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
  • C08K5/49—Phosphorus-containing compounds
  • C08K5/51—Phosphorus bound to oxygen
  • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
  • C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
  • C08K5/5333—Esters of phosphonic 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
  • C08K3/26—Carbonates; Bicarbonates
• • 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
  • C08K9/00—Use of pretreated ingredients
  • C08K9/04—Ingredients treated with organic substances

Definitions

• the invention relates to a filler-containing plastic molding composition consisting of 90 to 20 parts by weight of a polyolefin
• R 1 is an alkyl group with 1 to 18 carbon atoms, an alkenyl group with 2 to 18 carbon atoms, an aralkyl group with 7 to 13 carbon atoms, the alkyl chain of which has 1 to 3 carbon atoms, or an aralkenyl group with 8 to 13 carbon atoms, the alkenyl chain has 2 or carbon atoms
• R 2 and R 3 are identical or different and are hydrogen, an alkyl radical with 1 to 8 carbon atoms, an aryl radical with 6 to 10 carbon atoms, an aralkyl radical with 7 to 13 carbon atoms, the alkyl chain of which has 1 to 3 carbon atoms, or an alkenyl radical with 3 to 5 carbon atoms.
• the organophosphorus compounds of the formula (I) to be used according to the invention are phosphonic acids and their esters.
• R 1 is an alkyl radical having 1 to 18, preferably 3 to 8, in particular 2 to 6 carbon atoms.
• the alkyl radical can be straight-chain or branched or ring-shaped.
• R 1 also denotes an alkenyl radical with 2 to 18, preferably 2 to 12 carbon atoms, or an aralkyl radical with 7 to 13, preferably 7 to 10, in particular 7 to 9 carbon atoms, the alkyl chain of which has 1 to 3, preferably 1 or 2, carbon atoms, or an aralkenyl radical having 8 to 13, preferably 8 to 10, in particular 8 to 9 carbon atoms, the alkenyl chain of which has 2 or 3 carbon atoms.
• the aromatic radical is a carbocyclic nucleus with 6 or 10 ring carbon atoms, which optionally carries side chains.
• R 2 and R 3 are the same or different and each represents hydrogen, an unbranched or branched or cyclic alkyl radical having 1 to 8, preferably 2 to 8 carbon atoms, an aryl radical having 6 to 10, preferably 6 to 8 carbon atoms, an aralkyl radical having 7 to 13, preferably 7 to 10 carbon atoms, the alkyl chain of which has 1 to 3, preferably 1 or 2 carbon atoms, or an alkenyl radical with 3 to 5, preferably 3 or 4 carbon atoms.
• Aromatic radicals are preferably carbocyclic nuclei with 6 or 10 ring carbon atoms, which can optionally carry side chains.
• the phosphonic acids and phosphonic acid esters to be used according to the invention can be prepared by known methods.
• the phosphonic acids can be removed from their tetra- or dihalides by reaction with water, by saponification of the corresponding esters, by disproportionation of phosphonic acids or by adding phosphorous acid to olefinic double bonds; the phosphonic acid esters by reacting the phosphonic acid tetra- or dihalides with alcohols or from esters of phosphorous acid with alkyl halides (Kosolapoff, Organophosphorus Compounds, Wiley and Sons, New York, 1950; Houben-Weyl, Vol. XII / 1, Thieme Verlag Stuttgart ).
• Suitable phosphonic acids are, for example, methanephosphonic acid, ethanephosphonic acid, propanephosphonic acid, butanephosphonic acid, n-hexanephosphonic acid, cyclohexanephosphonic acid, 2,3-dimethylbutanephosphonic acid, octanephosphonic acid, decanephosphonic acid, dodecanephosphonic acid, octadecanephosphonic acid, phenylmethanephosphonic acid, 2-phosphonic acid, 2-phosphonic acid 2-phenyl-vinylphosphonic acid-1, 2,4-dimethyl-4-methyl-pentane-phosphonic acid, dimethyl-2-methylpropane-phosphonic acid and 2,4-dimethyl-butane-phosphonic acid.
• Vinylphosphonic acid, propanephosphonic acid, hexanephosphonic acid, octanephosphonic acid, dodecanephosphonic acid, 2,4-dimethyl-4-methylpentane-phosphonic acid, dimethyl-2-methylpropane-phosphonic acid and 2,4-dimethyl-butane-phosphonic acid are preferably used.
• Suitable phosphonic acid esters are, for example, Methanphosphonklathylester, ethanephosphonic acid-diäthyiester, ethanephosphonic acid dibutyl, Butanphosphonklare dibutyl, n-Hexanphosphonklathylester, n-hexanephosphonic diphenyl, Octanphosphonklathylester, dodecanephosphonic acid dimethyl ester, Octadecanphosphonklare acid diethyl ester, vinylphosphonic acid dimethyl ester, vinylphosphonic acid diethyl ester, vinylphosphonic acid-di- (2-ethylhexyl) ester, vinylphosphonic acid dioctyl ester, vinylphosphonic acid diallyl ester, allylphosphonic acid diallyl ester, allylphosphonic acid dimethallyl ester, phenylmethane phosphonic acid monoethyl ester, methanephosphonic acid e
• the phosphonic acids and phosphonic acid esters to be used according to the invention are added to the molding composition in an amount of 0.1-10% by weight, preferably 0.5-2% by weight, based on the filler. Mixtures of different phosphonic acids or phosphonic acid esters, or mixtures of phosphonic acid with phosphonic acid esters can also be used.
• the filler can be a natural or synthetic, i.e. precipitated alkaline earth carbonate.
• Suitable carbonates are, for example, limestone powder, chalk, precipitated calcium carbonate, natural magnesite, natural hydromagnesite, synthetic basic magnesium carbonate, calcium magnesium carbonate, dolomite. Calcium carbonates are preferably used.
• the alkaline earth metal carbonates to be used according to the invention have an average particle diameter of 0.1 to 50 ⁇ m, preferably 1 to 10 ⁇ m. Mixtures of different alkaline earth carbonates can also be used.
• the phosphonic acid or the phosphonic acid ester can be introduced into the molding composition in various ways.
• the filler in an organic solvent, alcohols such as methanol, ethanol, butanol, hydrocarbons such as hexane, benzene, toluene, ethers such as diethyl ether, di-iso-propyl ether or ketones such as acetone, diethyl ketone serve as solvents.
• alcohols such as methanol, ethanol, butanol
• hydrocarbons such as hexane, benzene, toluene
• ethers such as diethyl ether, di-iso-propyl ether or ketones such as acetone, diethyl ketone
• ketones such as acetone, diethyl ketone
• the adhesion promoter is liquid, it can be added directly to the filler or diluted with a suitable solvent in a high-speed mixer or sprayed onto the filler from a spray device in the form of a mist. In this way, solid adhesion promoters can also be applied to the filler dissolved in a suitable solvent.
• the adhesion promoter can be mixed with the polymer in a mixer and then the untreated filler can be added, or all three components, namely the polymer, the filler and the adhesion promoter can be mixed at the same time.
• This simultaneous mixing can take place in a premixer, but also in the granulating extruder.
• the filler is preferably first treated with the adhesion promoter.
• Suitable base polymers for the plastic molding compositions according to the invention are 1-olefin homopolymers and copolymers, for example polyethylene of high density and low density, polypropylene, polybutene-1, poly- (4-methyl) -pentene-1, olefin copolymers such as ethylene Propylene copolymers and ethylene-butene copolymers, mixtures of these polymers and mixtures of these polymers with rubber-like polymers are used.
• Polyethylene is particularly preferably used.
• the polymer content of the molding compositions is 90 to 20, preferably 70 to 30,% by weight.
• the molding compositions according to the invention can contain the usual additives which facilitate processing and improve the physical properties. As such, new light and heat stabilizers, antioxidants, antistatic agents and the like. as well as color pigments, flame retardants.
• the first group is generally contained in the molding compositions in an amount of from 0.01 to 5 percent by weight, based on the amount of polymer plus filler. Color pigments and flame retardants Medium are used in an amount according to needs.
• An effective stabilizer composition for poly-1-Oiefine such as high, medium and Niederdruckpolymerisate of C 2 - to C 4- 1-olefins, especially polyethylene and polypropylene, or of copolymers of such 1-olefins, for example, consist, in each case based per 100 parts by weight of polymer, from 0.05 to 4 parts by weight of a phenolic stabilizer, optionally 0.01 to 4 parts by weight of a sulfur-containing costabilizer, and optionally 0.01 to 3 parts by weight of a basic or neutral metal soap, such as calcium stearate or zinc stearate, and optionally 0.1 to 4 parts by weight of a phosphite and optionally 0.01 to 4 parts by weight of a known UV stabilizer from the group of alkoxyhydroxybenzophenones, hydroxyphenylbenzotriazoles, benzylidenmalonic acid monotrilesters or the so-called Quencher (eg nickel chelates).
• Quencher eg nickel chel
• a polymerization initiator for example benzoyl peroxide, dicumyl peroxide, tert-butyl hydroperoxide, tert-butyl peroctoate, azobisisobutyronitrile in an amount of 0.01 to 1 percent by weight, based on the amount of unsaturated phosphonic acid or phosphonic acid esters can be added.
• thermoplastic molding composition according to the invention have very good impact strength and impact strength, which makes them particularly suitable for the production of technical articles.
• adhesion promoters to be used according to the invention are that they have a favorable influence on the flow behavior of the polymer melt during injection molding and, for example, facilitate the filling of the mold in the production of complicated injection molded parts.
• test specimens are listed in Table I.
• a 1/2 standard rod is used as a test specimen.
• Elongation and tensile strength are determined according to DIN 53 455, impact strength according to DIN 53 453 (30 mm jaw spacing, transverse position) impact strength according to DIN 53 448, ball indentation hardness according to DIN 52 456 and the modulus of elasticity according to DIN 53 457.
• Example 1 The same calcium carbonate as in Example 1 is treated with different phosphonic acids or phosphonic acid esters in different concentrations, based on the amounts of calcium carbonate. 300 parts of the calcium carbonate thus treated are mixed with 700 parts of the same polyethylene and the mixture is processed as described in Example 1. The properties of the test specimens are listed in Table 11.
• Example 15 is repeated, except that 3 parts of dodecanephosphonic acid are used instead of octanephosphonic acid to modify the calcium carbonate.
• the properties of the test specimens are listed in Table III.
• a solution of 5 parts of octadecanephosphonic acid in 50 parts of acetone is converted into 500 parts in 30 minutes in a high-speed mixer at 1200 to 500 parts of calcium carbonate of calcite type with an average particle diameter of 5 microns and a specific surface area (BET) of 1 m 2 / g RPM sprayed.
• BET specific surface area
• Example 17 is repeated, except that 5 parts of vinylphosphonic acid bis (2-ethylhexyl) ester are used without solvent instead of octadecanephosphonic acid.
• the mixture is further processed as described in Example 1.
• the properties of the test specimens are listed in Table 111.
• Example 17 is repeated, except that 10 parts of vinylphosphonic acid are used instead of octadecanephosphonic acid.
• the mixture is further processed as described in Example 1.
• the properties of the test specimens are listed in Table 111.
• a mixture of untreated calcium carbonate and polyethylene is prepared in accordance with Example 15.
• a comparison sample with unmodified, precipitated calcium carbonate is also produced here.
• Example 21 is repeated with the proviso that instead of acetone, methanol is used as the solvent and instead of vinylphosphonic acid, octanephosphonic acid is used as a modifier for precipitated calcium carbonate.
• methanol is used as the solvent
• vinylphosphonic acid instead of vinylphosphonic acid, octanephosphonic acid is used as a modifier for precipitated calcium carbonate.
• the properties of the test specimens are listed in Table IV.
• the mixture is further processed as described in Example 1.
• the properties of the test specimens are listed in Table V.
• Example 23 is repeated, an additional 0.04 part of tert-butylhydroxyperoxide being added in the high-speed mixer.
• the mixture is further processed as described in Example 1.
• the properties of the test specimens are listed in Table V.
• 1,050 parts of the polyethylene treated in this way are mixed well with 450 parts of calcium carbonate (average particle diameter 5 ⁇ m, specific surface area 1 m 2 / g) in a plow blade mixer.
• the mixture is further processed as described in Example 1.
• the properties of the test specimens are listed in Table V.
• Example 25 is repeated with the change that dodecanephosphonic acid is used instead of octanephosphonic acid.
• the properties of the test specimens are listed in Table V.
• Example 1 1,050 parts of polyethylene (density 0.96 g / cm 3 , melt index 23 g / 10 min., Stabilized as in Example 1), 450 parts of calcium carbonate (average particle diameter 5 ⁇ m, specific surface area 1 m 2 / g) and 4.5 Parts of octanephosphonic acid are mixed at 80 ° C in a high-speed mixer for 30 minutes. The extrusion and testing are carried out as described in Example 1.
• polyethylene density 0.96 g / cm 3 , melt index 23 g / 10 min., Stabilized as in Example 1
• calcium carbonate average particle size 5 ⁇ m, specific surface area 1 m 2 / g
• test specimens are examined for impact strength. The results are shown in Table VI.
• test specimens are produced and tested as described in Example 1.
• test specimens are produced and examined as described in Example 1.
• the same polyethylene is mixed with further amounts of the same calcium carbonate, which was modified with 1 percent by weight octanephosphonic acid, based on the amount by weight of filler, and processed further.
• mixtures with untreated calcium carbonate are produced as a comparison.

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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)
• Pigments, Carbon Blacks, Or Wood Stains (AREA)

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• 1977
  • 1977-08-04 DE DE19772735160 patent/DE2735160A1/de not_active Withdrawn
• 1978
  • 1978-07-25 DE DE7878100497T patent/DE2860857D1/de not_active Expired
  • 1978-07-25 EP EP78100497A patent/EP0000726B1/de not_active Expired
  • 1978-08-02 US US05/930,397 patent/US4174340A/en not_active Expired - Lifetime
  • 1978-08-02 IT IT26423/78A patent/IT1097922B/it active
  • 1978-08-03 AU AU38612/78A patent/AU518651B2/en not_active Expired
  • 1978-08-03 JP JP9417978A patent/JPS5428349A/ja active Pending
  • 1978-08-03 CA CA308,720A patent/CA1115444A/en not_active Expired
  • 1978-08-03 ZA ZA00784405A patent/ZA784405B/xx unknown

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