• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    PVC is stabilized against the effects of heat by formulating therewith minor amounts of [1] a mixed organometallic salt couplet, [2] a polyol, and [3] a beta -diketone.
    公开号:SU713536A3
    申请号:SU772496803
    申请日:1977-06-28
    公开日:1980-01-30
    发明作者:Гай Мишель
    申请人:Рон-Пуленк Эндюстри (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to vinyl chloride based polymer compositions that are stabilized to heat.
    A known composition based on polymers of vinyl chloride, containing, and as a stabilizing additive, a mixture of metal salts of organic acids and sorbitol 1.
    However, this stabilizing system does not provide sufficiently reliable protection of polymers from heat shrinkage.
    The closest in technical essence and the achieved result to the proposed is composition 2 on the basis of polyvinyl chloride, containing as stabilizers bivalent metal stearates and oxo compound of general formula I
    R, -CO-CHR, -CO-R ,,
    wherein RI and R2 may be the same or different and are hydrogen; alkyl or alkenyl linear or branched radical, aralkyl radical with 7 carbon atoms, phenyl radical or cycloaliphatic radical with 6 carbon atoms; the radicals RI and RS can be modified by the presence of one group-O-; they may be substituted by phenyl, methyl or ethyl radicals;
    Ra is hydrogen; alkyl or alkenyl radical С; -С, which may contain groups -O-
    O / -C ,, ---; radical of the formula
    -COR4,
    R4 is an alkyl radical of Ci- € 4 with the following ratio of components, weight,%:
    Polyvinyl chloride 99.00-99.85
    Bivalent stearate
    metal0,1-5,0
    The compound of formula I 0.05-5.0
    However, this composition has insufficiently high resistance to thermal aging. The aim of the invention was to increase the thermal stability of the composition.
    The goal is achieved by the fact that a polyvinyl chloride based composition containing a stabilizing mixture comprising stearates of divalent metals and an oxo compound of formula I, additionally contains a polyol selected from the group including D-xylitol, /) - sorbitol, / -mannite, glycerol, ( 4-hydroxy 3,3,5,5-β-tetraoxymethyltetrahydropyrin) trioxyethylazocyanate, polyvinyl alcohol, trimethylolpropane, trimethylol ethane tetramethylolcyclohexane, quinna acid ribitol, a-methyl glucoside, glycerin, in the following ratio of components weight. %: Bivalent metal stearates 0.1-5 Oxo compound 0.05-5 Polyol 0.05-1 Polyvinyl chloride Remaining Antioxidants, light stabilizers or UV absorbers can also be added to the composition. Stearate is used in the form of such pairs as calcium-zinc, barium-cadmium, calcium, or barium-zinc. A mixture of calcium and zinc salts is preferred because of their non-toxicity. These metal salt pairs may in some cases be associated with organotin mercats. The proposed stabilizing system may also contain an epoxy compound, epoxidized soybean oil in an amount of up to 8% relative to the polymer. Adding these compounds further improves thermostability. Compositions may contain various additives commonly used to facilitate processing or to impart special properties to the shaped article. Any type of polyvinyl chloride (PVC) can be used in the composition, regardless of how it is prepared: bulk polymerization, in suspension, in dispersion or any other way, and from its characteristic fluid. Compositions intended for the preparation of solid folded objects usually contain impact modifiers and in some cases pigments, fillers, lubricants, etc., in addition to the polymer and stabilizer. The oxo compounds of the formula I can be used individually or in a mixture. Among the compounds of particular interest are benzoyl acetone, lauroylbenzoylmethane, myristoylbenzoylmethane, palmitoylbenzoylmethane, stearoylbenzoylmethane, etc. The preparation of compositions according to the invention is carried out by any known method. The various stabilizers can be shifted with the plasticizer either individually or after mixing with each other, and then introduced into the polymer. Any of the techniques used in this field may be suitable for mixing the ingredients. Homogenization of the mixture can be carried out successfully using a mixer or rollers. The reaction temperature so that the mass is liquid for mixing is about 100 ° C. The compositions can be processed in accordance with any technology commonly used to process PVC compositions, for example extrusion, injection, calendering, molding, casting or deposition on a substrate. Examples 1-20. A composition A is prepared which can be used, for example, for blown extrusion for making bottles. In a ball mill, g: 2000 PVC powder having a viscosity index of 80 (normal NFT 51 013) obtained by polymerization of vinyl chloride in an aqueous suspension (trade name Lyukovil PC 8 000) is mixed; 200 impact-hardening filler, which is a copolymer of butadiene, styrene and methyl methacrylate; 20 grease, which is a rosin ester wax (called Wax E (Cyr. E); 10 calcium stearate; 14 zinc stearate; 60 epoxidized soybean oil; 6 trinonylphenylphosphite. The mixture is treated on rollers for 15 hours. Twenty sandboxes with a capacity of 250 cm containing several porcelain balls are loaded with 56 g of compositions, which additionally contain the components shown in Table 1. A homogeneous composition is obtained by rolling on rollers for 15 h. Of these compositions is obtained on a calender heated to 180 ° C, Plasti 2.5 mm thick (molding time at 180 ° C for about 3 minutes). Rectangular samples of 10X20 mm sizes are cut out from the plates and placed in a ventilated furnace at 180 ° C for various times. Then the color of the samples is determined by Calais Gardner using the Loviond disk. The test results are given in abl 2. Examples 21–24 The composition is prepared using the same procedure as Composition A described in Example 1 and with the same composition. Stabilizers are, g: Calcium stearate 8 Zinc stearate4 Epoxidized soybean oil60 Trinonylphenylphosphate6 Four 250 kg sandboxes containing several porcelain balls are loaded with 56g of compositions B and additionally containing compositions shown in Table. 3
    Table I
    eight
    Table 3
    Thermal strength tests were carried out as previously described, but at 185 ° C. The results are shown in Table. 3
    Examples 25-42. Composition B is prepared in such a manner as composition A described in Example 1 with the following components: 2000 g PVC, obtained by bulk polymerization, having a viscosity index of 95 sold under the trade name Lokovil GB 9550;
    The sheet is produced by calendering at 160 ° C (processing time at this temperature for about 3 minutes).
    Thermal Stability Test
    dioctyl phthalate;
    calcium stearate;
    zinc stearate.
    In eighteen sandboxes with a capacity of 250 cm containing several porcelain balls, load 70 g of compositions B and additionally containing components listed in Table. four.
    Table 4
    conducted according to a previously described description; m method at 180 ° C.
    Get results, clothes in the table. 5 and 5a.
    Examples 43-45. Composition D is prepared as composition C, but replacements with calcium stearate and barium stearate.
    The following compositions are obtained: coloring index through time, min.
    Examples 1.21 and 25 show the effect of metal salts only: Examples 2, 3, 26, 27 and 28 show the effect of only metal salts and polyols; examples 4, 14, 18, 22 and 29 contain only metal salts and table 5
    Table 5a
    the role is composition D as such; stearoyl acetophenone 0.2 g
    Get the results given in
    tab. 6
    Table b
    compounds. All other examples show a significant increase in the stabilizing effect when sharing the three components, according to the invention.
    eleven
    权利要求:
    Claims (2)
    [1]
    1. US patent number 3004000, cl. 260-45.75, publ. 10.10.61.
    [2]
    2. For the USSR USSR number 2306603 / 23-05, according to which the decision to grant a patent, cl. From 08L 27/06, 10.01.75.
    类似技术:
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    US4267083A|1981-05-12|Heat-stabilized vinyl chloride polymers
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    EP0471745A1|1992-02-26|Ultraviolet light stable polymeric compositions.
    SU673183A3|1979-07-05|Polymeric composition
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    US3019205A|1962-01-30|Stabilized asbestos filled polyvinyl chloride resins
    US3326839A|1967-06-20|Plasticized vinyl chloride polymers stabilized with an alkyl diphenylamine
    同族专利:
    公开号 | 公开日
    TR19648A|1979-09-14|
    JPS5811897B2|1983-03-05|
    GB1577555A|1980-10-22|
    NO150123C|1984-08-22|
    FI68642B|1985-06-28|
    CA1090932A|1980-12-02|
    NO772263L|1977-12-29|
    NZ184466A|1980-03-05|
    DE2728862C3|1986-10-23|
    DD131031A5|1978-05-24|
    DE2728862B2|1978-10-26|
    AU506035B2|1979-12-13|
    IT1086297B|1985-05-28|
    SE417833B|1981-04-13|
    AR223954A1|1981-10-15|
    US4123400A|1978-10-31|
    PT66715B|1978-11-22|
    JPS533442A|1978-01-13|
    FR2356674A1|1978-01-27|
    BE856215A|1977-12-28|
    ES460175A1|1978-12-16|
    CS234005B2|1985-03-14|
    CH622274A5|1981-03-31|
    FR2356674B3|1979-03-23|
    PT66715A|1977-07-01|
    NL178081B|1985-08-16|
    FI68642C|1985-10-10|
    FI771997A|1977-12-29|
    ZA773799B|1978-05-30|
    AU2646977A|1979-01-04|
    LU77614A1|1978-07-11|
    BR7704168A|1978-03-28|
    DK284177A|1977-12-29|
    NO150123B|1984-05-14|
    NL7706975A|1977-12-30|
    MX4450E|1982-05-11|
    GR61600B|1978-12-02|
    SE7707409L|1977-12-29|
    DE2728862A1|1978-01-05|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US2711401A|1951-11-23|1955-06-21|Ferro Corp|Stabilized chlorine containing vinyl resins|
    DE1073201B|1955-04-27|1960-01-01|Badische Anilin- &. Soda Fabrik Aktiengesellschaft, Ludwigshafen/Rhem|Plastic masses made of polymers of vinyl chloride or vinyl chloride, stabilized against the action of light|
    DE1251522B|1960-03-15|1967-10-05|S A Argus Chemical N V , Brüssel|Stabilization of vinyl chloride polymers|
    US3004000A|1960-03-15|1961-10-10|Argus Chem|Polyvinyl chloride resin compositions stabilized for use in food packaging|
    US3310525A|1963-03-22|1967-03-21|Eastman Kodak Co|Ultraviolet light stabilized polyester and polyolefin compositions|
    DE1569391A1|1963-06-20|1970-09-24|Carlos Sena Lazcano|Stabilizing agent for polyvinyl chloride and other halogen-containing resins|
    GB1054584A|1963-07-02|
    NL131106C|1964-01-22|
    US3373130A|1965-02-08|1968-03-12|Allied Chem|Vinyl chloride polymer insulation compositions containing ortho-hydroxybenzaldehyde|
    NL146519B|1965-05-21|1975-07-15|Cincinnati Milacron Chem|PROCESS FOR PREPARING A RESINOUS COMPOSITION WITH LESS LIGHT SENSITIVITY.|
    US3492267A|1966-12-02|1970-01-27|Grace W R & Co|Stabilizing poly|
    GB1141971A|1966-12-02|1969-02-05|Grace W R & Co|Improvements relating to stabilizers|
    FR2078616A5|1970-02-17|1971-11-05|M & T Chemicals Inc|
    CS196295B2|1975-01-10|1980-03-31|Rhone Poulenc Ind|Stabilized materials based on polymers or copolymers vinylchloride|US4221687A|1977-07-07|1980-09-09|Argus Chemical Corp.|Anti-yellowing composition|
    JPS5724378B2|1978-01-31|1982-05-24|
    US4416797A|1980-03-03|1983-11-22|Adeka Argus Chemical Co., Ltd.|Chlorinated organic compounds having their resistance to deterioration enhanced by 1,3-dicarbonyl compounds|
    JPS6121494B2|1980-06-09|1986-05-27|Kyodo Yakuhin Kk|
    JPS6320262B2|1980-08-14|1988-04-27|Adeka Argus Chemical Co Ltd|
    US4381360A|1981-01-14|1983-04-26|Phoenix Chemical Corporation|1,3-Dicarbonyl compounds and polyvinyl halide resin compositions containing the same|
    JPS6234271B2|1981-03-16|1987-07-25|Adeka Argus Chemical Co Ltd|
    US4472295A|1981-11-17|1984-09-18|Rca Corporation|Conductive molding composition and discs therefrom|
    JPH0472360B2|1982-09-20|1992-11-18|Hitachi Shomei Kk|
    DK277585A|1984-07-06|1986-01-07|Lonza Ag|STABILIZER MIXTURES FOR VINYL CHLORIDE POLYME MASSES|
    CS253651B1|1984-12-29|1987-12-17|Vaclav Svorcik|Light stability agent for polymers,especially for polypropylene,polyethylene,polystyrene and for polymers containing chlorine|
    NZ217159A|1985-08-26|1989-04-26|Goodrich Co B F|Clear polyvinyl chloride compositions|
    WO1989003858A1|1987-10-23|1989-05-05|The Dow Chemical Company|Vinylidene chloride interpolymer possessing improved extrudability|
    CA1339763C|1988-03-01|1998-03-24|Michael A. Croce|Stability at moderate temperatures of motor vehicle components shaped from polyvinyl chloride resin compositions|
    DE3927777A1|1989-08-23|1991-02-28|Solvay Werke Gmbh|SOFTENER-FREE MOLDING MATERIAL BASED ON POLYVINYL CHLORIDE, METHOD FOR THE PRODUCTION AND USE THEREOF|
    DE4018293A1|1990-06-07|1991-12-12|Neynaber Chemie Gmbh|STABILIZERS CONTAINING KETOFENE ACID GLYCERIDES FOR CA / ZN-STABILIZED PVC MOLDING|
    US5439954A|1991-10-11|1995-08-08|The Procter & Gamble Company|Substituted phenyl-1,3-diketones as protectants against skin damage|
    DE4134325C2|1991-10-17|1997-12-18|Henkel Kgaa|Process for the stabilization of polymers of vinyl chloride and means for carrying out the process|
    US5322872A|1993-04-14|1994-06-21|The Lubrizol Corporation|Stabilized compositions of mixed metal carboxylates|
    ES2117240T3|1993-04-16|1998-08-01|Ciba Geigy Ag|STABILIZED POLY .|
    US6362264B1|1996-12-20|2002-03-26|Ck Witco Corporation|Stabilizer for food contact and medical grade PVC|
    DE102007033970A1|2007-07-19|2009-01-22|Kuraray Europe Gmbh|Use of tempered polyvinyl alcohols as stabilizer additive of PVC|
    DE102007033971A1|2007-07-19|2009-01-22|Kuraray Europe Gmbh|Use of carboxyl-containing polyvinyl alcohols as stabilizer additive of PVC|
    EP2135896A1|2008-06-16|2009-12-23|Kuraray Europe GmbH|Polyvinyl alcohol as co-stabilizer for PVC|
    US9346939B2|2013-11-01|2016-05-24|Galata Chemicals Llc|Flexible PVC compounds having a low metals content|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    FR7620180A|FR2356674B3|1976-06-28|1976-06-28|
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