WO1994016006A1 - Use of monosalicylates of bivalent metals to stabilize chlorine-containing polymers - Google Patents
Use of monosalicylates of bivalent metals to stabilize chlorine-containing polymers Download PDFInfo
- Publication number
- WO1994016006A1 WO1994016006A1 PCT/EP1994/000002 EP9400002W WO9416006A1 WO 1994016006 A1 WO1994016006 A1 WO 1994016006A1 EP 9400002 W EP9400002 W EP 9400002W WO 9416006 A1 WO9416006 A1 WO 9416006A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- salicylate
- metal
- chlorine
- containing polymers
- polymers
- Prior art date
Links
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
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
Definitions
- Polymers containing chlorine such as polyvinyl chloride (PVC) are decomposed under the influence of heat and / or light, which leads to undesirable discoloration and impairment of the properties of use.
- PVC polyvinyl chloride
- stabilizers are added to the polymers.
- these stabilizers still predominantly contain organic and inorganic compounds of lead. This applies above all to applications with high long-term requirements with regard to weathering and thermal stability, such as window and roller shutter profiles and cables, where basic lead salts such as basic lead sulfate or basic lead phosphite are still predominantly used.
- these lead compounds are e.g. Metal barium and cadmium soaps combined to form highly effective stabilizers.
- example 32 it is known to also use calcium salicylate in a stabilizer mixture for PVC composed of zinc stearate, sorbitol and the thioglycolate of bishydroxymethyl-1,4-cyclohexane.
- this calcium salicylate is a conventional calcium salicylate of the formula Ca (salicylate) 2, ie calcium to salicylate is contained in a molar ratio of 1: 2 in this compound. Even these complex assemblies Stabilizer mixtures do not meet the desired requirements.
- the object of the present invention is to overcome the above-mentioned disadvantages of the prior art by using stabilizers which have not yet been used.
- This object is achieved according to the invention by using at least one optionally substituted salicylate of at least one divalent metal, where salicylate and metal are present in a molar ratio of about 1: 1, for stabilizing chlorine-containing polymers against degradation by heat and light.
- the salicylates of divalent metals used according to the invention are in a molar ratio of 1: 1, i.e. only one salicylate residue is present on a divalent metal cation.
- the salicylates of divalent metals used according to the invention are therefore monosalicylates - in contrast to the usual disalicylates.
- the special metal salicylates used according to the invention are particularly suitable for stabilizing chlorine-containing polymers against degradation by heat and light.
- the metal salicylates used according to the invention can be prepared by methods known per se, cf. e.g. Babko, A.K. and Ertushenko, N.P., Ukr. Khi. Zh 1969, pp. 295-302.
- the metal salicylates used according to the invention are presumably in form I at 105 ° C.
- the metal salicylates used according to the invention can be prepared, for example, by reacting salicylic acid with the corresponding metal hydroxide in a molar ratio of 1: 1.
- the acid component used for the reaction can be salicylic acid (2-hydroxybenzoic acid) or a salicylic acid substituted in the 3-, 4-, 5- or 6-position; the substituents can, for example, be selected from the group consisting of hydroxyl, alkyl and aryl, it being possible for the substituents to contain further functional groups, such as oxygen, sulfur and nitrogen.
- the metals contained in the metal salicylates used according to the invention can be, for example, alkaline earth metals or Be zinc, with magnesium, calcium, strontium and zinc, and in particular calcium and zinc being preferred; combinations of two or more of these divalent metals can also be used.
- the metal salicylates used according to the invention are generally added to the chlorine-containing polymer to be stabilized in amounts of 0.5 to 5 parts by weight per 100 parts by weight of chlorine-containing polymer.
- the metal salicylates used according to the invention can be surface-treated for better incorporation into the chlorine-containing polymers to be stabilized.
- the metal salicylates used according to the invention can be used to stabilize chlorine-containing polymers, in particular to stabilize polymers of vinyl chloride and especially to stabilize PVC. Furthermore, the metal salicylates used according to the invention can be used in graft polymers or mixtures consisting of different polymers.
- the chlorine-containing polymers to be stabilized can be produced both by mass, suspension and emulsion polymerization processes and copolymers of vinyl chloride with e.g. Vinyl acetate, vinylidene chloride, vinyl ether, acrylonitrile, acrylic acid ester, maleic acid, mono- or di-ester or olefins.
- vinyl chloride e.g. Vinyl acetate, vinylidene chloride, vinyl ether, acrylonitrile, acrylic acid ester, maleic acid, mono- or di-ester or olefins.
- the metal salicylates used according to the invention can be combined with other heat, light and anti-aging agents.
- Such compounds which are usually used as additives, for example for PVC, can be, for example: compounds of metals, such as alkaline earth metals and / or zinc, for example monocarboxylates of Cs to C3o carboxylic acids, which may also contain basic fractions; Oxides or hydroxides of metals, for example calcium hydroxide or zinc oxide, hydrotalkites, basic Ca / Al compounds, zeolites or tin-containing stabilizers; further organic stabilizers, such as 1,3-diketones (eg dibenzoylmethane) or their metal salts, polyols (eg dipentaerythritol), isocyanurates (tris-hydroxyethyl isocyanurate), dihydropyridines and phosphites can be used.
- compounds of metals such as alkaline earth metals and / or zinc, for example monocarboxylate
- additives usually used such as fillers (e.g. chalk, anhydrite), pigments (e.g. Ti0 2 and / or zinc sulfide), flame retardants (e.g. magnesium hydroxide, aluminum hydroxide and / or antimony trioxide), reinforcing agents (e.g. glass fibers and / or talc) and plasticizers (eg di-2-ethylhexyl phthalate and / or diisodecyl phthalate).
- fillers e.g. chalk, anhydrite
- pigments e.g. Ti0 2 and / or zinc sulfide
- flame retardants e.g. magnesium hydroxide, aluminum hydroxide and / or antimony trioxide
- reinforcing agents e.g. glass fibers and / or talc
- plasticizers eg di-2-ethylhexyl phthalate and / or diisodecyl phthalate.
- lubricants such as paraffin waxes, low molecular weight polyolefins, ester lubricants made from mono- or polyvalent alcohols and mono- or dicarboxylic acids or amide waxes can be added to the chlorine-containing polymers.
- additives such as e.g. Antioxidants, sterically hindered amines, optical brighteners, epoxides and sulfur-containing compounds, in particular the sulfur-containing organic compounds which are used for the production of tin-containing stabilizers, are added in order to achieve or to enhance the desired properties of the chlorine-containing polymers.
- compositions labeled "B” are compositions stabilized according to the invention, while the compositions labeled “V” are comparative compositions not stabilized according to the invention.
- the compositions given in the tables were rolled in countercurrent on a two-roll mill (Collin roll) at 180 ° C. After 5 minutes the rolled skin was removed and its HCl stability determined in the Congo test. The fur was cut into strips that were stored in a Mathis oven at 200 ° C. The initial color and the gradient were checked on these strips.
- Alkamizer 1 (hydrotalkite, Kyowa) 4, 0 - 2, 5
- A.lkamizer 1 (hydrotalkite, Kyowa) 2.0 1.0
- a 10% by weight aqueous Ca (OH) 2 suspension (1 mol Ca (OH)) is heated to 50 ° C. 1 mol of salicylic acid is then added slowly with stirring so that the pH of the suspension does not fall below 11.5.
- the reaction product is filtered off and dried at 105 ° C.
- the product can be dewatered by further drying at about 170 ° C.
- the product dried to 105 ° C is presumably Form I given above and the product dried to 170 ° C is Form II given above.
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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
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP94904616A EP0677081A1 (en) | 1993-01-04 | 1994-01-03 | Use of monosalicylates of bivalent metals to stabilize chlorine-containing polymers |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEP4300059.2 | 1993-01-04 | ||
DE19934300059 DE4300059C1 (en) | 1993-01-04 | 1993-01-04 | Use of monosalicylates of divalent metals to stabilize chlorine-containing polymers |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1994016006A1 true WO1994016006A1 (en) | 1994-07-21 |
Family
ID=6477724
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1994/000002 WO1994016006A1 (en) | 1993-01-04 | 1994-01-03 | Use of monosalicylates of bivalent metals to stabilize chlorine-containing polymers |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP0677081A1 (en) |
DE (1) | DE4300059C1 (en) |
WO (1) | WO1994016006A1 (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19627258C2 (en) * | 1996-07-08 | 2001-04-12 | Chemson Polymer Additive | Process for producing a fusible stabilizer combination |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB808718A (en) * | 1956-03-15 | 1959-02-11 | Nopco Chem Co | Asbestos-containing vinyl floor tiles and compositions therefor |
FR2075302A5 (en) * | 1970-01-07 | 1971-10-08 | Cincinnati Milacron Chem | |
FR2207904A1 (en) * | 1972-11-22 | 1974-06-21 | Ciba Geigy Ag | |
JPH04161442A (en) * | 1990-10-24 | 1992-06-04 | Sakai Chem Ind Co Ltd | Chlorine-containing resin composition |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2459816A1 (en) * | 1979-06-26 | 1981-01-16 | Rhone Poulenc Ind | IMPROVED METHOD FOR THE THERMAL STABILIZATION OF POLYVINYL CHLORIDE COMPOSITIONS |
-
1993
- 1993-01-04 DE DE19934300059 patent/DE4300059C1/en not_active Expired - Fee Related
-
1994
- 1994-01-03 EP EP94904616A patent/EP0677081A1/en not_active Ceased
- 1994-01-03 WO PCT/EP1994/000002 patent/WO1994016006A1/en not_active Application Discontinuation
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB808718A (en) * | 1956-03-15 | 1959-02-11 | Nopco Chem Co | Asbestos-containing vinyl floor tiles and compositions therefor |
FR2075302A5 (en) * | 1970-01-07 | 1971-10-08 | Cincinnati Milacron Chem | |
FR2207904A1 (en) * | 1972-11-22 | 1974-06-21 | Ciba Geigy Ag | |
JPH04161442A (en) * | 1990-10-24 | 1992-06-04 | Sakai Chem Ind Co Ltd | Chlorine-containing resin composition |
Non-Patent Citations (1)
Title |
---|
DATABASE WPI Week 9229, Derwent World Patents Index; AN 92-238578 * |
Also Published As
Publication number | Publication date |
---|---|
EP0677081A1 (en) | 1995-10-18 |
DE4300059C1 (en) | 1994-06-23 |
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