Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
  • C07F5/06—Aluminium compounds
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C63/00—Compounds having carboxyl groups bound to a carbon atoms of six-membered aromatic rings
  • C07C63/14—Monocyclic dicarboxylic acids
  • C07C63/15—Monocyclic dicarboxylic acids all carboxyl groups bound to carbon atoms of the six-membered aromatic ring
  • C07C63/26—1,4 - Benzenedicarboxylic acid
  • C07C63/28—Salts thereof
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C55/00—Saturated compounds having more than one carboxyl group bound to acyclic carbon atoms
  • C07C55/02—Dicarboxylic acids
  • C07C55/08—Malonic acid
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C55/00—Saturated compounds having more than one carboxyl group bound to acyclic carbon atoms
  • C07C55/02—Dicarboxylic acids
  • C07C55/10—Succinic acid
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C55/00—Saturated compounds having more than one carboxyl group bound to acyclic carbon atoms
  • C07C55/02—Dicarboxylic acids
  • C07C55/14—Adipic acid
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
  • C07C57/02—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
  • C07C57/13—Dicarboxylic acids
  • C07C57/145—Maleic acid
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
  • C07C57/02—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
  • C07C57/13—Dicarboxylic acids
  • C07C57/15—Fumaric acid
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C63/00—Compounds having carboxyl groups bound to a carbon atoms of six-membered aromatic rings
  • C07C63/14—Monocyclic dicarboxylic acids
  • C07C63/15—Monocyclic dicarboxylic acids all carboxyl groups bound to carbon atoms of the six-membered aromatic ring
  • C07C63/16—1,2 - Benzenedicarboxylic acid
  • C07C63/20—Salts thereof
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C63/00—Compounds having carboxyl groups bound to a carbon atoms of six-membered aromatic rings
  • C07C63/14—Monocyclic dicarboxylic acids
  • C07C63/15—Monocyclic dicarboxylic acids all carboxyl groups bound to carbon atoms of the six-membered aromatic ring
  • C07C63/24—1,3 - Benzenedicarboxylic acid
• • 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

• the invention relates to basic
• Calcium aluminum hydroxide dicarboxylates a process for their preparation and their use as stabilizers for halogen-containing thermoplastic resins, in particular polyvinyl chloride.
• Thermoplastic, halogen-containing resins, especially PVC, are unstable to the effects of heat and light. So occurs already in the processing of z. B. unstabilized PVC thermal degradation of the resin. This manifests itself in a discoloration of the molded part and in the deterioration of the mechanical properties.
• heat stabilizers into the resin composition.
• organic and / or inorganic compounds of the metals lead, barium, cadmium, calcium, tin and zinc are usually added alone or in combinations.
• Other costabilizers such as epoxies, organic sulfur compounds, polyols and phosphites are also added.
• Basic lead compounds are preferably used to stabilize PVC articles such as pipes, plates, profiles and cable insulation.
• the most common basic lead compounds are of the sulfate, phosphite or stearate type.
• DE-PS 12 19 223 and DE-OS 24 19 379 teach that PVC cable insulation should preferably be stabilized with 2-basic lead phthalate, since this connection gives the cable excellent electrical properties.
• EP-A-0 313 113 mentions that 4-basic lead fumarate is the most effective basic lead compound for stabilizing soft-set halogen-containing vinyl polymer compositions. According to EP-A-0 319 086, 5-basic lead fumarate gives PVC moldings greater stability and a better degree of whiteness than other known lead stabilizers.
• FR-A 2 403 362 describes how to stabilize soft PVC for cable insulation with a mixture of calcium-zinc fatty acids, sorbitol and a ⁇ -diketone.
• EP-A-0256 872 describes the use of hydrotalkite and a diketone for stabilizing PVC resins.
• Alkaline alumosilicates in connection with other costabilizers for use in PVC have also been proposed (DE-A-31 13 442).
• all non-toxic stabilization systems proposed so far have disadvantages compared to stabilizers containing heavy metals. In this way, they usually do not achieve the required long-term stability. A good initial color and sufficient color retention can only be achieved by using large amounts of expensive "color improvers”.
• the metal-containing costabilizers hydrotalkite and zeolite are disadvantageous in that they split off volatile constituents at the processing temperatures necessary for the processing of, for example, PVC, which leads to the formation of bubbles in the molded part.
• PVC moldings stabilized with, for example, polyol and / or zeolite absorb water, which leads to considerable problems in further processing.
• A is an aliphatic, aromatic or heteroaromatic dicarboxylic acid anion or combinations thereof;
• the invention has for its object to provide new compounds and a process for their preparation, which are particularly suitable as a stabilizer for halogen-containing polymers, without having the above-mentioned disadvantages of the known stabilizers, in particular as non-toxic.
• A is an aliphatic, aromatic or heteroaromatic dicarboxylic acid anion or combinations thereof.
• x preferably denotes 2-8, particularly preferably 3-6 and m preferably denotes 2-4.
• the dicarboxylic acid anions indicated with A are derived, for example, from malonic acid, succinic acid, Adipic acid, fumaric acid, maleic acid, phthalic acid, isophthalic acid, terephthalic acid and pyridinedicarboxylic acids.
• the fumarate and phthalate anions are preferred dicarboxylic acid anions.
• the calcium aluminum hydroxide dicarboxylates according to the invention give halogen-containing, thermoplastic resins and the moldings produced therefrom, comparable heat stability to basic lead compounds.
• the initial colors and the color retention of e.g. Rigid PVC moldings which are stabilized with one of the new compounds according to the invention are equivalent to the same moldings which contain known non-toxic stabilizer systems.
• the object on which the invention is based is, on the other hand, achieved by a process for the preparation of the calcium aluminum hydroxide dicarboxylates according to the invention, which is characterized in that mixtures of calcium hydroxide and / or oxide, aluminum hydroxide and sodium hydroxide or of calcium hydroxide and / or oxide and reacting sodium aluminate with the corresponding dicarboxylic acid in amounts corresponding to the preparation of the desired compounds in an aqueous medium, and the reaction product is separated off and recovered in a manner known per se.
• the reaction product obtained directly from the above-described reaction can be separated from the aqueous reaction medium by known processes, preferably by filtration.
• the separated reaction product is also worked up in a manner known per se Way, for example by washing the filter cake with water and drying the washed residue at temperatures of, for example, 60-130 ° C., preferably at 90-120 ° C.
• Both a finely divided, active aluminum hydroxide in combination with sodium hydroxide and a sodium aluminate can be used for the reaction.
• Calcium can be used in the form of finely divided calcium oxide or hydroxide or mixtures thereof.
• reaction temperatures are preferably between about 25 and 100.degree. C., more preferably between about 40 and 85.degree. C.
• Catalysts or accelerators are not required, but can optionally be used.
• the water of crystallization can be removed completely or partially by thermal treatment.
• the compounds according to the invention can be coated in a known manner with surface-active agents.
• the calcium aluminum hydroxide dicarboxylates according to the invention can contain halogen-containing, thermoplastic resins are stabilized.
• Particularly suitable for this purpose are polyvinyl chlorides, homopolymers and copolymers thereof, and mixtures thereof with other polymers, such as ABS (copoly er from acrylonitrile / butadiene / styrene), CPVC, (post-chlorinated PVC), acrylates and the like.
• additives can of course be incorporated into the resin.
• additives are: organotin compounds, organic phosphites, epoxy compounds, amino compounds, polyhydric alcohols, metal soaps from C g - C 22 fatty acids with the metals Ca, Zn, Mg or Al, antioxidants, UV absorbers, carbonyl compounds, antistatic agents, lubricants, Plasticizers, pigments and fillers.
• the mixtures used in the following examples are homogenized and plasticized on a laboratory rolling mill at 180 ° C. for 5 minutes. Square sample sheets with an edge length of 15 mm are cut from the approximately 1 mm thick skin thus produced. The sample sheets are annealed in a warming cabinet at 190 °. One leaflet is taken every 10 minutes and attached to a test card. This process is repeated until the test leaves have turned black.
• Example 3

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)

Priority Applications (5)

Applications Claiming Priority (2)

Publications (1)

Family

ID=6426160

Family Applications (1)

Country Status (15)

Cited By (3)

Families Citing this family (30)

Citations (1)

Family Cites Families (14)

• 1991
  • 1991-02-28 DE DE4106404A patent/DE4106404C2/de not_active Expired - Fee Related
• 1992
  • 1992-02-21 DE DE59206246T patent/DE59206246D1/de not_active Expired - Fee Related
  • 1992-02-21 KR KR1019930702586A patent/KR100190265B1/ko not_active Expired - Fee Related
  • 1992-02-21 AT AT92905167T patent/ATE137732T1/de not_active IP Right Cessation
  • 1992-02-21 US US08/098,307 patent/US5312941A/en not_active Expired - Fee Related
  • 1992-02-21 JP JP4504859A patent/JPH06505015A/ja active Pending
  • 1992-02-21 IE IE055192A patent/IE920551A1/en not_active Application Discontinuation
  • 1992-02-21 CA CA002104779A patent/CA2104779A1/en not_active Abandoned
  • 1992-02-21 EP EP92905167A patent/EP0573475B1/de not_active Expired - Lifetime
  • 1992-02-21 ES ES92905167T patent/ES2089501T3/es not_active Expired - Lifetime
  • 1992-02-21 AU AU12631/92A patent/AU1263192A/en not_active Abandoned
  • 1992-02-21 WO PCT/DE1992/000143 patent/WO1992015545A1/de not_active Ceased
  • 1992-02-24 ZA ZA921335A patent/ZA921335B/xx unknown
  • 1992-02-26 TR TR00198/92A patent/TR26951A/xx unknown
  • 1992-02-27 PT PT100171A patent/PT100171A/pt not_active Application Discontinuation
  • 1992-02-28 MX MX9200884A patent/MX9200884A/es unknown

Patent Citations (1)

Also Published As

Similar Documents

Legal Events