Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/16—Halogen-containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
  • C08K5/37—Thiols
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
  • C08K5/57—Organo-tin compounds

Definitions

• the present invention relates to a process for stabilizing blends based on halogenated polymers or copolymers during their transformation, as well as the stabilization systems provided for this purpose.
• the method of the invention involves compositions stabili ⁇ cient for the protection of polymers and copolymers of halogen-containing and, in particular, polymers and copolymers of vinyl chloride (PVC), against the adverse effects of es heat, during their passage through processing machines such as calenders, extruders, kneaders, injection and coating machines and gelification tunnels. This process ensures the desired initial color and maintains color stability and thermal stability for sufficiently long periods of time.
• PVC vinyl chloride
• thermal stabilizers chemical compounds, commonly called thermal stabilizers, whose role is fourfold: a) to ensure at the start the desired color or the absence of coloring, b) maintaining the initial color of the molten material, without annoying change, for a sufficient duration; c) prevent thermal degradation of the molten material for a sufficiently long period and, d) in the case of finished products which must be transparent, not to compromise the intrinsic transparency of the polymer.
• the temperature of the melt is, in the case of PVC, between 160 ° C and 230 ° C, depending on different factors: nature of PVC (plasticized 'or rigid), K-value of PVC and finally the shear speed which the molten material undergoes in the machine.
• the temperature is, for plasticized PVC, between 160 ° C and 190 ° C and for rigid PVC, between 200 ° C and 230 ° C.
• the duration of the color stability and that of the thermal stability are, for a given mixture, inversely proportional to the temperature of the melt. Each time the temperature increases by 10 ° C, these times decrease by about half. This means, for example, that a system of thermal stabilizers which is satisfactory for the transformation of a mixture of PVC plasticized at 180 ° C, may be totally unsuitable for the transformation of rigid PVC at 220 ° C.
• organotin oxides or with organo-antimony oxides (DE-C-1 217609).
• R methyl, butyl or octyl.
• this type of stabilizer is the only one to satisfy, in the best condition of simplicity, the quadruple role mentioned above, in the case of transformation of rigid PVC at temperatures ranging from 200 ° C to 230 ° C .
• These stabilizers are used, almost exclusively, for the transformation of PVC into transparent rigid sheets and films, into hollow bodies - except bottles for mineral water, for organo-leptic reasons - and into rigid tubes in the United States and Japan and partly also in Europe, replacing lead stabilizers.
• the main disadvantages of these stabilizers are the complexity of their manufacture, the high rate of tin, from 1 to 20% and the high price.
• the object of the present invention is to provide thermal stabilizer compositions capable of fulfilling the performance of stabilizers of the thio-organotin type in the transformation of rigid PVCs while having significant advantages: simplicity of manufacture, reduction of the quantity of metal to around 1% and very significant reduction in the cost of stabilization.
• the inventor has surprisingly discovered that the addition, to a mixture of rigid PVC containing one or more -SH functions (thiol compound), of a very small amount of a metallic or organometallic halide had the effect of 'remarkably improve the initial color, to extend both the duration of color stability and the duration of thermal stability.
• metal halides - without organic radicals - added in very small quantities to PVC mixtures containing thiol compound produce effects similar to the additions of organometallic halide; however, the intensity of these effects depends on the level of acidity of the metal halide.
• the process for stabilizing halo-vinyl resins according to the invention is characterized in that it consists in adding, to the polymer to be protected, a system consisting of at least one organic compound containing one or more -SH- functions and a very small amount of at least one halide chosen from metallic and organometallic halides.
• halogenated resins to which the invention applies are the homopolymers and / or copolymers of vinyl chloride, of vinylidene chloride, of chlorofluoroethylene with the following comonomers: vinyl acetate, acrylonitrile, maleic anhydride, ethylene, propylene and other monomer copolymerizable with vinyl halides, as well as halogenated polyolefins and other halogenated polymers and elastomers, natural or synthetic.
• the thiol compounds used in the process according to the invention have the following general formula:
• - R is the remainder of a monohydroxyl alcohol of any chemical nature such as: aliphatic, olefinic, cyclic, heterocyclic, aromatic, or the rest . of a monomeric polyol such as: glycerol, glycoi, pentaerythritis, sorbitol, pentites, hexites, monosaccharides, or the rest of a polymeric polyol such as polyethylene glycol, polypropylene glycol, polyvinyl alcohol, cellulose, starch and other polysaccharides , R being able to carry various functions such as etheroxide, -carboxylic ester -thiocarbonic, -sulfonic or / and ester of other anorganic acids.
• a monomeric polyol such as: glycerol, glycoi, pentaerythritis, sorbitol, pentites, hexites, monosaccharides, or the rest of a polymeric polyol such as polyethylene
• - R '-SH is the remainder of a monoacid or of a polycarboxylic acid, containing one or more -SH functions, linked to R by esterification, such as, for example, -thioglycolic acid, -mercaptopropionic acid, -mercaptosuccinique, -dimercaptosuccinique, -thiosalicyiique.
• - x is the number of -SH linked to R '.
• the added amount of organic compound containing one or more -SH function (s) is between 0.1 and 5 parts by weight per 100 parts by weight of resin and preferably between 0.3 and 1.5 parts by weight per 100 parts by weight of resin.
• organometallic halides used in the process according to the invention have the following general formula:
• R is an aliphatic, cyclic, heterocyclic, aromatic organic residue, containing or not containing radicals and / or simple or mixed functions.
• - n is the number of R linked to the metal Me.
• - Me Sn, Al, B, Sb, Fe, Cd, Zn, Ti, Hg, Bi, Mn or Ga.
• - Me is a metal of which the halogen salt gives, in aqueous solution of approximately 35 meq. of halogen per liter of distilled water at around 23 ° C, a pH equal to or less than 5, preferably a pH equal to or less than 3.
• - v is the valence of Me.
• - Hal chlorine, bromine, iodine, fluorine.
• the term mixture corresponds to the material intended for processing, obtained by homogenization of several components and the basic component of which is one or more polymers or / and halogenated copolymers and comprising, in addition to the adjuvants I, II or / and III described above, one or more other components such as: anti-shock additives, processing aids, known PVC stabilizers, plasticizers, fillers, dyes, anti-static agents and any usual adjuvant.
• PVC mixtures the components of which are specified in each example, are prepared in a rapid laboratory mixer.
• the quantities of the components are indicated in part by weight per 100 parts by weight of PVC (pcr).
• the quantities of organo-metallic halide and metal halide are, in addition, indicated in brackets by the content in halogen, expressed in milliequivents of halogen per kg of PVC.
• Test method for determining the initial color, color stability and thermal stability.
• a 60 gram portion of the mixture is subjected to kneading on a laboratory cylinder mixer, the cylinders of which are heated to 210 ° C. by circulation of oil.
• the diameter of the two cylinders is 250 mm.
• the distance between the cylinders is kept constant during the test at 0.6 mm.
• the respective rotational speed of the cylinders is 18 rpm and 20 rpm.
• a sample of a small rectangle is taken every minute of mixing.
• the samples are fixed successively on a cardboard display.
• the initial color is assessed visually on the sample at two minutes. Color stability is determined by the duration of mixing leading to a noticeable change in the original color.
• the thermal stability is determined by the mixing time leading to the color changing to dark brown or dark red.
• the thiol compound, pentaerythritis tetra-mercaptoacetate is prepared in the laboratory by esterification of one mole of pentaerythritis containing approximately 4% of -OH functions, with four moles of mercaptoacetic acid, of iodometric purity of 99.96.
• the acid is first introduced into the reactor with 2% water and 0.25% para-toluene sulfonic acid. At 80 ° C, pentaerythritis is added; then the temperature is maintained at 145 ° C until the release of water stops. ' 0.25% of lime carbonate is then introduced and hot filtration is carried out.
• organotin chloride there is a limit on the rate of addition of organotin chloride, after which a reduction in color and thermal stability occurs.
• the metal halide is introduced into the mixture in the form of a very dilute aqueous solution by dissolving, in 250 cc of distilled water, 0.77 grams of SnCl. 5H 2 0 or one gram of chemically pure CdCl-2,5H_O.

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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)
• Compositions Of Macromolecular Compounds (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Polysaccharides And Polysaccharide Derivatives (AREA)
• Saccharide Compounds (AREA)
• Polyesters Or Polycarbonates (AREA)
• Processes Of Treating Macromolecular Substances (AREA)

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• 1987
  • 1987-06-26 FR FR8709279A patent/FR2617175B1/fr not_active Expired
• 1988
  • 1988-06-22 DE DE88420212T patent/DE3880033T2/de not_active Expired - Fee Related
  • 1988-06-22 CA CA000570128A patent/CA1335012C/fr not_active Expired - Fee Related
  • 1988-06-22 AT AT88420212T patent/ATE87952T1/de not_active IP Right Cessation
  • 1988-06-22 BR BR888807588A patent/BR8807588A/pt not_active Application Discontinuation
  • 1988-06-22 EP EP88420212A patent/EP0299882B1/fr not_active Expired - Lifetime
  • 1988-06-22 WO PCT/FR1988/000332 patent/WO1988010282A1/fr not_active Application Discontinuation
  • 1988-06-22 KR KR1019890700355A patent/KR890701674A/ko not_active Application Discontinuation
  • 1988-06-22 ES ES198888420212T patent/ES2040885T3/es not_active Expired - Lifetime
  • 1988-06-22 EP EP19880905881 patent/EP0365577A1/fr active Pending
  • 1988-06-22 HU HU884233A patent/HU205962B/hu not_active IP Right Cessation
  • 1988-06-22 US US07/457,768 patent/US5166241A/en not_active Expired - Fee Related
  • 1988-06-22 AU AU19668/88A patent/AU625411B2/en not_active Ceased
  • 1988-06-22 JP JP63505520A patent/JPH02504038A/ja active Pending
  • 1988-06-22 RO RO143511A patent/RO105578B1/ro unknown
  • 1988-12-06 IL IL88604A patent/IL88604A/xx not_active IP Right Cessation
  • 1988-12-12 ZA ZA889283A patent/ZA889283B/xx unknown
  • 1988-12-27 CN CN88105832A patent/CN1043723A/zh active Pending

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