyneladende massefylde, og det er kendt, at det er en fordel at føde forarbejdningsmaskineme med blandinger, der har en høj tilsyneladende massefylde og gode gel- . dannelsesegenskaber.After drying, a vinyl chloride suspension polymer is capable of absorbing a certain amount of plasticizer and / or various additives by simple mixing in a Henschel or Papenmeier type blender to form a dry powder, also called "drying agent". blend "which can be used directly to feed processing machines. This mixing operation is accompanied by an increase in the apparent density of the product, and it is known that it is advantageous to feed the processing machines with mixtures having a high apparent density and good gel. formation properties.
De ved fremgangsmåden ifølge opfindelsen fremstillede vinylchlorid-polymere er særligt fordelagtige, fordi de ved fremstillingen af tørre blandinger i hurtigblanderen ved en given blandingstemperatur giver blandinger med en højere tilsyneladende massefylde end blandingerne opnået ud fra en sædvanlig vinylchlorid-suspensionspolymer.The vinyl chloride polymers prepared by the process of the invention are particularly advantageous because in the preparation of dry mixtures in the quick mixer at a given mixing temperature they yield mixtures with a higher apparent density than the mixtures obtained from a conventional vinyl chloride suspension polymer.
Det har endvidere vist sig, at de fremstillede polymere udmær- 8 147160 ker sig ved særdeles korte smeltningstider, dvs. at de, når de udsættes for varmebehandling under belastning, f.eks. i en forarbejdningsmaskine, smelter efter kortere tid end sædvanlige suspensionspolymere. Denne forbedring i smeltetiden observeres også ved tørre blandinger, fremstillet ud fra disse polymere.Furthermore, it has been found that the polymers produced are characterized by very short melting times, ie. that when exposed to heat treatment under load, e.g. in a processing machine, melts after a shorter time than usual suspension polymers. This improvement in the melting time is also observed in dry mixtures prepared from these polymers.
Anvendelsen af den anden udførelsesform for fremgangsmåden ifølge opfindelsen fører til vinylehlorid-polymere, der har højere pla-stificeringsmiddel-absorptionsevne end suspensionspolymere opnået med det samme beskyttelseskolloidsystem.The use of the second embodiment of the process of the invention results in vinyl chloride polymers having higher plasticizer absorbency than suspension polymers obtained with the same protective colloid system.
Fremgangsmåden ifølge opfindelsen illustreres nærmere ved nedenstående eksempler, hvoraf eksemplerne 4, 10 og 12 er sammenlignings-eksempler .The process according to the invention is further illustrated by the following examples, examples 4, 10 and 12 being comparative examples.
De opnåede karakteristika for produkterne, der er angivet i de forskellige tabeller, bestemmes på følgende måde:The characteristics obtained for the products listed in the various tables are determined as follows:
Den tilsyneladende massefylde af formstoffer og tørre blandinger bestemmes efter normen A.F.N.O.R. I 51 042.The apparent density of resins and dry mixtures is determined according to the standard A.F.N.O.R. I 51 042.
Smeltningstideme bestemmes ved hjælp af et Brabender-apparat på tørre blandinger fremstillet i en Papenmeier-blander ved 120°c ud fra følgende bestanddele .(vægtdele): .The melting times are determined by a Brabender apparatus on dry mixtures prepared in a Papenmeier mixer at 120 ° C from the following constituents (parts by weight):.
Polyvinylchloridformstof 100Polyvinyl chloride resin 100
Calciumstearat 1,2Calcium stearate 1.2
Voks 0,6 Målingerne foretoges under følgende betingelser:Wax 0.6 Measurements were made under the following conditions:
Blandingskammer 170° CMixing chamber 170 ° C
Omdrejningshastighed for rotorer 30 o/min.Rotary speed of rotors 30 rpm.
Belastning 60,5 g.Load 60.5 g.
Formstoffemes evne til at absorbere plastificeringsmiddel vurderes ved bestemmelse af optagelsestiden for plastificeringsmiddel i en ovn.The ability of the plastics to absorb plasticizer is assessed by determining the uptake time of plasticizer in an oven.
9 147160 100 gram polyvinylchlorid-formstof “blandes med 70 g dioctylphthalat (D.O.P.), og denne blanding anbringes på en glasplade i en ovn ved 80° C.9 147160 100 grams of polyvinyl chloride resin "are mixed with 70 g of dioctyl phthalate (D.O.P.) and this mixture is placed on a glass plate in an oven at 80 ° C.
Optagelsestiden for plastificeringsmidlet defineres som det tidspunkt, fra hvilket en prøve udtaget fra ovnen ikke fugter et ark filtrerpapir under følgende betingelser: Et ark filtrerpapir, pulver, et ark filtrerpapir, en glasplade og en belastning på 5 kg i nævnte rækkefølge ovenpå en glasplade.The recording time of the plasticizer is defined as the time from which a sample taken from the furnace does not wet a sheet of filter paper under the following conditions: A sheet of filter paper, powder, a sheet of filter paper, a glass plate and a load of 5 kg in that order on top of a glass plate.
Nedenstående eksempler 1 - 3 illustrerer den første udførelsesform for opfindelsen, hvorved man foretager polymerisationen i nærværelse af et polyvinylchlorid-formstof fremstillet ved en forudgående polymerisationsoperation. Eksemplerne 4-13 illustrerer den anden udførelsesform for opfindelsen, hvor hele mængden af polymer opnås i løbet af en enkelt polymerisationsoperation.Examples 1 to 3 below illustrate the first embodiment of the invention by conducting the polymerization in the presence of a polyvinyl chloride resin prepared by a prior polymerization operation. Examples 4-13 illustrate the second embodiment of the invention wherein the entire amount of polymer is obtained in a single polymerization operation.
EKSEMPEL 1 20 kg deioniseret vand, 4,70 kg suspensions-polyvinylchlorid, der forhandles af ansøgerne under handelsnavnet "Ekavyl SK.64 , samt 22 g natriumlaurat indføres successivt i en 30 liters autoklav, der er glaseret indvendigt og forsynet med en omrører. Der etableres et vakuum i autoklaven, mens omrøreren roterer ved 160 o/min., og der indføres 2 kg vinylchlorid.EXAMPLE 1 20 kg of deionized water, 4.70 kg of suspension polyvinyl chloride marketed by the applicants under the trade name "Ekavyl SK.64," and 22 g of sodium laurate are successively introduced into a 30 liter autoclave which is glazed internally and fitted with a stirrer. a vacuum is established in the autoclave while the stirrer is rotating at 160 rpm and 2 kg of vinyl chloride is introduced.
Reaktionsmidlets temperatur hæves til 60° C, og der indføres en opløsning af 4,5 g kaliumpersulf at i 100 g vand, idet autoklaven holdes under nitrogentryk.The temperature of the reactant is raised to 60 ° C and a solution of 4.5 g of potassium persulfate is introduced into 100 g of water, keeping the autoclave under nitrogen pressure.
Efter 1 time og 45 minutters polymerisation ved denne temperatur, medens omrøringshastigheden er 160 o/min., er manometertrykket i autoklaven faldet med 3 bar. Man afkøler derpå reaktionsmediet og afgasser .residualmonomeren..After 1 hour and 45 minutes of polymerization at this temperature, while the stirring speed is 160 rpm, the pressure gauge in the autoclave has decreased by 3 bar. The reaction medium is then cooled and the residual monomer is degassed.
Produktet, der let filtreres, giver et klart filtrat. Efter tørring opnås 5,90 kg formstof.The product, which is easily filtered, gives a clear filtrate. After drying, 5.90 kg of resin is obtained.
10 14716010 147160
De væsentlige Karakteristika for det opnåede formstof er samlet i nedenstående tabel I sammenlignet med "Ekavyl SK.64".The essential characteristics of the obtained plastic material are summarized in Table I below as compared to "Ekavyl SK.64".
EKSEMPEL 2EXAMPLE 2
Man går frem som i eksempel 1, idet man dog hæver natriumlaurat-mængden til 66 gram. Efter polymerisation i 2 timer er manometertrykket i autoklaven faldet med 3 bar. Der opsamles 6,10 g tørt formstof.Proceed as in Example 1, however, raising the sodium laurate to 66 grams. After polymerization for 2 hours, the pressure gauge in the autoclave has decreased by 3 bar. 6.10 g of dry resin are collected.
De væsentlige karakteristika er angivet i tabel I.The essential characteristics are given in Table I.
EKSEMPEL 3 I den ovennævnte autoklav indføres 20 kg deioniseret vand, 4,70 kg suspensions-polyvinylchlorid forhandlet af ansøgeren under handelsnavnet "Ekavyl SK.66®' og 22 g natriumlaurat successivt. Der etableres et vakuum i autoklaven, mens omrøreren roterer ved 160 o/min., og der tilsættes 2 kg vinylchlorid. Temperaturen af reaktionsblandingen hæves til 58,5° 0, og der indføres en opløsning af 4,5 g kaliumpersulfat i 100 g vand, idet man opretholder et nitrogentryk. Efter polymerisation i 4 timer ved denne temperatur, idet omrøringshastigheden holdes ved 160 o/min., er manometertrykket i autoklaven faldet med 3 bar. Reaktionsmediet afkøles, og residu-almonomeren afgasses.EXAMPLE 3 In the above autoclave, 20 kg of deionized water, 4.70 kg of suspension polyvinyl chloride negotiated by the applicant under the trade name "Ekavyl SK.66®" and 22 g of sodium laurate are successively introduced. A vacuum is established in the autoclave while the stirrer is rotating at 160 ° C. The temperature of the reaction mixture is raised to 58.5 ° 0 and a solution of 4.5 g of potassium persulfate in 100 g of water is maintained, maintaining a nitrogen pressure. this temperature, keeping the stirring speed at 160 rpm, the pressure gauge in the autoclave has dropped by 3 bar, the reaction medium is cooled and the residual monomer is degassed.
Efter filtrering og -tørring opsamles 5,70 kg formstof.After filtration and drying, 5.70 kg of resin is collected.
De væsentlige karakteristika ved det opnåede formstof til sammenligning med "Ekavyl SK.66" er opført i nedenstående tabel I.The essential characteristics of the obtained plastic material for comparison with "Ekavyl SK.66" are listed in Table I below.
TABEL ITABLE I
Middel- Tilsynela- Tilsyneladende masse- granu- dende mas- Smelt- fylde af tør blanding lometri sefylde ningstid fremstillet vedMedium Vision - Apparent mass granular mass - Melting density of dry mix lometry filling time produced by
pm (g/cm3) (min.) 50°C 80°C 120°Cpm (g / cm 3) (min) 50 ° C 80 ° C 120 ° C
Ekavyl SK.64 155 0,58 6 0,63 0,63 0,66 1 152 0,58 4 0,68 0,71 0,73 2 149 0,57 1,5 0,67 0,68 0,75Ekavyl SK.64 155 0.58 6 0.63 0.63 0.66 1 152 0.58 4 0.68 0.71 0.73 2 149 0.57 1.5 0.67 0.68 0.75
Ekavyl SK.66 135 0,57 0,63 0,64 0,66 3 148 0,58 0,66 0,66 0,70 EKSEMPEL 4 11 .Equilibrium SK.66 135 0.57 0.63 0.64 0.66 3 148 0.58 0.66 0.66 0.70 Example 4 11.
147160 (Sammenligningseksempel for eksempel 5-9)147160 (Comparative Example for Examples 5-9)
En konventionel vinylchlorid-suspensionspolymer fremstilles som angivet nedenfor ud fra følgende ingredienser:A conventional vinyl chloride suspension polymer is prepared as set forth below from the following ingredients:
Deioniseret vand 20 kgDeionized water 20 kg
Vinylchlorid 6,75 kgVinyl chloride 6.75 kg
Polyvinylacetat med en hydrolysegrad udtrykt i molprocent på 72 f> og med en viskositet af en 4 $> vandig opløsning ved 20°C på 5 cp. 13,5 gPolyvinyl acetate with a degree of hydrolysis expressed in mole percent of 72 f> and with a viscosity of a 4 $> aqueous solution at 20 ° C of 5 cp. 13.5 g
Methylcellulose 3»4 gMethyl cellulose 3 »4 g
Acetylcyelohexansulfonylperoxid 1 gAcetylcyelohexanesulfonyl peroxide 1 g
Tert.-butylperpivalat 1,7 gTert.-butyl perpivalate 1.7 g
Kolloideme opløses først i 10 kg vand, hvorpå opløsningen af kolloider, 10 kg vand og de olieopløselige polymerisationsini-tiatorer indføres i den i eksempel 1 beskrevne autoklav. Der etableres derefter vakuum i autoklaven, mens omrøreren roterer ved 160 o/min., og de 6,75 kg vinylchlorid indføres. Temperaturen af reaktionsmediet hæves til 59,5° 0. Efter polymerisation i 8 timer og 45 minutter ved denne temperatur og den ovennævnte omrøringshastighed er manometertrykket i autoklaven faldet med 1 bar. Reaktionsmediet afkøles, og residualmonomer afgasses.The colloids are first dissolved in 10 kg of water and then the solution of colloids, 10 kg of water and the oil-soluble polymerization initiators is introduced into the autoclave described in Example 1. Vacuum is then established in the autoclave while the stirrer is rotating at 160 rpm and the 6.75 kg of vinyl chloride is introduced. The temperature of the reaction medium is raised to 59.5 ° 0. After polymerization for 8 hours and 45 minutes at this temperature and the above stirring rate, the pressure gauge in the autoclave is decreased by 1 bar. The reaction medium is cooled and residual monomer is degassed.
Det opnåede produkt filtreres, og der opsamles 5,4 kg farmstof efter tørring.The obtained product is filtered and 5.4 kg of substance is collected after drying.
De væsentlige karakteristika for produktet er angivet i nedenstående tabel III, hvor de kan sammenlignes med formstofferne opnået nedenfor i eksempel 5-8.The essential characteristics of the product are given in Table III below, where they can be compared with the resins obtained below in Examples 5-8.
EKSEMPEL 5EXAMPLE 5
En vinylchloridpolymer fremstilles som beskrevet nedenfor ud fra følgende ingredienser: 12 147160A vinyl chloride polymer is prepared as described below from the following ingredients: 12 147160
Beioniseret vand ’ 20 kgBeionized water 20 kg
Vinylchlorid 6,75 kgVinyl chloride 6.75 kg
Polyvinylacetat med en hydrolyse identiskPolyvinyl acetate with a hydrolysis identical
med eksempel 4 13,5 Swith Example 4 13.5 S
Methylcellulose 3,4 gMethyl cellulose 3.4 g
Acetylcyclohexansulfonylperoxid 1 gAcetylcyclohexanesulfonyl peroxide 1 g
Tert.-hutylperpivalat 1,2 gTert.-Hutyl Perpivalate 1.2 g
Natriumlaurat 2 gSodium laurate 2 g
Kaliumpersulfat 5,4 gPotassium persulfate 5.4 g
Kolloideme opløses først i 10 kg vand, hvorpå henholdsvis natriumlaurat og kaliumpersulfat opløses i 100 g vand.The colloids are first dissolved in 10 kg of water and then sodium laurate and potassium persulfate are dissolved in 100 g of water, respectively.
Opløsningen af kolloider, 9,8 kg vand og olieopløselige polymeri-sationsinitiatorer indføres i autoklaven beskrevet i eksempel 1.The solution of colloids, 9.8 kg of water and oil-soluble polymerization initiators is introduced into the autoclave described in Example 1.
Ber etableres derpå et vakuum i autoklaven, mens omrøreren roterer ved 160 o/min., og der tilsættes 6,75 kg vinylchlorid. Temperaturen af reaktionsmediet hæves til 59,5° C. Efter polymerisation i 7 timer ved denne temperatur og ved den ovennævnte omrøringshastighed indføres natriumlauratopløsningen og derpå kaliumper sulf atopløsningen, mens man opretholder et nitrogentryk, og polymerisationen fortsættes i yderligere 2 timer og 15 minutter. Manomertrykket i autoklaven er så faldet med 2 bar. Reaktionsmediet afkøles, Og residualmonomeren afgasses.Ber is then established in a vacuum in the autoclave while the stirrer is rotating at 160 rpm and 6.75 kg of vinyl chloride is added. The temperature of the reaction medium is raised to 59.5 ° C. After polymerization for 7 hours at this temperature and at the above stirring rate, the sodium laurate solution and then the potassium sulfate solution are introduced while maintaining a nitrogen pressure and the polymerization is continued for an additional 2 hours and 15 minutes. The pressure gauge in the autoclave is then decreased by 2 bar. The reaction medium is cooled and the residual monomer is degassed.
Produktet, der let filtreres, giver et klart filtrat. Ber opsamles 4,7 kg formstof efter tørring.The product, which is easily filtered, gives a clear filtrate. Berries collect 4.7 kg of plastic material after drying.
Be væsentlige karakteristika for formstoffet er angivet i tabel III.Essential characteristics of the resin are given in Table III.
EKSEMPEL 6-9EXAMPLES 6-9
Man går frem scm i eks. 4, idet man dog varierer mængden af natriumlaurat, polymerisationstiden t^ før indføring af natriumlaurat- og kaliumpersulfatopløsningeme i autoklaven og polymerisationstem- · peraturen tg efter indføring af opløsningerne. Porsøgsbetingelserne er angivet i nedenstående tabel II.Example 4 is presented, however, the amount of sodium laurate, the polymerization time t ^ before the introduction of the sodium laurate and potassium persulfate solutions into the autoclave, and the polymerization temperature tg after the solutions are varied. The test conditions are given in Table II below.
TABBI IITABBI II
13 147160 Mængde Trykfald ved for- Opsamlet natrium- + + søgets afslutning mængde13 147160 Quantity Pressure drop at pre- Collected sodium + + end of search quantity
Eks, laurat U1 τ2 polymer 6 4 g 7b 2h 30min. 1 Bar 4,8 kg 7 27 g 73a. 1h 45min. 1 bar 5,1 kg 8 27 g 7b 3b l5min. 2 bar 6,1 kg 9 30 g 8b 1h 45min. 1,5 bar 5,7 kgEx, laurate U1 τ2 polymer 6 4 g 7b 2h 30min. 1 bar 4.8 kg 7 27 g 73a. 1h 45min. 1 bar 5.1 kg 8 27 g 7b 3b l5min. 2 bar 6.1 kg 9 30 g 8b 1h 45min. 1.5 bar 5.7 kg
De væsentlige karakteristika for de opnåede formstoffer er angivet i tabel III.The essential characteristics of the obtained materials are given in Table III.
TABEI IIITABLE III
Middel- Optagelsestid Tilsyneladende massefylde granu- for plastifi- Smelt- (g/cm2) for tørblanding lometri ceringsmiddel ningstid fremstillet vedMean Absorption Time Apparent Density Granu- For Plastici Melt (g / cm2) for Dry Mixture Lometriation Time Prepared at
Eks. (μιη) (min.) (min.) 50°C 80°C 120°CEx. (μιη) (min) (min) 50 ° C 80 ° C 120 ° C
4 135 17 6 0,62 0,63 0,67 5 145 14 4,5 0,61 0,64 0,69 6 128 8 3 0,64 0,64 0,73 7 140 9 2,5 0,62 0,65 0,70 8 125 14 4 0,61 0,64 0,68 9 133 14 4,5 0,61 0,65 0,70 EKSEMPEL· 10 (sammenligningseksempel)4 135 17 6 0.62 0.63 0.67 5 145 14 4.5 0.61 0.64 0.69 6 128 8 3 0.64 0.64 0.73 7 140 9 2.5 0.62 0.65 0.70 8 125 14 4 0.61 0.64 0.68 9 133 14 4.5 0.61 0.65 0.70 EXAMPLE · 10 (Comparative Example)
En konventionel vinylchlorid-suspensionspolymer fremstilles som angivet nedenfor ud fra følgende ingredienser:A conventional vinyl chloride suspension polymer is prepared as set forth below from the following ingredients:
Deioniseret vand 20 kgDeionized water 20 kg
Vinylcblorid 6,75 kgVinyl chloride 6.75 kg
Hydroxypropylme thylc ellulo s e 17 gHydroxypropylme thylc ellulo s e 17 g
Aeetylcyclobexansulfonylperoxid 1,3 gEthylcyclobexanesulfonyl peroxide 1.3 g
Tert.-butylperpivalat 21, gTert.-Butyl Perpivalate 21, g
Hydroxypropylmetbylcellulosen opløses i 10 kg vand.The hydroxypropylmethyl cellulose is dissolved in 10 kg of water.
14 14716014 147160
Opløsningen af kolloider, 10 kg vand og de olieopløselige polymeri-sationsinitiatorer indføres i den i eksempel 1 beskrevne autoklav. Per etableres et vakuum, mens omrøreren roterer ved 160 o/min,, og der tilsættes 6,75 kg vinylchlorid. Efter polymerisation i 5 timer og 45 minutter ved denne temperatur og ved den ovennævnte omdr ejningshastighed er manometertrykket i autoklaven faldet med 1 bar. Reaktionsmediet afkøles, og residualmonomeren afgasses.The solution of colloids, 10 kg of water and the oil-soluble polymerization initiators is introduced into the autoclave described in Example 1. Per, a vacuum is established while the stirrer is rotating at 160 rpm, and 6.75 kg of vinyl chloride is added. After polymerization for 5 hours and 45 minutes at this temperature and at the above mentioned speed of rotation, the pressure gauge in the autoclave has decreased by 1 bar. The reaction medium is cooled and the residual monomer is degassed.
Pet opnåede produkt filtreres, og der opsamles 5,4 kg formstof efter tørring.The obtained product is filtered and 5.4 kg of plastic material is collected after drying.
De væsentlige karakteristika for formstoffet er angivet i nedenstående tabel IT til sammenligning med produktet ifølge eksempel 2 fremstillet ifølge opfindelsen.The essential characteristics of the resin are given in Table IT below for comparison with the product of Example 2 prepared according to the invention.
EKSEMPEL 11EXAMPLE 11
En vinylchloridpolymer fremstilles som angivet nedenfor ud fra følgende ingredienser:A vinyl chloride polymer is prepared as indicated below from the following ingredients:
Deioniseret vand 20 kgDeionized water 20 kg
Vinylchlorid 6,75 kgVinyl chloride 6.75 kg
Hydroxypropylmethylcellulose 17 gHydroxypropyl methyl cellulose 17 g
Acetylcyclohexansulfonylperoxid 1,3 gAcetylcyclohexanesulfonyl peroxide 1.3 g
Tert.-butylperpivalat 21, gTert.-Butyl Perpivalate 21, g
Natriumlaurat 27 gSodium laurate 27 g
Kaliumpersulfat^ 4,5 gPotassium persulfate ^ 4.5 g
Hydroxypropylmethylcellulosen opløses i 10 kg vand. Natriumlau-ratet og kaliumpersulfat opløses hver for sig i 100 g vand.The hydroxypropyl methyl cellulose is dissolved in 10 kg of water. The sodium laurate and potassium persulfate are dissolved separately in 100 g of water.
Opløsningen af kolloider, 9,8 kg vand og olieopløselige polymeri-sationsinitiatorer indføres i autoklaven beskrevet i eksempel 1.The solution of colloids, 9.8 kg of water and oil-soluble polymerization initiators is introduced into the autoclave described in Example 1.
Der etableres et vakuum i autoklaven, mens omrøreren roterer ved 160 o/min., og der indføres 6,75 kg vinylchlorid. Temperaturen i reaktionsmediet hæves til 59,5° C. Efter polymerisation i 4 timer og 15 minutter ved denne temperatur og ved den ovennævnte omdrejningshastighed tilsættes opløsningerne af natriumlaurat og derpå kaliumpersulfat, idet der opretholdes et nitrogentryk, og polymerisationen fortsættes i yderligere 1 time og 15 minutter.A vacuum is established in the autoclave while the stirrer is rotating at 160 rpm and 6.75 kg of vinyl chloride is introduced. The temperature of the reaction medium is raised to 59.5 ° C. After polymerization for 4 hours and 15 minutes at this temperature and at the above rate of rotation, the solutions of sodium laurate and then potassium persulfate are added, maintaining a nitrogen pressure and the polymerization is continued for an additional 1 hour and 15 minutes. minutes.
15 14716015 147160
Manometertrykket i autoklaven er så faldet med 0,8 bar. Reaktionsmediet afkøles, Og residualmonomeren afgasses.The pressure gauge in the autoclave has then decreased by 0.8 bar. The reaction medium is cooled and the residual monomer is degassed.
Produktet, der let filtreres, giver et klart filtrat, og efter tørring opsamles 5,4 kg formstof, hvis karakteristika er angivet i tabel IV.The product, which is easily filtered, gives a clear filtrate and, after drying, 5.4 kg of resin is collected, the characteristics of which are given in Table IV.
EKSEMPEL· 12 (sammenligningseksempel)EXAMPLE · 12 (Comparative Example)
En konventionel vinylchlorid-suspensionspolymer fremstilles som angivet nedenfor ud fra følgende ingredienser:A conventional vinyl chloride suspension polymer is prepared as set forth below from the following ingredients:
Deioniseret vand 20 kgDeionized water 20 kg
Vinylchlorid 6,75 kgVinyl chloride 6.75 kg
Polyvinylacetat med en hydrolysegrad udtrykt i molprocent på 85 ψ og med en viskositet af en 4 # vandig opløsning ved 20° C på 25 cp. 17 gPolyvinyl acetate with a degree of hydrolysis expressed in mole percent of 85 ψ and with a viscosity of a 4 # aqueous solution at 20 ° C of 25 cp. 17 g
Acetylcyclohexansulfonylperoxid 1,3 g lert.-butylperpivalat 2,1 gAcetylcyclohexanesulfonyl peroxide 1.3 g lert-butyl perpivalate 2.1 g
Opløsningen af kolloider, 10 kg vand og de olieopløselige polyme-risationsinitiatorer indføres derpå i autoklaven beskrevet i eksempel 1. Der etableres derpå et vakuum i autoklaven, mens omrø-reren roterer ved 160 o/min., og der tilsættes 6,75 kg vinylchlorid. Efter polymerisation i 6 timer ved denne temperatur og ved den ovenfor angivne omdrejningshastighed er manometertrykket i autoklaven faldet med 1 bar. Reaktionsblandingen- afkøles, og re- -sidualmonomeren af gasses.The solution of colloids, 10 kg of water and the oil-soluble polymerization initiators is then introduced into the autoclave described in Example 1. A vacuum is then established in the autoclave while the stirrer is rotating at 160 rpm and 6.75 kg of vinyl chloride is added. . After polymerization for 6 hours at this temperature and at the above speed of rotation, the pressure gauge in the autoclave has decreased by 1 bar. The reaction mixture is cooled and the residual monomer is gassed.
Det opnåede produkt filtreres, og der opsamles 5,3 kg formstof efter tørring.The product obtained is filtered and 5.3 kg of plastic material is collected after drying.
De væsentlige egenskaber er angivet i tabel V, hvor de kan sammenlignes med formstoffet ifølge eksempel 13, fremstillet ifølge opfindelsen.The essential properties are given in Table V, where they can be compared with the resin of Example 13 prepared according to the invention.
EKSEMPEL 13EXAMPLE 13
En vinylchlorid-polymer fremstilles som angivet nedenfor ud fra følgende ingredienser: 16 147160A vinyl chloride polymer is prepared as indicated below from the following ingredients: 16 147160
Deioniseret vand 20 kgDeionized water 20 kg
Vinylchlorid 6,75 kgVinyl chloride 6.75 kg
Polyvinylacetat identisk med eks. 12 17 gPolyvinyl acetate identical to Example 12 17 g
AcetyleyclohexansulfonyIperoxid 1,3 gAcetylcyclohexane sulfonyl peroxide 1.3 g
Tert.-butylperpivalat 2,1 gTert.-butyl perpivalate 2.1 g
Natriumlaurat 27 gSodium laurate 27 g
Kaliumpersulfat 4,5 gPotassium persulfate 4.5 g
Kolloidet opløses i 10 kg vand. Natriumlaurat og kaliumpersulfat opløses liver i 100 g vand.The colloid is dissolved in 10 kg of water. Sodium laurate and potassium persulfate are dissolved in 100 g of water.
Opløsningen af kolloider, 9,8 kg vand og olieopløselige polymeri-sationsinitiatorer indføres i autoklaven "beskrevet i eksempel 1,The solution of colloids, 9.8 kg of water and oil-soluble polymerization initiators is introduced into the autoclave "described in Example 1,
Der etableres et vakuum i autoklaven, mens omrøreren roterer ved 160 o/min., og der indføres 6,75 kg vinylchlorid. Temperaturen af reaktionsmediet hæves til 59,5° C. Efter polymerisation i 3,5 timer ved denne temperatur og ved den ovennævnte omdrejningshastighed indføres opløsningerne af natriumlaurat og kaliumpersulfat, idet man opretholder et nitrogentryk, og polymerisationen fortsættes i yderligere 2 timer. Manometertrykket i autoklaven er så faldet med 1 har. Reaktionsmediet afkøles, og residualmonomeren afgasses.A vacuum is established in the autoclave while the stirrer is rotating at 160 rpm and 6.75 kg of vinyl chloride is introduced. The temperature of the reaction medium is raised to 59.5 ° C. After polymerization for 3.5 hours at this temperature and at the above rate of rotation, the solutions of sodium laurate and potassium persulphate are maintained, maintaining a nitrogen pressure and the polymerization is continued for an additional 2 hours. The pressure gauge in the autoclave is then decreased by 1 ha. The reaction medium is cooled and the residual monomer is degassed.
Produktet, der let filtreres, giver et klart filtrat. Efter tørring opsamles 5,4 kg formstof, hvis egenskaber er angivet i tabel V.The product, which is easily filtered, gives a clear filtrate. After drying, 5.4 kg of resin, the properties of which are listed in Table V.
TABEL 17TABLE 17
Middel- Optagelsestid Tilsyneladende massefylde granu- for plastifi- Smelt- (g/cm3) for tør blanding lometri ceringsmiddel ningstid fremstillet vedMean Recording Time Apparent Density Granu- For Plastici Melt (g / cm3) For Dry Mixture Lometriation Time Prepared By
Eks. (pm) (min.) (min.) 50°G 80°C 120°CEx. (pm) (min) (min) 50 ° G 80 ° C 120 ° C
10 142 44 15 0,66 0,69 0,71 11 126 13 4f 0,69 0,72 0,7410 142 44 15 0.66 0.69 0.71 11 126 13 4f 0.69 0.72 0.74
TABEL VTABLE V
147160 17147160 17
Middel- Optagelsestid Tilsyneladende massefylde granu- for plastifi- Smelt- (g/ccP) for tør blanding lometri ceringsmiddel ningstid fremstillet vedMean Absorption Time Apparent Density Granu- For Plastici Melt (g / ccP) For Dry Mixture Lometriation Time Prepared By
Eks. (pm) (min.) (min.) 50°C 80°0 120°CEx. (pm) (min) (min) 50 ° C 80 ° 0 120 ° C
12 117 58 15 0,68 0,70 0,72 13 142 19 7 0,72 0,75 0,7612 117 58 15 0.68 0.70 0.72 13 142 19 7 0.72 0.75 0.76
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR7226304A FR2193034B1 (en) | 1972-07-21 | 1972-07-21 | |
FR7226304 | 1972-07-21 |
Publications (2)
Publication Number | Publication Date |
---|---|
DK147160B true DK147160B (en) | 1984-04-30 |
DK147160C DK147160C (en) | 1984-10-29 |
Family
ID=9102173
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DK403273A DK147160C (en) | 1972-07-21 | 1973-07-20 | PROCEDURE FOR PREPARING VINYL CHLORIDE POLYMERS |
Country Status (10)
Country | Link |
---|---|
JP (1) | JPS5121829B2 (en) |
BE (1) | BE801880A (en) |
DE (1) | DE2337361C3 (en) |
DK (1) | DK147160C (en) |
FR (1) | FR2193034B1 (en) |
GB (1) | GB1415050A (en) |
IE (1) | IE37918B1 (en) |
IT (1) | IT996584B (en) |
LU (1) | LU68048A1 (en) |
NL (1) | NL180111C (en) |
-
1972
- 1972-07-21 FR FR7226304A patent/FR2193034B1/fr not_active Expired
-
1973
- 1973-07-04 BE BE1005214A patent/BE801880A/en not_active IP Right Cessation
- 1973-07-17 IE IE120573A patent/IE37918B1/en unknown
- 1973-07-19 LU LU68048D patent/LU68048A1/xx unknown
- 1973-07-19 JP JP8055573A patent/JPS5121829B2/ja not_active Expired
- 1973-07-20 DK DK403273A patent/DK147160C/en not_active IP Right Cessation
- 1973-07-20 GB GB3478273A patent/GB1415050A/en not_active Expired
- 1973-07-20 IT IT6918873A patent/IT996584B/en active
- 1973-07-20 NL NL7310146A patent/NL180111C/en not_active IP Right Cessation
- 1973-07-23 DE DE19732337361 patent/DE2337361C3/en not_active Expired
Also Published As
Publication number | Publication date |
---|---|
DE2337361A1 (en) | 1974-02-14 |
DE2337361C3 (en) | 1980-12-11 |
DE2337361B2 (en) | 1980-04-17 |
FR2193034A1 (en) | 1974-02-15 |
LU68048A1 (en) | 1973-09-26 |
IE37918B1 (en) | 1977-11-09 |
IE37918L (en) | 1974-01-21 |
BE801880A (en) | 1973-11-05 |
FR2193034B1 (en) | 1974-10-25 |
JPS4985179A (en) | 1974-08-15 |
GB1415050A (en) | 1975-11-26 |
DK147160C (en) | 1984-10-29 |
NL7310146A (en) | 1974-01-23 |
AU5827873A (en) | 1975-01-23 |
IT996584B (en) | 1975-12-10 |
NL180111B (en) | 1986-08-01 |
NL180111C (en) | 1987-01-02 |
JPS5121829B2 (en) | 1976-07-05 |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUP | Patent expired |