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WO2002094927A1 - Pvc souple plastifie au citrate stabilise - Google Patents

Pvc souple plastifie au citrate stabilise Download PDF

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Publication number
WO2002094927A1
WO2002094927A1 PCT/EP2002/005206 EP0205206W WO02094927A1 WO 2002094927 A1 WO2002094927 A1 WO 2002094927A1 EP 0205206 W EP0205206 W EP 0205206W WO 02094927 A1 WO02094927 A1 WO 02094927A1
Authority
WO
WIPO (PCT)
Prior art keywords
flexible pvc
pvc according
citrate
pvc
sheets
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/EP2002/005206
Other languages
English (en)
Inventor
Karl-Josef Kuhn
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Galata Chemicals GmbH
Original Assignee
Crompton Vinyl Additives GmbH
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.)
Filing date
Publication date
Priority claimed from DE10129857A external-priority patent/DE10129857A1/de
Application filed by Crompton Vinyl Additives GmbH filed Critical Crompton Vinyl Additives GmbH
Publication of WO2002094927A1 publication Critical patent/WO2002094927A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/11—Esters; Ether-esters of acyclic polycarboxylic 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • 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
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1515—Three-membered rings

Definitions

  • the present invention relates to flexible PVC (polyvinyl chloride) stabilized by epoxy compounds and perchlorates using citrate plasticizers, a process for its preparation, and its use.
  • PVC polyvinyl chloride
  • PVC can be stabilized by a number of additives.
  • Heavy-metal compounds of lead and cadmium are particularly suitable, but are objectionable today for ecological reasons due to their heavy metal content (cf. "Plastics Additives", R. Gachter and H. M ⁇ ller (editors), Hanser Verlag, Kunststoff, Vienna, New York, 3rd edition, 1990, pages 287-295, and Kunststoff Handbuch PVC, Volumes 1 and 2, Beck/Braun, Carl Hanser Verlag, Kunststoff).
  • Epoxy compounds have long been known as co-stabilizers for PVC. Epoxidized soybean oil is frequently used (cf., for example, "Plastics Additives", R. Gachter and H. M ⁇ ller (editors), Hanser Verlag, 3rd edition, 1990, pages 303/4, and US-3,928,267).
  • PVC Epoxidized soybean oil
  • glycidyl ethers of novolak resins as stabilizers is also described, for example, in DE-A-34 02 408 and EP-A-0 677 551 and EP- A-0 677 550.
  • DE 35 46 725 C2 relates to polyvinyl chloride compositions comprising citrate esters as plasticizers, and a process for its preparation. These respectively contain Ca/Zn stabilizers.
  • R respectively represents a straight- or branched-chain alkyl residue having from 4 to 18 carbon atoms, and R a represents H or CH3-CO-.
  • Ri and R 3 are hydrogen
  • R 2 is hydrogen or methyl, and n equals 0;
  • Ri and R 3 together form -CH 2 -CH 2 - or -CH 2 ⁇ CH 2 -CH 2 -, R 2 is hydrogen, and n is 0 or 1; the epoxy residue being directly bound to a carbon, oxygen, nitrogen or sulfur atom.
  • it may also contain additional organic or inorganic zinc compounds and/or tin compounds, such as Zn stearate, Zn oleate, Zn octoate, Zn acetate, Zn citrate, ZnCI 2 and/or dimethyl-, dibutyl-, dioctyl-, didodecyltin thioglycolates or tin carboxylates.
  • additional organic or inorganic zinc compounds and/or tin compounds such as Zn stearate, Zn oleate, Zn octoate, Zn acetate, Zn citrate, ZnCI 2 and/or dimethyl-, dibutyl-, dioctyl-, didodecyltin thioglycolates or tin carboxylates.
  • the Japanese unexamined Patent Publication JP Hei 3-122149 proposes a rigid PVC composition which contains solid epoxides and perchlorates.
  • citrate-plasticized flexible PVC stabilized by a mixture of a perchlorate and a terminal epoxide has an excellent thermal stability with a good initial color and color preservation.
  • the citrate-plasticized flexible PVC stabilized according to the invention meets the high requirements which are met, for example, by PVC stabilized with barium/zinc compounds. It is to be pointed out that excellent storage stability and light stability are achieved. Further, a good stabilization is achieved independently of the state of aggregation of the epoxide, i.e., liquid terminal epoxides may also be employed without disadvantage.
  • a citrate plasticizer can often be used in a reduced quantity while the properties of the plasticized polymer remain comparable.
  • the flexible PVC according to the invention does not contain any lead or cadmium compounds.
  • "flexible PVC” means PVC mixtures which contain at least one citrate plasticizer in an amount sufficient to achieve properties of flexible PVC.
  • PVC having a freezing temperature of more than 70 °C is not considered a flexible PVC according to the invention.
  • flexible PVC according to the invention is defined by being suitable for the preparation of flexible PVC molded parts due to its plasticizer content.
  • plasticizer content include, in particular, cable and wire coatings, roof sheets, book sheets, decorative sheets, foams, agrarian sheets, office sheets, automotive sheets (also foam-backed with polyurethane), flexible tubes, sealing profiles and the like.
  • PVC component for the compositions according to the invention are blends, copolymers or graft polymers of PVC with polymerizable compounds, such as acrylonitrile, vinyl acetate, or (co)polymers such as ABS, which may be suspension, bulk or emulsion polymers and their mixtures.
  • examples of such components (a) include compositions comprising (i) from 20 to 80 weight parts of a vinyl chloride homopolymer (PVC), and (ii) from 80 to 20 weight parts of at least one thermoplastic copolymer based on styrene and acrylonitrile, especially selected 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.
  • ASA acrylate- based styrene-acrylonitrile copolymers
  • flexible PVC which contains (i) 100 weight parts of PVC and (ii from 0 to 300 weight parts of ABS and/or SAN- modified ABS, and from 0 to 80 weight parts of the copolymers NBR, NAR and/or EVA, but especially EVA, and from 3 to 60 weight parts of citrate plasticizer per 100 weight parts of (i) and (ii).
  • C4-C14 alkanols which may be branched or unbranched and whose alkanol residues may be the same or different, linear ones being particularly preferred.
  • mixtures of different plasticizers may also be used.
  • mixtures of plasticizers there may be used, in particular, those disclosed, for example, in EP-A-0 677 551, which is included herein by reference.
  • Such additional plasticizers include, for example, phthalic acid esters, esters of aliphatic dicarboxylic acids, trimellitic acid esters, epoxy plasticizers, polymer plasticizers, phosphoric acid esters, chlorinated hydrocarbons, and paraffins, hydrocarbons, monoesters, glycol esters as mentioned in EP 0 677 551 or in "Plastics Additives", R. Gachter and H. M ⁇ ller (editors), Hanser Verlag, 1990, page 284, chapters 5.9.14.2 and 5.9.14.1, and "PVC Technology", W.V. Titow (editor), 4th edition, Elsevier Publishers, 1984, pages 171-173, chapter 6.10.2, page 174, chapter 6.10.5, page 173, chapter 6.10.3, and pages 173-174, chapter 6.10.4.
  • Perchlorates include, for example, phthalic acid esters, esters of aliphatic dicarboxylic acids, trimellitic acid esters, epoxy plasticizers, polymer
  • the perchlorates mentioned above as component (b) correspond to the formula M(CIO 4 ) n , wherein M represents H, Na, K, Mg, Ca, Ba or Al, and n corresponds to the valence of M.
  • the respective perchlorate may be employed in different usual dosage forms, for example, as a salt or aqueous or organic solution, or charged onto a carrier material, such as PVC, Ca silicate, chalk, zeolites or hyd rota I cites, or incorporated into a hydrotalcite by a chemical reaction, or dissolved in the plasticizer itself.
  • a carrier material such as PVC, Ca silicate, chalk, zeolites or hyd rota I cites, or incorporated into a hydrotalcite by a chemical reaction, or dissolved in the plasticizer itself.
  • They may be employed in an amount of, for example, from 0.001 to 5, conveniently from 0.01 to 3, more preferably from 0.01 to 2.0 weight parts, based on 100 weight parts of PVC.
  • the terminal epoxy compounds (c) which can be used according to the invention may have an aliphatic, aromatic, cycloaliphatic, araliphatic or heterocyclic structure; they contain epoxy groups as pendant groups.
  • the epoxy groups are preferably linked to the residual molecule as glycidyl groups through ether or ester linkages, or they are N-glycidyl derivatives of heterocyclic amines, amides or imides. Epoxy compounds of these types are generally known and commercially available.
  • the epoxy compounds contain at least one epoxy residue of formula II
  • Ri and R 3 are both hydrogen, R 2 is hydrogen or methyl, and n equals 0; or wherein Ri and R 3 together form -CH 2 -CH 2 - or -CH 2 -CH 2 - CH 2 -, R 2 is hydrogen, and n is 0 or 1; the epoxy residue being directly bound to a carbon, oxygen, nitrogen or sulfur atom.
  • epoxy compounds are known to the skilled person from EP 0 506 617 A, which is included herein by reference.
  • the citrate-plasticized flexible PVC stabilized according to the invention may contain further additives.
  • these include, for example, fillers and reinforcing agents (such as calcium carbonate, silicates, glass fibers, talcum, china clay, chalk, mica, metal oxides and hydroxides, carbon black or graphite), metal soaps (such as zinc octoate/stearate or calcium stearate) and other metal stabilizers (dialkyltin thioglycolates or dialkyltin carboxylates, for example, T22, 17MOK, T9, T4 or T7, all of which are products of the Crompton Vinyl Additives GmbH), antioxidants, polyols, zeolites, dawsonites, hydrotalcites, organic phosphites, 1,3-diketo compounds, dihydropyridines, phenylindoles, pyrroles, ⁇ -naphthol, hydroxydiphenylamines, sterically hindered amines (H
  • a mixture of zinc, tin, alkaline earth, aluminum, lanthanum or lanthanoide compounds of different structures may be employed.
  • organic zinc, tin, aluminum, lanthanum or lanthanoide compounds may be coated onto a support, such as alumosalt compounds; see also DE-A- 40 31 818, which is included herein by reference.
  • Suitable organotin compounds are described in US 4,743,640 (columns 3-5), which is included herein by reference.
  • a stabilized citrate-plasticized flexible PVC containing from 0.001 to 5.0 parts per 100 parts of PVC of a perchlorate or perchloric acid, and from 0.1 to 50 parts per 100 parts of PVC of a terminal epoxy compound, and optionally an antioxidant, especially from 0.01 to 10.0 parts per 100 parts of PVC. Further preferred is a stabilized citrate-plasticized flexible PVC containing an alkali metal perchlorate as component (b).
  • a stabilized citrate-plasticized flexible PVC containing a terminal epoxy compound comprising an aromatic group, especially a bisphenol derivative, as component (c).
  • a stabilized citrate-plasticized flexible PVC containing (b) from 0.001 to 3.0 parts per 100 parts of PVC of a perchlorate, and (c) from 0.1 to 5.0 parts per 100 parts of PVC of a terminal epoxy resin.
  • a stabilized citrate-plasticized flexible PVC which additionally contains pigments and/or fillers, especially chalk.
  • a stabilized citrate-plasticized flexible PVC which additionally contains one or more metal soaps, especially zinc soaps.
  • a stabilized citrate-plasticized flexible PVC which has been foamed by chemical or mechanical blowing agents and additionally contains several metal soaps, especially zinc soaps.
  • a stabilized citrate-plasticized flexible PVC which additionally contains at least one additive selected from the group consisting of disaccharide alc ⁇ f ⁇ ols, organic phosphites, zeolites, hydrotalcites, dawsonites, aminocrotonates, polyols, diketones, pyrroles, ⁇ -naphthol or dihydropyridines.
  • a stabilized citrate-plasticized flexible PVC which additionally contains a sterically hindered amine, especially from 0.01 to 5 parts per 100 parts of PVC.
  • a stabilized citrate-plasticized flexible PVC which optionally contains an organic or inorganic Zn compound, such as Zn stearate, Zn oleate, Zn octoate, Zn acetate, Zn citrate and/or ZnCI 2 .
  • an organic or inorganic Zn compound such as Zn stearate, Zn oleate, Zn octoate, Zn acetate, Zn citrate and/or ZnCI 2 .
  • a stabilized citrate-plasticized flexible PVC which optionally contains an organic tin compound, such as dialkyltin carboxylates or dialkyltin thioglycolates.
  • the perchlorates or perchloric acids are preferably employed in combination with a terminal epoxy compound for stabilizing PVC.
  • a terminal epoxy compound for stabilizing PVC e.g., PVC, PVC, PVC, PVC, PVC, PVC, PVC, PVC, PVC, PVC, PVC, PVC, PVC, PVC, PVC, PVC, PVC, PVC, PVC, PVC, PVC, PVC, the above illustrated preferences apply, and also, one of the above described further components may be additionally employed.
  • the citrate-plasticized flexible PVC stabilized according to the invention can be prepared in a per se known manner by mixing the stabilizers mentioned and optionally further additives with the PVC using per se known devices, such as calenders, mixers, kneaders, extruders, dissolvers and the like.
  • the stabilizers may be added singly or in admixture, or also in the form of so-called master batches.
  • the invention also relates to a process for the preparation of stabilized citrate-plasticized flexible PVC, characterized by mixing components (b) and (c) and optionally further additives with the PVC using devices such as calenders, mixers, kneaders, extruders, dissolvers and the like.
  • the citrate-plasticized flexible PVC stabilized according to the invention can be formed into the desired shape in a per se known manner. Such methods include, for example, milling, calendering, extruding, injection- molding, sintering or spinning, and also extrusion-blowing or processing by the plastisol method.
  • the stabilized citrate-plasticized flexible PVC can also be processed into foams.
  • the citrate-plasticized flexible PVC stabilized according to the invention is particularly suitable for flexible formulations, especially in the form of wire coatings, cable insulations, decorative sheets, foams, agrarian sheets, flexible tubes, sealing profiles and office sheets, and for automotive applications.
  • a citrate-plasticized flexible PVC composition was prepared by mixing the individual components according to the following Tables (quantities stated in weight parts).
  • the components (PVC powder, plasticizer, stabilizer mixture, additives etc.) were homogenized using a plastisol mixer (dissolver) for about 3 minutes and coated onto release liner using a coating knife to give 0.5 mm thick films, and gelled to solid sheets in a Mathis oven at 190 °C for 3 min. These were subjected to a static heat test or other methods for determining thermal stability in the known manner.
  • VDE test Another determination of long-term stability was effected by establishing the thermal stability according to DIN VDE 0472.
  • the specimen was placed into a glass tube sealed at the bottom (AR glass supplied by Peco-Labor site GmbH, Darmstadt), heated in an oil bath at 200 °C, and the time was determined at which a visible reddening (corresponding to a pH value of 3) of the pH universal indicator paper was observed.
  • DHC test dehydrochlorination test
  • PVC sheets of dimensions 10 x 10 x 2 mm were prepared. Then, they were stored in an oven at a defined temperature of between 100 and 132 °C ( ⁇ 0.5 °C) for a respectively defined time (3, 7, 14 days), and their consistency was determined, or they were subjected to the above described dehydrochlorination test. Permanent rolling test
  • the PVC mixture was rolled at a temperature of 180 °C on a rolling mill having a gap width of 0.5 mm, and every 5 minutes, a sample was taken, and its yellowness index, YI, was measured after cooling.
  • Linplast ® 68 CT supplied by Condea
  • diisononyl phthalate diisononyl phthalate
  • bisphenol-A diglycidyl ether Aldit ® GY 250, supplied by Ciba
  • Linplast ® 68 CT linear 6,8-alcohol citrate ester

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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)

Abstract

En utilisant un perchlorate et un composé époxyde terminal, on obtient un PVC souple plastifié au citrate à forte stabilisation.
PCT/EP2002/005206 2001-05-18 2002-05-11 Pvc souple plastifie au citrate stabilise Ceased WO2002094927A1 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
DE10124711.7 2001-05-18
DE10124711 2001-05-18
DE10124255 2001-05-18
DE10124255.7 2001-05-18
DE10129857A DE10129857A1 (de) 2001-05-18 2001-06-21 Stabilisiertes citratweichgemachtes Weich-PVC
DE10129857.9 2001-06-21

Publications (1)

Publication Number Publication Date
WO2002094927A1 true WO2002094927A1 (fr) 2002-11-28

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PCT/EP2002/005206 Ceased WO2002094927A1 (fr) 2001-05-18 2002-05-11 Pvc souple plastifie au citrate stabilise

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WO (1) WO2002094927A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112494116A (zh) * 2020-11-26 2021-03-16 鹰潭荣嘉集团医疗器械实业有限公司 一次性使用动静脉穿刺器
CN114605758A (zh) * 2022-04-24 2022-06-10 苏州华苏塑料有限公司 用于地暖地板的pvc耐磨层及其制备方法、地暖地板
EP4180569A1 (fr) 2021-09-16 2023-05-17 Benecke-Kaliko AG Films en pvc souple a faible souillure de cafe

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1508345A (fr) * 1966-11-24 1968-01-05 Composition de résines vinyliques, notamment pour pellicules rétractables
DE3520750A1 (de) * 1984-06-11 1986-02-06 Morflex Chemical Co., Inc., Greensboro, N.C. Verfahren zur herstellung von citratestern und deren verwendung fuer medizinische artikel
JPH06192523A (ja) * 1992-10-14 1994-07-12 Kureha Chem Ind Co Ltd 塩化ビニリデン系共重合体組成物
US5492949A (en) * 1993-04-16 1996-02-20 Ciba-Geigy Corporation Stabilized polyvinyl chloride
US5846601A (en) * 1993-07-21 1998-12-08 Henkel Kommanditgesellschaft Auf Aktien Use of selected polyvinyl acetate dispersions for the surface stabilization of sand and/or soil

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1508345A (fr) * 1966-11-24 1968-01-05 Composition de résines vinyliques, notamment pour pellicules rétractables
DE3520750A1 (de) * 1984-06-11 1986-02-06 Morflex Chemical Co., Inc., Greensboro, N.C. Verfahren zur herstellung von citratestern und deren verwendung fuer medizinische artikel
JPH06192523A (ja) * 1992-10-14 1994-07-12 Kureha Chem Ind Co Ltd 塩化ビニリデン系共重合体組成物
US5492949A (en) * 1993-04-16 1996-02-20 Ciba-Geigy Corporation Stabilized polyvinyl chloride
US5846601A (en) * 1993-07-21 1998-12-08 Henkel Kommanditgesellschaft Auf Aktien Use of selected polyvinyl acetate dispersions for the surface stabilization of sand and/or soil

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 199432, Derwent World Patents Index; Class A14, AN 1994-260689, XP002215394 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112494116A (zh) * 2020-11-26 2021-03-16 鹰潭荣嘉集团医疗器械实业有限公司 一次性使用动静脉穿刺器
EP4180569A1 (fr) 2021-09-16 2023-05-17 Benecke-Kaliko AG Films en pvc souple a faible souillure de cafe
EP4180569B1 (fr) * 2021-09-16 2025-03-26 Benecke-Kaliko AG Films en pvc souple a faible souillure de cafe
CN114605758A (zh) * 2022-04-24 2022-06-10 苏州华苏塑料有限公司 用于地暖地板的pvc耐磨层及其制备方法、地暖地板

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