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
  • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L27/00—Compositions of homopolymers or 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; Compositions of derivatives of such polymers
  • C08L27/02—Compositions of homopolymers or 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; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L27/04—Compositions of homopolymers or 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; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
  • C08L27/06—Homopolymers or copolymers of vinyl chloride
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
  • C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
  • C08L23/22—Copolymers of isobutene; Butyl rubber; Homopolymers or copolymers of other iso-olefins

Definitions

• the intenvion relates to a homo- or copolymer of vinyl chloride containing ⁇ - olefins.
• Polyvinyl chloride is pricewise an economical thermoplastic suitable for a large number of applications.
• various additives such as stabilizers, lubricants, pigments and/or modifiers, are added to the resin obtained in the polymerization.
• the additives are generally admixed into the PVC polymer afterwards before use.
• JP 61155401 is described a suspension polymerization method, wherein 0.1-5 weight-% of C 6 -C 20 --olefin is copolymerized with vinyl chloride.
• the polymer has a residual monomer content, which is lower than the usual content, and which polymer contains less fish eyes.
• the homo- or copolymer of vinyl chloride according to the invention is characterized in that it contains 0.01-50% by weight of an oligomer of a C 4 -C 20 ⁇ -olefin or of an internal olefin or of their mixtures.
• the ohgomer of the ⁇ -olefin apparently acts as an internal lubricant, which decreases or removes the need for using other lubricants or lubricating aids usually applied.
• the oligomer may be added into the polymerization reactor before the beginning of the polymerization or later during the polymerization or after the polymerization reaction. In some applications, the oligomer may also be added to the final polymer by admixing, whereby it acts like a conventional lubricant.
• the oligomer according to the invention When the oligomer according to the invention has been added to the vinyl chloride polymer into the polymerization reactor during the polymerization, it is easily dispersed uniformly in the polymer. This gives good product properties and the processing of the polyvinyl chloride is possible without the addition of other lubricants or it decreases the need for other lubricants. Also, the need for other additives is lower and the mechanical properties of the product are better than those of a PVC prepared in a conventional manner.
• the polyvinyl chloride prepared according to the invention may be used for the same applications as that prepared with conventional methods.
• the ohgomer in a homo- or copolymer of vinyl chloride may be prepared from C 4 -C2o ⁇ -olefins or internal olefins or their mixtures.
• suitable olefins are butenes, pentenes, hexenes, octenes, heptenes, decenes, etc.
• Extremely suitable are C 8 -C 14 ⁇ -olefins and especially suitable are decenes, such as 1-decene, 1-dodecene, 1-hexadecene and 1-tetra- decene.
• the oligomer to be used in the inventive polymers may be a dimer, trimer, tetramer, pentamer or hexamer or their mixture, i.e. the length of the carbon chain may preferably be in the range of C 2 O-C 10 .
• the oligomers may contain reactive double bonds or they may be hydrated. The application of the polymer determines the most suitable oligomer type.
• the polymerization is performed by means of any conventional vinyl-chloride polymerization method, but most usually by means of suspension polymerization.
• the polymerization occurs as a batch process in a reactor provided with a mixer, the contents of which reactor may be heated or cooled with water flowing in the reactor shell.
• the content of the polymerization mixture is typically as follows: 120-200 parts by weight of water, 100 parts by weight of vinyl chloride monomer, 0.05-0.15 parts by weight of suspending agent and 0.03-0.07 parts by weight of an initiator soluble in vinyl chloride. From the reactor, which contains the other ingredients except for the monomer, air is sucked off and the vinyl chloride is added to the mixture.
• the suspending agent such as polyvinyl alcohol, stabilizes the mixture.
• the polymerization starts in the monomer droplets, when the temperature has been increased to 50°C, whereafter the temperature is adjusted to the desired value (50-75°C).
• the batch is transferred into gas-removal and stripping containers.
• the remaining monomer is removed from the polymer particles by steam stripping.
• the mixture is centrifugalized and the solid polymer is usually dried by means of a fluidized-bed or drum method.
• the molar mass of PVC is adjusted by means of the polymerization temperature.
• the size of the polymer molecules decreases.
• the porosity of the particles depends on the temperature; when the temperature increases, the porosity decreases.
• azo- or peroxy compounds such as dicetyl peroxides, peroxide carbonates, alkyl peroxide esters or azodi-isobutyl nitrile.
• the rate of the polymerization depends on the initiator. E.g. lauiyl peroxide and azodi-isobutylnitrile may best be used in higher polyme ⁇ rization temperatures, whereas easily decomposing compounds such as acetyl cyclohexyl sulfonyl peroxide or di-2-ethylhexyl peroxide carbonate may be used in lower temperatures. In many cases, it is prerable to use a mixture of two initi ⁇ ators. The total time of the polymerization is usually 4-10 hours.
• suspending (disperging) agent polyvinyl alcohol or celluloce deriva ⁇ tives, such as methyl-, hydroxyethyl-, hydroxypropyl methyl- or hydroxypropyl celluloce or their mixtures. Part of the dispersing agent is often added later during the polymerization.
• hydrochloric acid formed from the vinyl chloride during the polymerization as well as the acids formed from some initiators are neutralized by bases or buffer compounds, such as sodium or magnesium hydroxide or carbonate.
• the necessary additives are admixed with the polymer before the processing.
• VCM vinyl chloride monomer
• a disperging agent 0.57 g of polyvinyl alcohol / kg of VCM.
• 0.7 g of the dispersing agent / kg of VCM was added during the polymerization.
• an initiator was used dicetyl peroxide carbonate.
• the oligomer was added to the polymerization reactor at the start of the polymerization.
• an oligomer was used an oligomer of decene containing double bonds, which oligomer mainly contained trimer (C ⁇ ) and tetramer (C ⁇ ).
• the polymerization temperature was 57°C.
• the polymerization tests are shown in Table 1.
• Example Volume weight Granular size K value Viscosity DOP g/1 D50, ⁇ m %
• the polymerizations were performed in a similar manner, but as an ohgomer was used a hydrated ohgomer of decene, which mainly contained tetramer ( r ⁇ ), but also trimer (C ⁇ ) and pentamer (C 50 ). The amount of initiator was used 1.25 g / kg of VCM. The polymerizations are shown in Table 3 and the resin analyses in Table 4.
• the resins obtained in the polymerizations were prepared into stabilized mix- tures.
• the thermal stability was determined according to the ISO R 182 method and the VICAT softening point by means of the ISO R 306 standard.
• the MS pressu ⁇ re refers to a gelling test performed by means of the Maclow-Smith plastometer. The results are shown in Table 7.
• VCM vinyl chloride monomer
• dispersing agent totally 1.4 kg of polyvinyl alcohol / kg of VCM.
• dicetyl peroxide carbonate 1.3 g /kg VCM.
• the used oligomer was hydrated decene oligomer containing tetrames (C ⁇ ), pentamers (C 50 ) and heptamers (C ⁇ ). Oligomer is added:
• Example 15 in the beginning of the polymerization reaction
• Example 16 during the reaction, 40 min from the beginning Example 17: during the reaction, before the pressure release
• Example 18 to the slurry, after gas removal
• Example 19 reference, no oligomer Table 8.
• Polymerization was performed in the same method as in Example 15, except that the ohgomer used was made from internal olefin mixture containing 90% C ⁇ olefin and 10% C 16 olefin.
• the oligomer contained 48% of dimers, 39% trimers and 13% tetramers.
• the polymerization results were:

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Polymerisation Methods In General (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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• 1992
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