WO2012143794A1 - Système stabilisateur de polymères pour polymères halogénés - Google Patents

Système stabilisateur de polymères pour polymères halogénés Download PDF

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WO2012143794A1
WO2012143794A1 PCT/IB2012/000861 IB2012000861W WO2012143794A1 WO 2012143794 A1 WO2012143794 A1 WO 2012143794A1 IB 2012000861 W IB2012000861 W IB 2012000861W WO 2012143794 A1 WO2012143794 A1 WO 2012143794A1
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composition
disodium
halogen
polycarboxylic acid
weight
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Johannes Kaufhold
Thomas Hopfmann
Karl-Josef Kuhn
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Galata Chemicals GmbH
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Galata Chemicals GmbH
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    • 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
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • 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 invention relates to halogen-containing polymer compositions comprising a halogen-containing polymer, at least one organotin stabilizer, and at least one aqueous solution containing a metal salt of a polycarboxylic acid.
  • Halogen-containing polymers such as polyvinyl chloride (PVC), which are thermoplastic in nature and, thus, require heat exposure during certain fabrication operations, may be stabilized by a large number of additives against the deleterious effect of heat.
  • PVC polyvinyl chloride
  • stabilizing additives include certain metal-containing additives such as organotin stabilizers.
  • Organotin stabilizers useful in the stabilization of halogen-containing polymers are well-known (cf. Plastics Additives Handbook, 6 th edition, Carl Hanser Publishers, Kunststoff 2001, pg. 444 -453).
  • organotin stabilizers as stabilizing additives for halogen-containing polymers.
  • U.S. Patent No. 5,100,946 describes a stabilized halogen-containing polymer composition wherein the composition contains at least one metal salt selected from the group consisting of at least one carboxylic acid or derivative thereof having at least two carboxyl groups, at least one carboxyl group and at least one hydroxyl group, at least one carboxyl group and at least one mercaptan, and an aromatic carboxylic acid having at least one carboxyl group.
  • the metal salt is most preferably disodium adipate.
  • G.B. Patent No. 1,032,409 discloses a stabilizing composition for polyvinyl chloride and other halogen-containing resins comprising (A) an organotin salt of an unsaturated polycarboxylic acid, or a partial ester thereof with a mono- or polyhydric alcohol; (B) an acidic partial ester of an unsaturated polycarboxylic acid with a mono- or polyhydric alcohol; and (C) a hydrocarbon-substituted phenol.
  • Patent No. 1,351,484 describes stabilized compositions based on vinyl chloride polymers plasticized by means of chlorinated plasticizers in which the stabilizer system contains from 0.1 to 5 parts by weight of one or more organic tin compounds and from 0.1 to 5 parts by weight of one or more alkali salts of unsaturated monocarboxylic acids and/or of one or more alkali salts of unsaturated dicarboxylic acids or unsubstituted saturated dicarboxylic acids containing more than 2 carbon atoms per molecule per 100 parts by weight of vinyl chloride polymer.
  • the compounds according to the invention are particularly suited as stabilizers for halogen- containing thermoplastic resins, in particular PVC.
  • U.S. Patent No. 5,744,525 describes vinyl chloride resins that are thermally stabilized by incorporating a composition based on hornopolymers and/or copolymers of vinyl chloride comprising the following compounds, expressed by weight relative to the weight of the polymers: (A) from 0.1% to 5% of one or more organotin salts and/or one or more divalent metal salts of a carboxylic acid or phenol; and (B) from 0,001% to 5% of one or more organic compounds of the general formula
  • U.S. Patent No. 5,985,959 discloses a composition based on polymer and/or copolymers of vinyl chloride comprising the following compounds expressed by weight percent relative to the weight of the polymer/co-polymer used: (A) from 0.1%-5% of one or more organotin salts and/or one or more divalent metal salts of a carboxylic acid or phenol; and (B) from 0.001%-5% of one or more metal salts of the organic compounds of general formula
  • U.S. Patent No. 6,232,380 describes stabilizer compositions useful for protecting clear polyvinyl chloride and other clear halogen-containing polymer compositions used in the manufacture of exterior weatherable products against discoloration and degradation caused by exposure to ultraviolet light and weathering in addition to heat comprising a latent mercaptan which degrades during processing of the composition at an elevated temperature to liberate free mercaptan, in combination with a synergistic amount of a free phenyl salicylate compound.
  • EP Application Publication No. 107,063 discloses an invention providing an improved heat stabilization of vinyl chloride polymers (which term includes postchlorinated polymers) utilizing a combination of an organotin or organoantimony primary stabilizer with sodium or potassium citrate.
  • the particle size of the citrate salt is less than 30 ⁇ .
  • JP 11343375 A describes, based on 100 parts by wt.of vinyl chloride resin, a composition containing (A) 0.5-10 parts by wt. of copolymer which is prepared from a monomer mixture comprising 5-50 mol.% long-chain (meth)acrylate having a 16-22 carbon atom alkyl or alkenyl group, 40-95 mol.% glycidyl (meth)acrylate, and 0-25 mol.% other copolymerizable monomer and has a wt. average mol.wt. of 2,000-500,000 and (B) 0.01-4 parts by wt. of organotin stabilizer and/or (C) 0.01-3 parts by wt. at least one metal carboxylate selected from among calcium, barium, magnesium, and zinc earboxylates.
  • A 0.5-10 parts by wt. of copolymer which is prepared from a monomer mixture comprising 5-50 mol.% long-chain (meth)acrylate having
  • U.S. Patent Application Publication 2005/0101716 discloses a stabilizer composition
  • a stabilizer composition comprising (A) a microernulsion of an overbased metal carbonate/carboxylate obtained from the reaction of an oxide and/or hydroxide of a metal selected from the group consisting of sodium, potassium, calcium, magnesium, zinc and mixtures thereof, an aliphatic carboxylic acid in which the aliphatic moiety contains up to about 30 carbon atoms and carbon dioxide in the presence of a solvent for the aliphatic carboxylic acid, a promoter and a microemulsion-forming amount of surfactant; and.
  • B at least one organotin stabilizer.
  • EP Application Publication No. 2,151,475 describes a composition for stabilizing halogen-containing polymers comprising sodium formate, at least one Cj— Ca 4 fatty acid or a salt thereof with a metal selected from the metals of Groups I and II of the Periodic Table, and an amorphous synthetic silica with BET area > 50 m 2 /g, wherein the composition is in the form of a powder having particles with granulometric distribution indices D50, in the range from 2 to 60 ⁇ , and D90 less than or equal to 100 ⁇ .
  • U.S. Patent Application Publication 2003/0018112 discloses a chlorinated vinyl chloride resin composition comprising 100 parts by weight of chlorinated vinyl chloride resin and a hydroxypolycarboxylic acid, e. g., sodium tartrate and/or 0.2 to 1.5 parts by wt. of zeolite. The composition exhibits improved thermal stability and is particularly suited to pipe extrusion.
  • U.S. Patent Application Publication 2005/00107504 describes stabilizer compositions that are employed to stabilize filled halogen-containing vinyl polymers tram, for example, degradation and discoloration.
  • the stabilizer compositions comprise a mercaptan-containing organic compound; and a zinc salt in an amount effective to provide 0.075 to 1.5 parts by weight of zinc, based on 100 parts by weight of the halogen-containing vinyl polymers,
  • U.S. Patent Application Publication 2009/0186989 discloses a composition for stabilizing halogen-containing polymers, in particular polyvinyl chloride (PVC) and chlorinated polyvinyl chloride (C-PVC) which includes (A) disodium adipate, and (B) at least one compound such as M(C10 4 ) k and (CF 3 S0 3 ) radicalM where M is H + , Li + , Na + , K + , Mg 2+ , Ca 2 ⁇ Ba 2+ , Zn 2i , Al 3+ or NH 4 and k and n are 1, 2 or 3 depending on the valency of M. Also described is a halogenated resin in a rigid or plasticized formulation having a halogen-containing polymer and a stabilizing composition.
  • PVC polyvinyl chloride
  • C-PVC chlorinated polyvinyl chloride
  • M is H + , Li + , Na + , K + , Mg 2+ ,
  • U.S. Patent Application Publication 2010/267873 describes a stabilized halogen- containing polymer composition comprising: (A) a halogenated polymeric material; (B) a methyl tin stabilizer comprising a mixture of mono methyltin stabilizer and dimethyltin stabilizer and (C) a salt of a polyacid material such as a polycarboxylic acid to form the stabilized halogen- containing polymer composition.
  • U.S. Patent Application Publication 2011/0166268 relates to high-purity monoalkyltin compounds, more specifically to alkyltin compound compositions containing monoalkyltin as major compound, and minor quantities of di- and/or trialkyltin compounds.
  • the invention is directed to a method of stabilizing a halogen- containing pol ymer comprising the steps of (i) dissolving a metal salt of a polycarboxylic acid in water or dissolving polycarboxylic acid in aqueous base, to provide an aqueous solution comprising the metal salt of a polycarboxylic acid; and (ii) providing a stabilized halogen- containing polymer composition comprising said aqueous solution, an organotin stabilizer, and a halogen-containing polymer.
  • the invention provides stabilized halogen-containing polymer compositions comprising an aqueous solution containing a metal salt of a polycarboxylic acid, an organotin stabilizer; and a halogen-containing polymer.
  • the aqueous solutions of the invention are prepared by dissolving (i) polycarboxylic acids in aqueous bases or (ii) metal salts of polycarboxylic acid in water.
  • the present invention generally relates to a halogen-containing polymer composition
  • a halogen-containing polymer composition comprising a halogen-containing polymer, at least one organotin stabilizer, and an aqueous solution comprising at least one metal salt of a polycarboxylic acid.
  • the organotin stabilizers of the invention include compounds containing one or more tetravalent tin atoms which each have at least one direct tin-to-sulfur or tin-to-o
  • Exemplary organotin stabilizers include those containing one or more tetravalent tin atoms having at least one direct tin to carbon bond and wherein the remaining valencies of the tin atom are satisfied by bonds to either oxygen, or sulfur as a residue resulting from removal of the hydrogen atom from the sulfur atom of a mercaptan, or mercaptoacid, mercaptoalcohol, mercaptoacid ester or mercapto-alcohol ester or a residue resulting from removal of the hydrogen atom from the oxygen atom of a carboxylic acid or alcohol or halogen acid with the provision that at least one valence site is oxygen or sulfur or a mixture thereof.
  • Organotin compounds include methyltin mercaptide, butyltin mercaptide, octyltin mercaptide, dodecyltin mercaptide, ester tin mercaptide, and reaction products of an organotin halide with alkaline metal sulfide and mercaptide, mercaptoacid esters, mercaptoalcohols, or mercaptoalcohol esters or mixtures of any two or more thereof.
  • organotin stabilizer compounds include organotin mercaptides, halogen containing sulfur or oxygen bridged organotin mercaptides, alkyltin carboxylates, and organotin alkoxides.
  • organotin stabilizers also include organotin chloride / organotin mercaptide combinations or alkyl chloro-tin carboxylates.
  • organotin stabilizers of the invention can be used alone or in combination, in the form of mixtures that react in situ, as described in U.S. Pat. No. 3,674,737 to Brecker, in the form of mixtures as described in U.S. Pat. No. 4,255,320 to Brecker and as blends as described in U.S. Pat. No. 4,576,984 to Bresser et al.
  • organotin stabilizers, mixtures, blends thereof and the like referred to above can be used in combination with organotin halides as disclosed by Larkin in U.S. Pat. No. 3,715,333.
  • organotin stabilizers useful herein are well-known for their ability to prevent formation of, or react with and neutralize, the hydrogen halide evolved when vinyl halide polymers are heated to processing temperatures.
  • the progressive elimination of hydrogen halide from the polymerization chain yields a polyene chain which is believed to be at least partially responsible for the change in viscosity and color that occurs during heating of the polymer.
  • i 1 or 2.
  • j is an integer from 1 to 6,
  • k is an integer from 1 to 3 and
  • n 1 to 4
  • Rj is Ci ⁇ Ci 2 alkyl or Ci - Q alkoxycarbonylethyl
  • Q has the meaning - ⁇ S- or 0 CO and
  • R 2 is C 3 ⁇ 4 rCi 8 alkyl, a radical -R3-COO-R4 or iCHj h O CO i. or ,
  • R 3 is methylene, ethylene, or o-phenylene
  • R4 is C 5 ⁇ Ci8 alkyl
  • R5 is Ci-Cis alkyl, C5-C7 cycloalkyl, or benzyl
  • R 6 is methylene, ethylene or o-phenylene
  • R(, is Ci ⁇ Cg alkyl, o-phenylene or the group ⁇ CH CH-,
  • R? is C2-C4 alkylene or C4-C8 alkylene which is interrupted by oxygen
  • R 3 ⁇ 4 is Ci ⁇ Ci8 alkyl, Cj-Cis alkenyl, phenyl, substituted phenyl, or a radical
  • X can be -0 ⁇ and'or -O-CO--R9- -COO-
  • R « is Ci-Ce alkyl, o-phenylene or a group -CH ⁇ CH- ,
  • Preferred organotin stabilizers also include reaction products of a mono-organotin trihalide, a diorgano-tin dihalide, or mixtures thereof, with an alkali-metal sulfide, alkali metal mercaptocarboxylate or thiocarboxylate ester, and one or more of a monocarboxylic acid, a polycarboxylic acid, and more preferably a mercaptan, a mercaptoacid, a mercaptoalcohol, a mercaptoacid ester or a mercaptoalcohol ester.
  • More preferred organotin stabilizers are bridged mercaptide compounds.
  • Preferred sulfur-bridged compounds nominally are represented by the formula
  • a and A 1 are alkyl of 1 to 12 carbon atoms, preferably methyl, butyl and octyl;
  • a 2 , A 3 , A and A 5 are lower alkylene having the formula— (01 ⁇ 4) ⁇ — ⁇
  • n is from 1 to 18, with an n of 1 or 2 preferred;
  • B and B' are selected from S and O;
  • D, D ! , D" and D 3 each, independently are selected from
  • organotin stabilizers of the invention are sulfide-containing tin mercaptide-type stabilizers. These com ounds contain
  • organotin stabilizers include monoalkyltin and dialkyltin mercaptides wherein the alkyl group preferably is methyl, butyl, dodecyl, and the like. Preferred are monoalkyltin and dialkyltin thioglycolates and mercaptoproprionates, and more preferred are monoalkyltin and dialkyltin isooctyl, 2-ethylhexyl, and ethyleneglycol thioglycolates, butylene thioglycolates and mercaptopropionates.
  • organotin stabilizers are non-sulfur stabilizing compounds where tin is bonded to oxygen. These compounds contain
  • Suitable examples in this group include dibutyltin maleate, dibutyltin bis(stearylmaleate), dibutyltin dilaurate, dibutyltin bis(ethylmaleate), dioctyltin bis(ethylmaleate), dioctyltin dilaurate, dioctyltin bis(isodecanoate), dioctyltin bis(2-ethylhexanoate), dioctyltin maleate, and mixtures of any two or more thereof.
  • Exemplary non-sulfur tin compounds which are utilized as excellent stabilizing materials, alone or in combination, are organotin carboxylases or organotin alkoxides.
  • the organotin stabilizers of the present invention may include combinations of any of the above compounds.
  • the combinations can be made by individually mixing the compounds together, or by actually forming two or more of the above-identified stabilizing compounds together in an in situ chemical synthesis.
  • Specific examples of useful organotin stabilizer compounds are listed in Plastics Additives Handbook, 6 ih edition, Carl Hanser Publishers, Kunststoff 2009, pp. 444-453 which are incorporated herein by reference.
  • organotin stabilizers useful in the invention include those available from Galata Chemicals, LLC (Hahnville, LA, USA) and Galata Chemicals GmbH (Lampertheim, Germany) under the Mark® tradename.
  • Exemplar methyltin- based organotin stabilizers include Mark® 1900, Mark® 1984E, Mark® 1995, and Mark® 1998.
  • Exemplary butyl-based organotin stabilizers include Mark® 17M, Mark® 292, Mark® 1367, Mark® 2288, Mark® T 634, Mark® 2100A, Mark® 2255, and Mark® 2284A.
  • Exemplary oetyltin-based organotin stabilizers include Mark® 17 MOK, Mark® 17 MOK-A, Mark® 17 MOK-D, Mark® 17 MOK-N, Mark® 17 MOK-P, Mark® 17 MOK-S, Mark® T 281, Mark® 3062, Mark® T 216GV, Mark® T 650, Mark® T 652, Mark® T 682, and Mark® T 161.
  • the polymer compositions of the present invention contain from 0.01 to 5,0 parts, preferably from 0.01 to 3.0, more preferably from 0.1 to 2.5, and most preferably from 0.3 to 1.5 parts by weight of the organotin stabilizer, based on 100 parts by weight of halogen- containing polymer.
  • the organotin stabilizer of the invention Considering the elemental tin to be the operative material in the organotin stabilizer of the invention, and without limiting the invention in any manner or being bound by specific theory, such stabilizers can alternatively be based on the weight of the elemental tin in the organotin stabilizer.
  • compositions contain from 0.005 to 1.0 parts and preferably from 0.005 to 0.5 parts of tin, based on 100 parts of halogen-containing polymer. More preferably the amount of tin is in the range of from 0.05 to 0.5 parts per 100 parts by weight of halogen-containing polymer.
  • the invention provides aqueous solutions comprising metal salts of polycarboxylic acids.
  • the aqueous solutions are prepared by dissolving the metal salts in water.
  • the aqueous solutions of the invention are prepared by dissolving polycarboxylic acids in aqueous bases to form the aqueous solutions.
  • aqueous bases include hydroxides of alkali metals.
  • Preferred aqueous bases include LiOH, NaOH, OH, and mixtures of at least two thereof. Most preferred are NaOH and KOH.
  • Suitable aqueous bases have a pH value in the range of from 6 to 12, and preferably from 8 to 12.
  • polycarboxylic acids can be dissolved in aqueous bases to form aqueous solutions containing metal salts of polycarboxylic acids.
  • polycarboxylic acids upon dissolution in aqueous base, may undergo reaction comprising neutralization of one or more carboxyl groups with the aqueous base.
  • polycarboxylic acids examples include malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, maleic acid, fumaric acid, tartaric acid, malic acid. tartronic acid, citric acid, polyacrylie acid, polymethacrylic acid, maleic acid copolymers, and the like.
  • At least 30 weight percent of the carboxyl groups of the polycarboxylic acid are neutralized, preferably 70 weight percent, more preferably 80 weight percent, and most preferably 100 weight percent.
  • the polycarboxylic acids are dissolved in aqueous bases containing at least 0.3 mole equivalents of base, preferably at least 0.5 mole equivalents, more preferably at least 0.75 mole equivalents, and most preferably at least 1 mole equivalent, to form the aqueous solutions of the invention.
  • aqueous solutions prepared by dissolving polycarboxylic acids in aqueous bases containing a molar excess of base.
  • the metal salts of a polycarboxylic acid include compounds having the formula (CHaJnCCOjM)! ,wherein M is an alkali metal as discussed above and n is an integer from 1 to 10, and preferably is an integer from 2 to 5.
  • Suitable examples of the metal salts are disodium malonate, dipotassium malonate, disodium succinate, dipotassium succinate, disodium glutarate, dipotassium glutarate, disodium adipate, dipotassium adipate, disodium suberate, dipotasum suberate, disodium sebacate, dipotassium sebacate, and mixtures of any two or more thereof.
  • Preferred are disodium adipate and dipotassium adipate, and most preferred is disodium adipate.
  • useful metal salts of a polycarboxylic acid include disodium maleate, dipotassium maleate, disodium fumarate, dipotassium fumarate, disodium tartrate, dipotassium tartrate, disodium malate, dipotassium malate, disodium tartronate, dipotassium tartronate, trisodium citrate, disodium citrate, tripotassium citrate, dipotassium citrate, and mixtures of any two or more thereof.
  • suitable metal salts of the invention include sodium poly(acrylate), sodium polyimethacrylate), alkali metal salts of maleic acid copolymers, and mixtures of any two or more thereof.
  • the concentration of the metal salt in the aqueous solution is from 0.1 to 60, preferably from 1 to 50, more preferably from 10 to 40, and most preferably from 15 to 30 percent by weight, based on weight of the aqueous solution.
  • the aqueous solution is added as a clear aqueous solution, that is, substantially without any visible haze, precipitation, and the like.
  • the clear aqueous solution may be added at a temperature from 5 to 80 °C, preferably from 10 to 60 °C, more preferably from 15 to 40 °C, and most preferably from 20 to 25 C
  • Examples of the amount used of the aqueous solution comprising the metal salt of a polycarboxylic acid are from 0.05 to 5, preferably from 0.2 to 3, and more preferably from 0.2 to 2 parts by weight, based on 100 parts by weight of halogen-containing polymer.
  • the stabilized halogen-containing polymer compositions of the invention comprise chlorine containing polymers.
  • Suitable examples of chlorine-containing polymers include polymers of vinyl chloride (P VC), of vinylidene chloride, vinyl resins whose structure contains vinyl chloride units, such as copolymers of vinyl chloride and alkylglycidyl acrylates, copolymers of vinyl chloride and vinyl esters of aliphatic acids, in particular vinyl acetate, copolymers of vinyl chloride with esters of acrylic or methacrylic acid and with acrylonitrile, copolymers of vinyl chloride with diene compounds and with unsaturated dicarboxylic acids or anhydrides of these, such as copolymers of vinyl chloride with diethyl maleate, diethyl fumarate or maleie anhydride, postchlorinated polymers and copolymers of vinyl chloride, copolymers of vinyl chloride and vinylidene chloride with unsaturated aldehydes, ketones
  • C-PVC postchlorinated PVC
  • suitable polymers are graft polymers of PVC with EVA, ABS or MBS.
  • Other preferred substrates are mixtures of the abovementioned homo- and copolymers, in particular vinyl chloride homopolymers, with other thermoplastic or/and elastomeric polymers, in particular blends with ABS, MBS, NBR, SAN, EVA, CPE, MBAS, PMA, PMMA, EPDM or with polylactones, in particular from the group consisting of ABS, NBR, NAR, SAN and EVA.
  • ABS acrylonitrile-butadiene-styrene
  • SAN styrene-acrylonitrile
  • NBR acrylonitrile-butadiene
  • NAR acrylonitrile-acrylate
  • EVA ethylene-vinyl acetate
  • Other possible polymers are in particular styrene-acrylonitrile copolymers based on acrylate (ASA).
  • the stabilized halogen-containing polymer compositions are non- plasticized or plasticizer-free or substantially plasticizer-free compositions.
  • the stabilized halogen-containing polymer compositions are plasticized compositions.
  • compositions of the invention are useful in particular, in the form of rigid formulations, for hollow articles (bottles), packaging films (thermoformable films), blown films, pipes, tubes, foams, heavy profiles (window frames), translucent-wall profiles, building profiles, films (including Luvitherm films), sidings, fittings, office films and equipment housings (computers and domestic appliances).
  • a particularly preferred composition of the present invention comprises polyvinyl chloride or PVC.
  • a preferred organotin stabilizer can include alkyltin mercaptide, alkyltin mercaptoacid ester compounds, and more preferably methyltin mercaptides, octyltin mercaptides, methyltin mercaptoacid esters, octyltin mercaptoacid esters, and most preferably methyltin and octyltin 2- ethylhexylthioglycolates, in an amount of from about 0.1 to about 2.5 parts by weight, based on 100 parts of PVC.
  • More preferred organotin stabilizers can include di-n-octyltin-bis(2- ethylhexylthioglycolate), mono-octyltin-tris(2.-ethylhexylthioglycOlate), di-n-octyltin 1 ,4- butanediol-bis-rnercaptoacetate, dimeihyltin-bis(2-ethylhexylthioglycolate). monomethyltin- tris(2-ethylhexylthioglycolate), and mixtures of at least two thereof.
  • the invention provides combinations of stabilized halogen- containing polymer compositions with at least one other conventional additive or stabilizer.
  • the invention includes combinations of stabilized halogen-containing polymer compositions comprising a halogen-containing polymer, an organotin stabilizer, and an aqueous solution comprising a metal salt of a polycarboxylic acid, and at least one other conventional additive or stabilizer.
  • phosphites Preference is given to phosphites, polyols and disaccharide alcohols, glycidyl compounds, hydrotalcites, zeolites (alkali metal aluminosilicates and alkaline earth metal aluminosilicates), fillers, metal soaps, alkali metal and alkaline earth metal compounds, lubricants, plasticizers, pigments, epoxidized fatty esters and other epoxy compounds, antioxidants, UV absorbers, light stabilizers, optical brighteners and blowing agents.
  • zeolites alkali metal aluminosilicates and alkaline earth metal aluminosilicates
  • fillers metal soaps, alkali metal and alkaline earth metal compounds, lubricants, plasticizers, pigments, epoxidized fatty esters and other epoxy compounds, antioxidants, UV absorbers, light stabilizers, optical brighteners and blowing agents.
  • epoxidized fatty acid esters and other epoxy compounds Particular preference is given to epoxidized fatty acid esters and other epoxy compounds, polyols, alkaline earth metal soaps, zeolites, hydrotalcites and phosphites. Very particular preference is given to phosphites.
  • polyols and disaccharide alcohols examples include pentaerythritol, dipentaerythritol, tripentaerythritol , trimethylolethane, bis(trimethylolpropane), polyvinyl alcohol, bis( trimethylolethane), trimethylolpropane, sugars, sugar alcohols.
  • Glycidyl compounds contain the glycidyl group
  • Ri and R3 ⁇ 4 together are— CH 2 — CH 2 — or — -C3 ⁇ 4 C3 ⁇ 4— -C3 ⁇ 4— , R2 then being hydrogen and n being 0 or 1.
  • the amounts used of the terminal epoxy compounds are preferably at least 0.1 parts by weight, preferably from 0.1 to 50 parts by weight, advantageously from 1 to 30 parts by weight and in particular from 1 to 25 parts by weight, based on 100 parts by weight of PVC.
  • Fillers such as calcium and magnesium carbonate, dolomite, wollastonite, magnesium oxide, magnesium hydroxide, aluminum hydroxide, silicates, china clay, talc, glass fibers, glass beads, wood flour, cellulose fibers, mica, carbon black, graphite, rock flour, heavy spar, glass fibers, talc, kaolin and chalk are used. Preference is given to chalk ("Handbook of PVC Formulating" by E. J. Wickson, John Wiley & Sons, Inc., 1993, pp. 393-449) and reinforcing agents (Plastics Additives Handbook, 6 th edition, Carl Hanser Publishers, Kunststoff 2009, pp. 919- 966).
  • the fillers may be used in amounts of preferably at least one part by weight, for example, 5 to 200 parts by weight, expediently 5 to 150 parts by weight and in particular from 5 to 100 parts by weight based on 100 parts by weight of PVC.
  • Suitable lubricants are: montan wax, paraffins, fatty acid esters, complex esters, PE waxes, amide waxes, chloroparaffins, glycerol esters and alkaline earth metal soaps, and fatty ketones, and also the lubricants, or combination of the lubricants, listed in EP 0259 783 and Plastics Additives Handbook, 6 th edition, Carl Hanser Publishers, Kunststoff 2009, pg. 564, the contents of which are incorporated by reference herein. Calcium stearate is preferred.
  • organic plasticizers include those from the following groups:
  • Phthalates (i) ortho phthalates such as preferably diisononyl and diisodecyl phthalate, also known by the common abbreviations DINP (diisononyl phthalate) and DIDP
  • terephthalates (als known as para phthalates) such as dioctyl and bis(2-ethylhexyl) terephthalate, also known by the common respective abbreviations DOTP and
  • esters of aliphatic and cycloaliphatic dicarboxylic acids in particular esters of adipic, azelaic or sebacic acid: preferably di-2-ethylhexyl adipate and diisooctyl adipate.
  • esters of cycloaliphatic dicarboxylic acids in this group include but are not limited to diisononyl cyclohexane-l,2-dicarboxylate, also known by the common abbreviation DINCH.
  • acetylated monoglycerols derived from vegetable oils such as castor oil, coca oil, palm oil, and the like,
  • C) Trimellitic esters such as tri-2-ethylhexyl trimellitate, triisodecyl trimellitate (mixture), triisotridecyl trimellitate, triisooctyl trimellitate (mixture), and also tri-CVCg-alkyl, tri- C6-Cio-alkyl, tri-C7-C 9 -alkyl and tri-CrCn-alkyl trimellitate.
  • Common abbreviations are TOTM (trioctyl trimellitate, tri-2-ethyl-hexyl trimellitate), TIDTM (triisodecyl trimellitate) and TITDTM (triisotridecyl trimellitate).
  • Epoxy plasticizers are primarily epoxidized unsaturated fatty acids, e.g. epoxidized soybean oil.
  • polyester plasticizers the most common starting materials for preparing polyester plasticizers are: dicarboxylic acids, such as adipic, phthalic, azelaic or sebacic acid; diols, such as 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol and diethylene glycol.
  • dicarboxylic acids such as adipic, phthalic, azelaic or sebacic acid
  • diols such as 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol and diethylene glycol.
  • Phosphoric esters a definition of these esters is given in the above mentioned Plastics Additives Handbook, 6 lh edition, Carl Hanser Publishers, Kunststoff 2009, pp. 485-514.
  • Examples of these phosphoric esters are tributyl phosphate, tri-2-ethylbutyl phosphate, tri-2- ethylhexyl phosphate, trichloroethyl phosphate, 2-ethylhexyl diphenyl phosphate, cresyl diphenyl phosphate, triphenyl phosphate, tricresyl phosphate and trixylenyl phosphate.
  • Glycol esters e.g. diglycol benzoates.
  • plasticizers A definition of these plasticizers and examples for the same is given in the plasticizers chapter in Plastics Additives Handbook, 6 th edition, Carl Hanser Publishers, Kunststoff 2009, pp. 485-514. In accordance with the present invention, mixtures of diff erent plasticizers may also be used.
  • the plasticizers may be used in amounts of, for example, 5 to 100 parts by weight, expediently 10 to 70 parts by weight, preferably for flexible PVC 20 to 50 parts by weight, based on 100 parts by weight of PVC.
  • Semi-rigid PVC comprises preferably up to 20%, particularly preferably up to 15%, of plasticizer, or no plasticizer.
  • Suitable substances are known to those skilled in the art.
  • inorganic pigments are Ti0 2 , pigments based on zirconium oxide, BaS0 4 , zinc oxide (zinc white) and lithopones (zinc sulfide/barium sulfate), carbon black, carbon black-titanium dioxide mixtures, iron oxide pigments, SbjOs, (Ti, Ba, SbO) 2 , Cr 2 0 3 , spinels, such as cobalt blue and cobalt green, Cd(S, Se), ultramarine blue.
  • organic pigments examples include azo pigments, phthalocyanine pigments, quinacridone pigments, perylene pigments, diketopyrrolopyrrole pigments and anthraquinone pigments. Ti0 2 in micronized form is also preferred. A definition and further descriptions are found in the Plastics Additives Handbook , 6 th edition, Carl Hanser Publishers, Kunststoff 2009, pp. 831-900.
  • Suitable phosphites are various mixed aryl dialkyl or alkyl diarylphosphites, such as phenyl dioctyl, phenyl didecyl, phenyl didodecyl, phenyl ditridecyl, phenyl ditetradecyl, phenyl dipentadecyl, octyl diphenyl, decyl diphenyl, undecyl diphenyl, dodecyl diphenyl, tridecyl diphenyl, tetradecyl diphenyl, pentadecyl diphenyl, oleyl diphenyl, stearyl diphenyl and dodecyl bis(2,4-di-tert-butylphenyl) phosphite.
  • phenyl dioctyl phenyl didecyl
  • phenyl didodecyl phenyl di
  • phosphites of various di- or polyols e.g., tetraphenyldipropylene glycol diphosphate, polydipropylene glycol phenyl phosphite, tet- raisodecyl dipropylene glycol diphosphite, tris(dipropylene glycol) phosphite, tetra- methylolcyclohexanol decyl diphosphite, tetramethylol-cyclohexanol butoxyethoxyethyl diphosphite, tetra-methyloleyclohexanol nonylphenyl diphosphite, bis(nonylphenyl) di(trimethylolpropane) diphosphite, bis(2-butoxyethyl) di(trimethylolpropane) diphosphite, tris(hydroxyethyl)
  • Exemplary amounts of the organic phosphites used are from 0,01 to 10, advantageously from 0.05 to 5, and in particular from 0,1 to 3 parts by weight, based on 100 parts by weight of PVC.
  • the stabilized halogen-containing polymer composition of the invention may additionally and preferably comprise at least one epoxidized fatty acid ester.
  • Suitable compounds here are especially esters of fatty acids from natural sources (fatty acid glycerides), such as soy oil or rapeseed oil.
  • synthetic products such as epoxidized butyl oleate.
  • Use may also be made of epoxidized polybutadiene and polyisoprene, if desired also in a partially hydroxylated form, or of glycidyl acrylate and glycidyl methacrylate as homo- or copolymer.
  • These epoxy compounds may also have been applied to an alumino salt compound; as has been discussed in DE-A-4 031 818, the contents of which is incorporated by reference herein.
  • Alkylated monophenols e.g. 2,6-di-tert-butyl-4-methyl -phenol
  • alkylthiomethylphenols e.g. 2,4-dioctylthi-omethyl-6-tert-butylphenol
  • alkylated hydroquinones e.g. 2,6-di-tert-butyl-4-methoxyphenol
  • hydroxylated thiodiphenyl ethers e.g. 2,2'-thiobi3(6-tert- butyl-4-methylphenol
  • alkylidenebisphenols e.g.
  • esters of beta-(3,5-di- tert-butyl-4-hydroxyphenyl)propionic acid esters of beta-(3,5-di- tert-butyl-4-hydroxyphenyl)propionic acid, beta-(5-teri-butyl-4 ⁇ hydroxy-3- methylphenyDpropionic acid, beta-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid, esters of 3,5-ditert-butyl-4-hydroxyphenylacetic acid with mono- or polyhydric alcohols, amides of beta- (3,5-ditert-butyl-4-hydrox phenyl-)propionic acid, such as, for example, N, N'-bis(3,5-ditert- butyl-4-hydroxyphenyl-propionyl)hexamethylenediaiTiine, vitamin E (tocopherol) and derivatives.
  • antioxidants used are from 0.01 to 10 parts by weight, advantageously from 0.1 to 10 parts by weight, and in particular from 0.1 to 5 parts by weight, based on 100 parts by weight of PVC,
  • UV Absorbers and Light Stabilizers UV Absorbers and Light Stabilizers
  • Examples of these are: 2-(2 , -hydroxyphenyl-)benzotriazoles, such as 2-(2'-hydroxy-5'- methylphenyl)-benzotriazole, 2-hydroxybenzophenones, esters of unsubstituted or substituted benzoic acids, such as 4-tert-butylphenyl salicylate, phenyl salicylate, acrylates, nickel compounds, oxalamides, such as 4,4-dioctyloxyoxanilide, 2,2'-dioctyloxy-5,5'-ditert- butyloxanilide, 2-(2-hydroxyphenyl)-l,3,5-triazines, such as 2,4,6-tris(2-hydroxy-4- octyloxyphenyl)-l, 3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyI)-4,6-bis(2,4-dimethylphenyl)- 1,3,5-triazin
  • blowing agents are organic azo compounds and organic hydrazo compounds, tetrazoles, oxazines, isatoic anhydride, and also soda and sodium bicarbonate. Preference is gi ven to azodicarbonamide and sodium bicarbonate and also mixtures of these.
  • the PVC polymer stabilized according to and also provided by the invention may be prepared in a manner known per se, by using equipment known per se, such as the above- mentioned processing apparatus, to mix the organotin stabilizers and aqueous solutions of the metal salts of a polycarboxylic acid of the invention and, if desired, other conventional stabilizers and additives, with the PVC.
  • the stabilizers and additives here may be added individually or in a mixture, or else in the form of what are known as masterbatches.
  • the invention provides for admixing the aqueous solutions comprising metal salts of a polycarboxylic acid with a carrier material.
  • the carrier material having thus incorporated the aqueous solutions may be admixed with the PVC polymer, by any known methods such as those described above, thereby providing for the incorporation of the aqueous solutions into the PVC polymer.
  • admixing the aqueous solutions with the carrier material may result in affixing the aqueous solutions onto the carrier material surface, external or internal, and/or incorporating the aqueous solutions into the carrier material as such.
  • Admixing the aqueous solutions with the carrier material i. e., affixing, incorporating, or both, may include the steps of adsorption, absorption, adhesion, coating, dispersing, suspending, spraying, applying, for example, with an applicator, blending, and the like.
  • suitable carrier materials include silicates, aluminosilicates, zeolites, hydrotalcites, silica gel, diatomite (diatomaceous earth, kieselguhr), calcium carbonate, chalk, dolomite, wollastonite, magnesium oxide, magnesium hydroxide, clay, talc, glass fibers, glass beads, wood flour, cellulose fibers, mica, metal oxides or metal hydroxides, carbon black, graphite, rock flour, heavy spar, and kaolin.
  • the aqueous solutions of the invention may contain thickening agents.
  • thickening agents include cellulose, cellulose ethers, xanthanes, xanthan gum, starch, modified starch, tragacanth, polyacrylamides, polyethylene glycols, polyaerylic acids, polyv inyl pyrrolidones, and mixtures of any two or more thereof.
  • the P VC stabilized as in the present invention may be brought into the desired shape in a known manner. Examples of processes of this type are grinding, calendering, extruding, injection molding and spinning, and also extrusion blow molding. The stabilized PVC may also be processed to give foams.
  • a PVC stabilized according to the invention is, for example, particularly suitable for hollow articles (bottles), packaging films (thermoformed films), blown films, pipes, foams, heavy profiles (window frames), translucent wall profiles, construction profiles, films (including Luvitherm films), profiles, sidings, fittings, office sheeting and apparatus housings (computers, household devices).
  • Examples of the use of the PVC according to the invention as plastisol are roof cladding, synthetic leather, floor coverings, textile coatings, wall coverings, coil coatings and underfloor sealing for motor vehicles.
  • Examples of sintered PVC applications of the PVC stabilized according to the invention are slush, slush mold and coil coatings for plastisol, semirigid and flexible formulations.
  • Adipic acid obtained from Lanxess
  • Example 1 Preparation of Aqueous Solutions
  • Example 1A Sodium Adipate
  • Example IB Sodium Adipate In situ
  • Example 1C Sodium Adipate In situ
  • Base formulation 100 parts Evipol SH 6030 (S-PVC from Ineos), 0.5 parts Loxiol G 74 (lubricant from Emery), 0.2 parts Complex Ester (lubricant from Emery), 6 parts Impact Modifier MBS type from Kaneka)
  • a dry mixture consisting of the base formulation and the stabilizers as indicated in Table 1 is plasticated on a mixer roll for 5 minutes at 180 C. Subsequently, test samples of 0.2 mm thickness are cut out of the center of the sheet at intervals of 5 minutes and subjected to heat in a Mathis Therrnotester Oven at 190 °C for the time indicated in Table 1. Yellowness Index of the test specimen was then determined in accordance with ASTM D 1925-70, and reported in Table 1. Low values denote minor discoloration, high values denote strong discoloration of the samples. Less discoloration means a more effective stabilizer composition.
  • Table 1 Comparison of aqueous DNA vs. solid DNA in an octyltin stabilizer- containing PVC formulation
  • Example 2 a portion of the octyltin stabilizer from Comparative Example A (Table 1 ) was replaced with either an aqueous DNA solution (Example C) or solid DNA (Comparative Example E).
  • Example C an aqueous DNA solution
  • Comparative Example E solid DNA
  • Equally surprising and unexpected are the results for Example D vs. Comparative Example E.
  • Example D which utilizes DNA aqueous solution, uses a significantly smaller amount of DNA (0.32 mmol) than Comparative Example E ( 1.07) mmol, which utilizes solid DNA, while showing approximately equivalent performance, as measured by YI at 40 minutes (29.66 and 29.52, respectively).
  • Example 3 Continuous Rolling Test [00130] Base formulation: 100 parts Evipol SH 6030 (S-PVC from Ineos), 0.5 parts Loxiol G 74 (lubricant from Emery), 0.2 parts Complex Ester (lubricant from Emery), 6 parts Impact Modifier (MBS type from Kaneka).
  • a dry mixture consisting of the base fomiulation and the stabilizers as indicated in Table 2 is plasticated on a mixer roll for 5 minutes at 180 °C. Subsequently, test samples of 0.3 mm thickness are cut out of the center of the sheet (0.3 mm thickness) at intervals of 5 minutes. YI was measured according to ASTM D 1925-70 at the intervals shown in Table 2. Low values denote minor discoloration, high values denote strong discoloration of the samples. Less discoloration means a more effective stabilizer composition.
  • Table 2 Comparison of aqueous DNA vs. solid DNA in an octyltin stabilizer- containing PVC formulation
  • Example 3 a portion of the octyltin stabilizer in Comparative Example F was replaced with either an aqueous DNA solution (Example H) or solid DNA (Comparative Example J).
  • Example H aqueous DNA solution
  • Comparative Example J solid DNA
  • Equally surprising and unexpected are the results for Example I vs. Comparative Example J.
  • Example I which utilizes DNA aqueous solution, uses a significantly smaller amount of DNA (0.32 mmol) than Comparative Example J (1.07) mmol, which utilizes solid DNA, while showing approximately equivalent performance, as measured by YI at 15 minutes (20.88 and 22.22, respectively).

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Abstract

La présente invention concerne une composition polymère halogénée stabilisée comprenant un polymère halogéné, de préférence du polychlorure de vinyle. La composition contient un stabilisateur d'organotine, de préférence un mercapture d'alkylétain, de préférence encore un ester de mercaptoacide d'alkylétain, et mieux encore un thioglycolate d'alkylétain. La composition comprend également des solutions aqueuses qui contiennent des sels métalliques d'acide polycarboxylique, notamment des solutions aqueuses d'adipate disodique. L'invention concerne également un procédé de stabilisation de polymères halogénés tels que le PVC avec des solutions aqueuses de l'invention. Le procédé consiste à obtenir des solutions aqueuses selon l'invention par dissolution de sels métalliques de l'acide polycarboxylique dans de l'eau ou de l'acide polycarboxylique dans une base aqueuse.
PCT/IB2012/000861 2011-04-18 2012-04-18 Système stabilisateur de polymères pour polymères halogénés Ceased WO2012143794A1 (fr)

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Cited By (5)

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Publication number Priority date Publication date Assignee Title
WO2014154520A1 (fr) * 2013-03-27 2014-10-02 Baerlocher Gmbh Compositions stabilisatrices contenant des sels d'acides dicarboxyliques et des polyols
US20160009896A1 (en) * 2013-03-15 2016-01-14 The Lubrizol Corporation Heavy metal free halogenated polymer compound
CN106566148A (zh) * 2016-10-18 2017-04-19 上海氯碱化工股份有限公司 含有丁二酸二钠的氯化聚氯烯乙树脂组合料
EP2970631B1 (fr) 2013-03-15 2017-05-03 Lubrizol Advanced Materials, Inc. Composition comprennant de chlorure de polyvinyle chloré sans métaux lourds
CN119708725A (zh) * 2024-12-25 2025-03-28 金发科技股份有限公司 一种pvc/abs合金及其制备方法

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160009896A1 (en) * 2013-03-15 2016-01-14 The Lubrizol Corporation Heavy metal free halogenated polymer compound
EP2970631B1 (fr) 2013-03-15 2017-05-03 Lubrizol Advanced Materials, Inc. Composition comprennant de chlorure de polyvinyle chloré sans métaux lourds
US10167376B2 (en) * 2013-03-15 2019-01-01 Lubrizol Advanced Materials, Inc. Heavy metal free halogenated polymer compound
US10202500B2 (en) 2013-03-15 2019-02-12 Lubrizol Advanced Materials, Inc. Heavy metal free CPVC compounds
EP2970630B1 (fr) 2013-03-15 2019-05-08 Lubrizol Advanced Materials, Inc. Composés polymères halogénés exempts de métal lourd
WO2014154520A1 (fr) * 2013-03-27 2014-10-02 Baerlocher Gmbh Compositions stabilisatrices contenant des sels d'acides dicarboxyliques et des polyols
CN106566148A (zh) * 2016-10-18 2017-04-19 上海氯碱化工股份有限公司 含有丁二酸二钠的氯化聚氯烯乙树脂组合料
CN119708725A (zh) * 2024-12-25 2025-03-28 金发科技股份有限公司 一种pvc/abs合金及其制备方法

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