BE577543A

BE577543A -

Info

Publication number: BE577543A
Authority: BE

Description

       

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  Procédé de polymérisation et/ou de conpolymérisation ae composés con- tenant une   insaturation   éthylénicue et polymères ainsi ootenus . 



   La présente invention concerne un procdédé   .le   polymérisation et/ou de copolymérisation ne composés contenant une insaturation éthylénique, ainsi que les polymères et/ou   copolymères     ootenus   par ce procédé, dans lequel il est fait usage ae nouveaux catalyseurs actifs et susceptiples de permettre la polymérisation et/ou la co- polymérisation aesdits composés a casses températures. 



   Le procédé,   faisant   l'objet de l'invention, consiste à polymériser et/ou à copolymériser, a une température inférieure à - 20 C, des composés de iormule générale 
 EMI1.1 
 dans laquelle R et R' représentent ae   1''hydrogène,   des radicaux   hy@rocarbonés   saturés et non saturés ou des atones et/ou groupements 

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 polaires tels que les halogènes, les groupements ester, éther, nitrile ou les radicaux   hyarocaroonés   substitués par les halogènes, au moins un des R et R' étant un groupement polaire, en présence d'un catalyseur constitué par un dérivé organique au   uore de   formule R"BX dans laquelle R" est un radical hyarocarooné   quelcon-   que et X un halogène. 



   En général, on préfère   operer   la polymérisation à une tem- pérature comprise entre -30 et - 60 C. 



   Parmi les composés susceptibles   d'être   pllumérisés ou copo- lymérisés conformément au procédé selon 1'invention, il convient   ae   mentionner, entre autres,   -Le   chlorure   ae   vinyle, le chlorure de vinyliaène, les esters vinyliques tels que l'acétate de vinyle, le méthacrylate de méthyle,   -Le   nitrile acrylique. 



   La quantité de catalyseur à retire en oeuvre est   ae   l'or- dre de 0,1 à 3% en poids de la quantité au monomère ou   aes   mono- mères a polymériser. 



   La polymérisation ou la copolymérisation peut être conduite en   niasse,   ou en présence de solvants. 



   Parmi les catalyseurs convenant pour   .l'exécution   du procédé faisant l'objet de l'invention, il convient de signaler, entre autres, les chlorures de Dore   dialkyle   tels que les chlorures de bore diéthyle, dipropyle, diisopropyle, dibutyle,   diisobutyle,   ditertiobutyle. 



   La demanderesse a observé que l'on peut éventuellement accroître l'activité des catalyseurs par adjonction d'une faible quantité d'oxygène. La proportion   d'oxygène   à introduire dans le milieu de réaction est généralement de   0,001     à   0,01% en poids du ou des monomères à polymériser. 



   Les produits obtenus conformément au procédé de l'invention se distinguent de ceux obtenus par les procédés habituels par un taux de cristallinité généralement plus élevé et par une stabilité thermique améliorée. 

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   Le procédé selon   l'invention   est   illustra  par l'exemple suivant qui ne limite en rine laportée de celle-ci car elleest susceptible de variantes qui ne sortent pasde son cadre. 



    EXEMPLE.-   
Dans un ballon de verre de 2 L à 3 tubulures équipe d'un agitateur et d'un thermomètre, on introduit successivenent, à l'abri de   l'air   et de l'humidité :   - 1500   gr de chlorure de vinyle   liquide   sec maintenu à la tempé- rature de - 40 C. 



    - 2   cm3 (1,72 gr) de chlorure de bore dioutyle. 



  - 0,112 gr d'oxygène. 



   On maintient le milieu durant quatre heures, à -40 C, sous atmosphère d'azote pur et sec, la pression totale étant égale à la pression atmosphérique, puis on filtre le   milieu   de réaction. On recueille de la sorte 49 gr de polychlorure de vi- nyle caractérisé par un poids moléculaire élevé   (Indice K   de FICKENTSCHER: 98) et un taux de   cristallinité   notablement plus élevé (20-25%) que celui des polychlorures de vinyle usuels. Le polymère obtenu peut, en outre, être utilisé à une   température   voisine de 100 C sans subir de déformation importante. 



   REVENDICATIONS. 

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  Process for the polymerization and / or polymerization of compounds containing ethylenic unsaturation and polymers thus obtained.



   The present invention relates to a process .the polymerization and / or copolymerization of compounds containing an ethylenic unsaturation, as well as the polymers and / or copolymers ootenus by this process, in which use is made of new active catalysts and capable of allowing the polymerization. and / or the co-polymerization of said compounds at break temperatures.



   The process, which is the object of the invention, consists in polymerizing and / or copolymerizing, at a temperature below - 20 ° C., compounds of the general iormule.
 EMI1.1
 in which R and R 'represent hydrogen, saturated and unsaturated hydrocarbon radicals or atoms and / or groups

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 polar such as halogens, ester, ether, nitrile or hyarocarbon radicals substituted with halogens, at least one of R and R 'being a polar group, in the presence of a catalyst consisting of an organic uorine derivative of formula R "BX wherein R" is any hyarocaroon radical and X is halogen.



   In general, it is preferred to carry out the polymerization at a temperature between -30 and -60 C.



   Among the compounds capable of being pllumérized or copolymerized in accordance with the process according to the invention, it is appropriate to mention, inter alia, vinyl chloride, vinyl chloride, vinyl esters such as vinyl acetate, methyl methacrylate, -Acrylic nitrile.



   The amount of catalyst to be removed is in the range of 0.1 to 3% by weight of the amount of monomer or monomers to be polymerized.



   The polymerization or copolymerization can be carried out in bulk, or in the presence of solvents.



   Among the catalysts suitable for carrying out the process forming the subject of the invention, it should be noted, among others, the dialkyl chlorides of Dore such as boron chlorides diethyl, dipropyl, diisopropyl, dibutyl, diisobutyl, ditertiobutyl .



   The Applicant has observed that the activity of the catalysts can optionally be increased by adding a small amount of oxygen. The proportion of oxygen to be introduced into the reaction medium is generally 0.001 to 0.01% by weight of the monomer or monomers to be polymerized.



   The products obtained according to the process of the invention are distinguished from those obtained by the usual processes by a generally higher degree of crystallinity and by an improved thermal stability.

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   The method according to the invention is illustrated by the following example, which does not limit the scope thereof because it is susceptible to variants which do not go beyond its scope.



    EXAMPLE.-
In a 2 L glass flask with 3 tubes fitted with a stirrer and a thermometer, are introduced successively, protected from air and humidity: - 1500 gr of dry liquid vinyl chloride maintained at a temperature of - 40 C.



    - 2 cm3 (1.72 gr) of diutyl boron chloride.



  - 0.112 g of oxygen.



   The medium is maintained for four hours, at -40 ° C., under a pure and dry nitrogen atmosphere, the total pressure being equal to atmospheric pressure, then the reaction medium is filtered. In this way 49 g of polyvinyl chloride are collected, characterized by a high molecular weight (FICKENTSCHER K index: 98) and a significantly higher degree of crystallinity (20-25%) than that of the usual polyvinylchlorides. The polymer obtained can also be used at a temperature in the region of 100 ° C. without undergoing significant deformation.



   CLAIMS.

** ATTENTION ** end of DESC field can contain start of CLMS **.

Claims

1. Process for the polymerization and / or copolymerization of compounds containing an ethylenic unsaturation corresponding to the general formula EMI3.1 in which R and R 'represent hydrogen, saturated or unsaturated hydrocarbon radicals or atoms and / or polar groups such as halogens, ester, ether or nitrile groups or hydrocarbon radicals substituted by halogens, <Desc / Clms Page number 4> at least one of R and R 'being a polar group, characterized in that the polymerization and / or the copolymerization is carried out at a temperature below -20 ° C. in the presence of a catalyst consisting of an organic derivative of Oore corresponding to the general formula R # BX in which R "is any hydrocarbon radical and X is halogen.

2. Process according to Claim 1, characterized in that the polymerization and / or the copolymerization is carried out at a temperature between - 30 and - 60 C.

3. Method according to claim 1, characterized in that the catalyst is a dialkylated boron halide.

4. Method according to claim 1, characterized in that the catalyst is boron diutyl chloride.

5. Method according to claim 1, characterized in that the amount of catalyst used is from 0.1 to 3% by weight of the amount of the monomer (s). to polymerize.

6. Process according to claim 1, characterized in that the polymerization and / or the copolymerization is carried out in bulk.

7. Process according to claim 1, characterized in that the polymerization and / or the copolymerization is carried out in an organic medium.

8. A method according to claims 1 to 7, characterized -in that the monomer to be polymerized is vinyl chloride.

9. As new industrial products, the polymers and / or copolymers obtained according to the process according to any one of claims 1 to 7.

10. As new industrial products, the high crystalline content and improved thermal resistance polyvinyl chlorides obtained according to the process according to claim 8. <Desc / Clms Page number 5>

11. The method of claim 1, characterized in that the catalyst is activated by adding oxygen in the proportions of 0.001 to 0.01% by weight of the monomer or monomers to be polymerized.