WO1999009094A1 - Beta-hydroxy mercaptans utilises comme costabilisants pour resines halogenees - Google Patents

Beta-hydroxy mercaptans utilises comme costabilisants pour resines halogenees Download PDF

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Publication number
WO1999009094A1
WO1999009094A1 PCT/US1998/017195 US9817195W WO9909094A1 WO 1999009094 A1 WO1999009094 A1 WO 1999009094A1 US 9817195 W US9817195 W US 9817195W WO 9909094 A1 WO9909094 A1 WO 9909094A1
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WIPO (PCT)
Prior art keywords
combination
group
composition according
resin
alkyl
Prior art date
Application number
PCT/US1998/017195
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English (en)
Inventor
Anbazhagan Natesh
Shailesh Shah
Michael P. Connor
William A. Zane
Louis J. Brandewiede
Ronald C. Lafreeda
Robert W. Decker
Original Assignee
Henkel Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Application filed by Henkel Corporation filed Critical Henkel Corporation
Priority to AU91996/98A priority Critical patent/AU9199698A/en
Publication of WO1999009094A1 publication Critical patent/WO1999009094A1/fr

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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
    • C08K5/36—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

Definitions

  • This invention relates to additives for processing halogenated resinous compounds, more particularly to costabilizers that enhance the performance of primary heat stabilizers used to improve the thermal stability of halogenated resins, particularly halogenated vinyl resins, and more particularly, polyvinyl chloride (PVC).
  • costabilizers that enhance the performance of primary heat stabilizers used to improve the thermal stability of halogenated resins, particularly halogenated vinyl resins, and more particularly, polyvinyl chloride (PVC).
  • This invention relates to additives for the processing of halogenated resins, particularly polyvinyl chloride.
  • These type resins are known to undergo rapid thermal degradation under the conditions found in the processes to which these resins are subjected, such as, for example, calendering, extrusion, and injection molding.
  • stabilizers in processing halogenated resins to counteract the harmful effects on resin properties of thermal degradation during processing.
  • polyvinyl chloride is known to undergo a rapid and sequi .tial elimination of hydrochloric acid, or dehydrochlorination., at elevated process temperatures.
  • Other halogenated resins are known to undergo similar dehydrohalogenation reactions.
  • Dehydrochlorination in PVC can initiate at at labile chlorines usually associated with irregularities in the molecular chain, such as branches or double bonds. Once free, the hydrochloric acid further degrades the polyvinyl chloride and can greatly accelerate the rate of degradation through autocatalytic unzipping of the chlorines along the polymer chain.
  • the primary function of heat stabilizers in PVC is to scavenge the free hydrochloric acid and to depress further hydrochloric acid elimination.
  • stabilizing additives have been developed to counteract the thermal degradation of halogenated organic resins.
  • Lead salt stabilizers are widely used for PVC, but are of increasingly limited applicability because of handling and toxicity concerns. They are also unusable in applications requiring transparency.
  • Mixed metal carboxylate soaps of barium, cadmium, calcium, and zinc are also know, but the resulting chlorides are Lewis acids that further encourage degradation, requiring the use of costabilizers such as epoxidized oils, polyols, and organic phosphites.
  • Barium-cadmium, barium-zinc, and calcium-zinc stabilizers also are know, though cadmium compounds are under increasing scrutiny for toxicologies! and cost considerations. These latter stabilizers also give rise to compatibility problems when used in higher concentrations and contribute to poor water and heat resistance in the resins.
  • Typical costabilizers known to the art for enhancing the performance of organometailic primary heat stablizers are sulfur-containing organic ligands having ester functionality. While these known costabilizers can provide excellent heat stability to halogenated organic resins, they typically offer poor resistance to light degradation and poor water resistance due to the ester chemistry. In addition, these costabilizers contribute to odor problems. Thus there remains a need for new, effective costabilizers for halogenated organic resins that avoid the drawbacks associated with the known costabilizers.
  • beta-hydroxy mercaptans unexpectedly improve the performance of primary stabilizers, particularly sulfur-containing organotin and sulfur-containing organoantimony compounds, in the heat stabilization of halogenated resins.
  • the combination provides a stabilizer system which permits more efficient use of primary stabilizers, thus offering resin formulators excellent stabilization at a substantially reduced cost.
  • the combination according to the invention also unexpectedly improves the processing properties of the resins, further providing cost and efficiency improvements to resin processors.
  • the inventive combination also reduces odor problems associated with the processing of resins stabilized thereby and provides increased resistance to resin yellowing associated with thermal degradation.
  • the present invention relates to a novel combination of beta-hydroxy mercaptan costabilizers and primary heat stabilizers for halogenated organic resins, halogenated organic resins containing the novel combination of mercaptan costabilizers and primary stabilizers, and methods of stabilizing halogenated organic resins with the novel combination of primary stabilizers and beta-hydroxymercaptan costabilizers.
  • the novel combination unexpectedly improves the performance of the primary stabilizers and provides unexpected improvement in the processing properties of the halogenated organic resins stabilized thereby.
  • the beta-hydroxy mercaptan costabilizers of the present invention are compounds of the formula wherein R is H or an aikyl, alkoxy, aryl, aryloxy, cycloaliphatic, or cyclooxy aliphatic group having one to twenty carbon atoms and n is 1, 2, 3, or 4.
  • R is C, to C 3U alkyl, more preferably a C 6 to C alkyl group.
  • Particularly preferred as a the costabilizer of the present invention is a 1- mercapto-2-hydroxy ⁇ ropyl ether derived from a C ⁇ to C l0 mixed glycidyl ether.
  • the beta-hydroxy mercaptans according to the invention can be prepared by methods known in the an per se.
  • One method entails reacting an epoxide compound with hydrogen sulfide, usually in an aqueous medium and optionally in the presence of a catalyst such as sodium hydroxide, porous clay, or alumina.
  • a catalyst such as sodium hydroxide, porous clay, or alumina.
  • a C, to C, 0 mixed fatty alcohol is reacted in the presence of a catalyst with epichlorohydrin to form a C, to C Pain mixed glycidyl ether.
  • the glycidyl ether is then reacted with hydrogen sultde in an aqueous medium in the presence of sodium hydroxide catalyst to form the beta-hydroxymercaptoalkyl ether costabilizer.
  • the primary stabilizer in the invention can be any of the primary stabilizers of the classes mentioned above, including lead salts, mixed metal carboxyiate soaps of barium, cadmium, calcium, or zinc, and barium-cadmium, barium-zinc, and calcium-zinc stabilizers.
  • the stabilizer is an organometallic compound of the formula
  • M is a metal having a valence y of 3 or 4
  • L is a reactive sulfur-containing ligand
  • x is less than y and is 1 , 2, or 3.
  • the metal M is tin or antimony
  • the reactive ligand L is selected from the group consisting of alk lthioalkanoate esters and mercaptoalkylalkanoate esters.
  • L is an isooctylthioglycolate or a 2- mercaptoethyloleate group.
  • the primary stabilizer is selected from the group consisting of dimethyltinbis(2-ethylhexylthioglycolate), methyltintris(2-ethyihexylthioglycolate), and mixtures thereof.
  • the primary stabilizer and the costabilizer are combined in a weight ratio that ranges between about 1:2 and about 2:1, preferably b ween about 2:3 and 3:2.
  • organometallic primary stabilizers suitable for use in this invention are disclosed and described in U.S. Patent Nos,: 2,641,588; 2,641,596; 2,680,726, 2,684,956; 2,726,254; 2,789,963; 2,809,956; 2,830,067; 2,855,417; 2,870,119; 2,914,506; 2,998,441; 3,021,302; 3,069,447; 3,126,400; 3,293,273; 3,340,285;
  • the resin used in the present invention can be any organic halogenated resin.
  • organic halogenated resin refers to halogen-containing vinyl and vinylidene polymers or resins in which the halogen is attached directly to the carbon atoms.
  • the polymer is a vinyl halide polymer, more particularly a vinyl chloride polymer.
  • the vinyl chloride polymer is made from monomers consisting of vinyl chloride alone or a mixture of monomers comprising, preferably, at least about 70% by weight based on the total monomer weight of vinyl chloride.
  • the stabilizer/costabilizer combination according to the present invention is added to the halogenated resin in an amount of 0.01 to 10 parts by weight, preferably
  • the stabilzer/costabilizer combination can be incorporated into ihe resin by any one of many known methods that provide for uniform distribution of additives throughout resin compositions, such as, for example, admixing in an appropriate mill or mixer.
  • additives can be added to the halogenated organic resins according to the invention, such as other stabilizers and costabilizers, lubricants, plasticizers, impact modifiers, fillers, pigments, anuoxidants, dyes, ultraviolet light absorbing agents, densifying agents and the like.
  • additives can be added to the resin separately from the stabilizer/costabilizer combination of the present invention, or they can be combined with the stabilizer/costabilizer combination of the invention to form a complete additive package for the halogenated resins.
  • a pressure reactor was charged with 150 ml of isopropyl alcohol, 6 g of sodium hydroxide catalyst in the form of a 49.7% aqueous solution, and 30 ml of deionized water. The reactor contents were then saturated with hydrogen sulfide at a pressure of 35 psi. following saturation with hydrogen sulfide, the reactor was charged over approximately three hours with 315 g of a C, to C, 0 mixed glycidyl ether, commercially available from CVC Specialty Chemicals, Cherry Hill, NJ, as Erisys GE-7, dissolved in isopropyl alcohol. The resulting mixture was allowed to react for approximately two hours at just under 30°C.
  • the vessel was evacuated of hydrogen sulfide using pressurized nitrogen.
  • the reaction mixture was then adjusted to pH 1-3 with concentrated sulfuric acid and stripped of volatiies under vacuum using a nitrogen sparge. After settling overnight, the contents of the reactor were removed to a seperatory funnel and filtered, yielding 284 g of l-mercapto-2-hydroxypropyl C, to C, sanction mixed alkyl ether, having a viscosity of 25 cps (Brookfield DVLT, #2 spindle), Gardner color ⁇ l, and SH alue of 3.51 meq/g.
  • Powdered resin compositions were prepared in accordance with the formulations given in the table below. The quantities are expressed in parts by weight.
  • Stabiol 1079 stabilizer available from Henkei Corp., Ambler, PA
  • TJFT stearic-coated calcium carbonate available from Omya
  • Ca-St 12b calcium stearate available from Ferro Corp.

Abstract

La présente invention concerne une nouvelle combinaison d'un stabilisant et d'un costabilisant permettant d'inhiber la dégradation thermique de résines organiques halogénées, des résines comprenant la combinaison stabilisant/costabilisant, ainsi que des procédés de stabilisation de résines organiques halogénées à l'aide de la combinaison, dans laquelle le costabilisant est un éther beta-hydroxymercaptoalcoylique de la formule R(CH2OCH2CH(OH)CH2SH)n.
PCT/US1998/017195 1997-08-21 1998-08-21 Beta-hydroxy mercaptans utilises comme costabilisants pour resines halogenees WO1999009094A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU91996/98A AU9199698A (en) 1997-08-21 1998-08-21 Beta-hydroxy mercaptans as costabilizers for halogenated resins

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US5647597P 1997-08-21 1997-08-21
US60/056,475 1997-08-21
US13758598A 1998-08-21 1998-08-21
US09/137,585 1998-08-21

Publications (1)

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WO1999009094A1 true WO1999009094A1 (fr) 1999-02-25

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6667357B2 (en) 2000-12-15 2003-12-23 The College Of William And Mary Organic thiol metal-free stabilizers and plasticizers for halogen-containing polymers
US6747081B2 (en) 2000-12-15 2004-06-08 The College Of William And Mary Organic thiol metal-free stabilizers and plasticizers for halogen-containing polymers
US6927247B2 (en) 2000-12-15 2005-08-09 The College Of William And Mary Organic thiol metal-free stabilizers and plasticizers for halogen-containing polymers
US7087193B2 (en) 2000-11-27 2006-08-08 Akzo Nobel N.V. Stabilizer composition for use in polyvinyl chloride formulations having a mixture of at least one organotin sulfide, at least one oranotin chloride, and at least one free mercaptan
US7312266B2 (en) 2000-12-15 2007-12-25 The College Of William And Mary Organic thiol metal-free stabilizers and plasticizers for halogen-containing polymers

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2641588A (en) * 1952-02-07 1953-06-09 Argus Chemical Lab Inc Halogen containing resin stabilized with an organo tin compound
US2726254A (en) * 1950-06-30 1955-12-06 William E Leistner Tin mercaptides
US2809956A (en) * 1953-10-05 1957-10-15 Carlisle Chemical Works Polymeric organo-tin mercapto compounds, method of making same, and halogen-containing resins stabilized therewith
US2914506A (en) * 1953-01-02 1959-11-24 Carlisle Chemical Works Halogen-containing resins stabilized with organo-tin mercapto compounds
US3293273A (en) * 1963-04-09 1966-12-20 M & T Chemicals Inc Organotin mercapto ethylene carboxylates and method for producing same
US3340285A (en) * 1964-04-24 1967-09-05 M & T Chemicals Inc Process for preparing diorgano antimony(iii) carboxylates and mercaptides
US4290942A (en) * 1977-09-30 1981-09-22 Ciba-Geigy Corporation Heat-stabilized chlorine-containing thermoplastic
US4303578A (en) * 1979-04-03 1981-12-01 Ciba-Geigy Corporation Organo-antimony compounds
US4357434A (en) * 1981-03-16 1982-11-02 Ajinomoto Company Incorporated Stabilized halogen-containing resin compositions

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2726254A (en) * 1950-06-30 1955-12-06 William E Leistner Tin mercaptides
US2641588A (en) * 1952-02-07 1953-06-09 Argus Chemical Lab Inc Halogen containing resin stabilized with an organo tin compound
US2914506A (en) * 1953-01-02 1959-11-24 Carlisle Chemical Works Halogen-containing resins stabilized with organo-tin mercapto compounds
US2809956A (en) * 1953-10-05 1957-10-15 Carlisle Chemical Works Polymeric organo-tin mercapto compounds, method of making same, and halogen-containing resins stabilized therewith
US3293273A (en) * 1963-04-09 1966-12-20 M & T Chemicals Inc Organotin mercapto ethylene carboxylates and method for producing same
US3340285A (en) * 1964-04-24 1967-09-05 M & T Chemicals Inc Process for preparing diorgano antimony(iii) carboxylates and mercaptides
US4290942A (en) * 1977-09-30 1981-09-22 Ciba-Geigy Corporation Heat-stabilized chlorine-containing thermoplastic
US4303578A (en) * 1979-04-03 1981-12-01 Ciba-Geigy Corporation Organo-antimony compounds
US4357434A (en) * 1981-03-16 1982-11-02 Ajinomoto Company Incorporated Stabilized halogen-containing resin compositions

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7087193B2 (en) 2000-11-27 2006-08-08 Akzo Nobel N.V. Stabilizer composition for use in polyvinyl chloride formulations having a mixture of at least one organotin sulfide, at least one oranotin chloride, and at least one free mercaptan
US6667357B2 (en) 2000-12-15 2003-12-23 The College Of William And Mary Organic thiol metal-free stabilizers and plasticizers for halogen-containing polymers
US6747081B2 (en) 2000-12-15 2004-06-08 The College Of William And Mary Organic thiol metal-free stabilizers and plasticizers for halogen-containing polymers
US6762231B2 (en) 2000-12-15 2004-07-13 The College Of William And Mary Organic thiol metal-free stabilizers and plasticizers for halogen-containing polymers
US6927247B2 (en) 2000-12-15 2005-08-09 The College Of William And Mary Organic thiol metal-free stabilizers and plasticizers for halogen-containing polymers
US7250457B2 (en) 2000-12-15 2007-07-31 The College Of William And Mary Organic thiol metal-free stabilizers and plasticizers for halogen-containing polymers
US7312266B2 (en) 2000-12-15 2007-12-25 The College Of William And Mary Organic thiol metal-free stabilizers and plasticizers for halogen-containing polymers

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