BE577543A - - Google Patents
Info
- Publication number
- BE577543A BE577543A BE577543DA BE577543A BE 577543 A BE577543 A BE 577543A BE 577543D A BE577543D A BE 577543DA BE 577543 A BE577543 A BE 577543A
- Authority
- BE
- Belgium
- Prior art keywords
- polymerization
- copolymerization
- catalyst
- process according
- carried out
- Prior art date
Links
- 238000000034 method Methods 0.000 claims description 14
- 238000006116 polymerization reaction Methods 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 10
- 238000007334 copolymerization reaction Methods 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical group 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- BZHJMEDXRYGGRV-UHFFFAOYSA-N vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 4
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 3
- 125000004429 atoms Chemical group 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- -1 dialkylated boron halide Chemical class 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atoms Chemical class [H]* 0.000 claims description 2
- 230000000875 corresponding Effects 0.000 claims 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims 1
- 229910052796 boron Inorganic materials 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- 125000004185 ester group Chemical group 0.000 claims 1
- 125000001033 ether group Chemical group 0.000 claims 1
- 125000002560 nitrile group Chemical group 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-Dimethylbutane Chemical group CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 description 1
- UWNADWZGEHDQAB-UHFFFAOYSA-N 2,5-Dimethylhexane Chemical group CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N 2-methyl-2-propenoic acid methyl ester Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229920001567 Vinyl ester Polymers 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000000379 polymerizing Effects 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C08F4/00—Polymerisation catalysts
- C08F4/06—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen
- C08F4/12—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen of boron, aluminium, gallium, indium, thallium or rare earths
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
<Desc/Clms Page number 1>
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
<Desc/Clms Page number 2>
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.
<Desc/Clms Page number 3>
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.
**ATTENTION** fin du champ DESC peut contenir debut de CLMS **.
<Desc / Clms Page number 1>
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
<Desc / Clms Page number 2>
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.
<Desc / Clms Page number 3>
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)
Publications (1)
Publication Number | Publication Date |
---|---|
BE577543A true BE577543A (en) |
Family
ID=190916
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
BE577543D BE577543A (en) |
Country Status (1)
Country | Link |
---|---|
BE (1) | BE577543A (en) |
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0
- BE BE577543D patent/BE577543A/fr unknown
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