FI64388B - POLYVINYLKLORIDFOERENINGAR VILKA AER STABILIZERADE MED RINGFORMIGA ALFA-ACYLKETONER - Google Patents

Description

Φ FINLAND I —FI N LAN D patent publication — patentkrft 64388 (5¾ Kv.l £ / lnt Cl? C 08 L 27/06, ® ^ Nv.nc/int.*-i. - Pacenunsöknlng 763329 jBgt 9 @ Application date - Ansökningsdag 19.11.76 @ Start date - Giltlghetsdag 19-11.76 © Published public - Bltvic offentlig 21.11.77 © Date of display and publication—

Ansökan utlagd och utl.skriften publicerad 29.07.83

National Board of Patents and Registration © Ratenttj granted-Patent meddelat 10.11.83

Patents and registries

Requested privilege - Begärd priority 20.05.76

France-France (FR) 76/15869 (73) Rh6ne-Poulenc Specialites Chimiques, "Les Miroirs", 18, Avenue d'Alsace, F-92 ^ 00 Courbevoie, France-France (FR) (72) Michel Crochemore, Oullins , Michel Gay, Lyon, France-France (FR) (71 *) Eerggren Oy Ab (5M Polyvinyl chloride compounds stabilized with ring-shaped Qi acyl ketones -

Polyvinyl chloride formulation with a stabilized ring-shaped c4-acyl ketoner

Finnish patent application No. 760040 describes vinyl chloride polymer blends that can withstand high temperatures of up to 230 ° C without yellowing and without thermal changes. These mixtures contain, based on the polymer: a) 0.1-5% by weight of one or more organic metal salts which are customarily used as stabilizers in vinyl chloride polymers b) 0.05-5% by weight of one or more organic β-diketone compounds, of the general formula: R 1 - CO - CHR 2 - CO - R 3, in which R 1 and R 2, identical or different, denote a saturated or unsaturated aliphatic radical, or an aromatic or cycloaliphatic radical, and R 2 represents a hydrogen atom or an alkyl or alkenyl radical , optionally with carbonyl groups.

The present invention relates to polyvinyl chloride compounds stabilized with cyclic α-acyl ketones 2,64388, containing from 0.1 to 5% by weight, based on the polymer, of one or more organic metal salts commonly used as stabilizers in PVC, and the stabilized compounds according to the invention are characterized in that they contain from 0.05 to 5% by weight of one or more organic compounds of the general formula CO - CH - CO - R2

L R] J

representing a divalent straight or branched alkylene or alkenylene group having up to 36 carbon atoms, an Aral alkylene group having 7 to 36 carbon atoms, or an arylene or cycloalkylene group having less than 14 carbon atoms, wherein the cycloaliphatic groups may optionally have carbon -carbon double bonds, the above-mentioned groups being optionally substituted by halogen atoms, or in aryl groups or cycloaliphatic groups by methyl or ethyl radicals, and the above-mentioned groups may also have modifications in the aliphatic chain by one or more bonds - O -, - fo and wherein R 2 is a straight or branched alkyl or alkenyl group having up to 36 carbon atoms, an aralkyl group having 7 to 36 carbon atoms, or an aryl or cycloaliphatic group having less than 14 carbon atoms, the cycloaliphatic groups may optionally have carbon carbon-carbon double bonds; wherein said groups are optionally substituted, for example, by halogen atoms, or in aryl groups or cycloaliphatic groups by methyl or ethyl radicals; and the above-mentioned groups may also have one or more bonds in the aliphatic chain as modifications -O-, -C-O-, -CO-,

O

64388 These β-ketones are usually prepared by classical synthetic methods described, for example, in "Organic Reactions", R. Adams et al., Edition 1954 part VIII page 59 et seq. Some specific syntheses are described in "Rec. Trav. Chem. Pays-Bas ", MJ Kramers 16 (1897) page 116, or "J. Chem. Soc." G. T. Morgan and E. Holmes 127 (1925) page 2891, or "J. Chem. Soc" R. Robinson and E. Seijo (1941) page 582 or "Bericht", Claisen 20 (1887) page 2188.

In one commonly used process, a solution of sodium, sodium amide, sodium hydride or sodium ethylate is reacted with an ester of cyclanone or β-tetralone.

Polyvinyl chloride mixtures are mixtures containing a vinyl chloride homopolymer or copolymer and various additives which are conventionally used to facilitate use or to impart special properties to the article produced.

All types of vinyl chloride homopolymers are suitable regardless of their method of preparation: bulk, suspension or dispersion polymerization or any other type, and regardless of their intrinsic viscosity.

Several vinyl chloride copolymers can also be stabilized against the effects of heat by means identical to those used for homopolymers. They include, for example, those copolymers obtained by copolymerizing vinyl chloride with other monomers having a polymerizable ethylene bond, for example with ethylene, with acrylic esters, styrene, vinyl esters, maleic acid or anhydride or with maleic esters.

Copolymers usually contain at least 50% by weight of vinyl chloride. However, the process according to the invention is particularly well suited for copolymers containing at least 80% by weight of vinyl chloride and whose second monomer is vinyl acetate or vinylidene chloride.

Homopolymers and copolymers can be either "rigid" or "flexible". When "rigid" polymers are used, these may contain 64388 impact modifiers, pigments and / or fillers, lubricants, etc. in addition to resin and stabilizers. When "flexible" polymers are used, they may contain plasticizers (primary and / or secondary), pigments and / or fillers, lubricants, etc. in addition to resin and stabilizers.

Lubricants, antioxidants, and "light" and UV stabilizers can also be added to the mixtures.

The stabilizing agents used in the compositions according to the invention are organometallic salts, in particular calcium, barium, zinc, lead or cadmium salts, formed with aliphatic organic acids or fatty acids which are saturated or unsaturated, substituted or unsubstituted. Commonly used salts include acetates, diacetates, stearates, oleates, laurates, palmitates, benzoates, hydroxystearates, ethyl 2-hexanoates.

They are usually used in the form of salt pairs, such as calcium / zinc or barium / cadmium, and account for between 0.1 and 5% by weight of the polymer.

The organic compounds are used according to the invention in an amount of about 0.05 to 5% by weight, in particular 0.1 to 1% by weight, of the polymer.

It is also possible to add to the stabilizers according to the invention other organic compounds which are known for their stabilizing effect, such as, for example, trihydroxyethyl pentaerythritol or isocyanurate.

The stabilizing agents according to the invention can be added to the mixture at the same time as other additives. They can also be mixed with each other or with some additives; in that case, they form a stabilizing mixture which is subsequently added to the polyvinyl chloride. All conventional methods known in the art are suitable for mixing the ingredients together. However, the homogenization of the mixture is preferably carried out using a stirrer.

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The mixtures according to the invention can be used according to all the usual working methods used in the treatment of PVC mixtures or copolymer mixtures thereof, for example by injection molding, extrusion, extrusion blow molding, calendering, rotational molding, etc.

Thanks to the combination of an organic stabilizing agent and stabilizing metal salt pairs, it is possible to delay the appearance of yellowing throughout the work and to obtain transparent, homogeneous finished products without sweating.

The following examples illustrate the invention:

Example 1 A 1000 ml flask equipped with a central stirrer, heat coater, condenser and flow tube is charged with 100 g of technical grade methyl stearate containing 40.5 g of a 50% sodium hydride suspension in oil in 400 cm 2 of toluene as an impurity in methyl palmitate.

The contents of the flask are heated to 75-80 ° C. Pour 61 g of α-tetralone over 2 h 45 min. The mixture is kept at 85 ° C for 4 h. Allow to cool and acidify by adding 230 g of a mixture of glacial acetic acid-water-ice (weight ratios 80-50-100). The toluene phase, which has a temperature of about 40 ° C, is separated from the aqueous phase. This phase is washed 3 times with 150 cm -1 of lukewarm water each time. Toluene is removed by distillation at atmospheric pressure. A crude residue is obtained which is brown in color and melts at about 60 [deg.] C. and weighs 160.9 g.

This crude product is purified by recrystallization from ethanol to give 60 g of a white solid, m.p. is about 52 ° C and which is stearyl tetralone and palmitoyl tetralone.

Examination of the mass spectrographically gives two molecular peaks corresponding to masses 384 and 412. The NMR spectrum is also consistent with the two 3-diketones obtained.

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Examples 2-6

Mixture A is prepared which can be used especially for extrusion blowing of bottles.

In a ball mill, mix: 1000 g of powdered PVC with a viscosity index of 80 (standard NF T 51 013) obtained by suspension polymerization and sold under the trade name Lucovyl RS 8000.

100 g of impact-strengthening agent, a copolymer of butadiene, styrene and methyl methacrylate.

10 g of rosin wax lubricant sold under the trademark Cire E.

10 g calcium stearate 7 g zinc stearate 30 g epoxidizing oil 3 g organic aryl phosphite.

Allow the wheels to roll for 15 h.

56 g of this mixture and one of the following are charged to six grinders with a capacity of 250 meals and porcelain balls: 0.3 g of stearyl tetralone prepared according to Example 1, 0.15 g of acetyl-2-tetralone, m.p. is 56-57 ° C and is prepared according to Example VIII of U.S. Patent No. 2,158,071 to Du Pont de Nemours.

0.10 g of acetyl-2-cyclohexanone, a strong-smelling liquid with a b.p. is 110-115 ° C and is obtained according to the method described in J. Am. Chem. Soc. 6J7 (1945) pages 1510-1511.

- 0.15 g of benzoyl-2-cyclohexanone, m.p. is 88 ° C and is prepared by F.W. Swamer and C.H. According to Hauser, J. Am. Chem.

Soc. 6JJ (1946) page 2647.

0.15 g of acetyl-2-cyclohexanedione-1,3.

Mixtures B, C, D, E and F are thus obtained; the sixth grinder contains only the original mixture and is used as a reference.

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Allow to rotate in a roller mixer for 15 h and thus obtain homogeneous mixtures.

From these mixtures, 2.5 mm thick plates are prepared using a hot calendar at 180 ° C.

From these plates, rectangular specimens measuring 10 x 20 mm are cut and placed in a ventilated drying oven at 180 ° C for various periods of time.

The color of the samples is then determined according to the Gardner scale using a Lovibond plate. The following results are obtained: Staining index after x min 0 7 14 21

Relationship A 8 3 8 9 B 1 1 1 1.5 C 1.5 1.5 1.5 1.5 D 1.5 1.5 1.5 2 E 1.5 2 2 4 F 1.5 2 4 6

It is noted that samples containing an organic stabilizing agent are much less stained during manufacture and have better thermal stability.

Claims (1)

Polyvinyl chloride compounds stabilized with ring-shaped α-acyl ketones, containing from 0.1 to 5% by weight, based on the polymer, of one or more organic metal salts commonly used as stabilizers in PVC, characterized in that they contain from 0.05 to 5% by weight. % by weight of one or more organic compounds of the general formula CO - CH - CO - R 2 L R 11 wherein R 1 represents a divalent straight or branched alkylene or alkenylene group having up to 36 carbon atoms, an Aral alkylene group having 7-36 carbon atoms, or an arylene or cycloalkylene group having less than 14 carbon atoms, the cycloaliphatic groups may optionally have carbon-carbon double bonds, the above groups being optionally substituted by halogen atoms, or aryl groups or cycloaliphatic groups having methyl or in the above-mentioned groups there may also be modifications in the aliphatic chain alone i or more bonds -O-, -C-O-, -CO-; O and wherein R 2 is a straight or branched alkyl or alkenyl group having up to 36 carbon atoms, an aralkyl group having 7 to 36 carbon atoms, or an aryl or cycloaliphatic group having less than 14 carbon atoms, wherein the cycloaliphatic groups may optionally have carbon carbon kaksoissidoksla; wherein the above groups are optionally substituted, for example, by halogen atoms, or in aryl groups or cycloaliphatic groups by methyl or ethyl radicals; and the aforementioned groups may also have one or more bonds -O-, -C-O-, -CO- in the aliphatic chain as variants. II o 9 64388 Polyvinyl chloride derivatives, stabilized with a ring-shaped α-acyl ketoner, with an active ring, having a polymer content of 0,1 to 5% by weight of an organic metal salt, with an anti-stabilizing agent for PVC, a string to 0.05-5% by weight of an organic compound having the following formula: CO - CH - CO - R2 L R1 or R1 is selected from the group consisting of alkylene and alkenylene groups up to 36 cholatomer, in which the aralkylengine group is 7-36 cholatomers, in which case the arylenyl or cycloalkylgene group is in the range of 14 cholaters, the cycloaliphatic group optionally having the same color; the colors of the present group may optionally be substituted with halo-genomics or, in the case of aryl groups and cycloaliphatic groups, with methyl or ethyl groups and the colors of the same groups may be substituted for the genome of the genome - C - O -, - CO-O in the aliphatic chain; and R2 is an alkyl group having an alkyl or alkenyl group having up to 36 chapters, an aralkyl group having a value of 7-36 cholatom, or an aryl group having a cycloaliphatic group having a double ring in the group consisting of 14 chapters, colors of the cycloalkate ; the color is optionally substituted with a halogen atom or, for example, an aryl group and a cycloaliphatic group, methyl or ethyl; and a group of ovarian groups and other modifiers of the genomic array of the group consisting of -O-, - C - O -, -coll O i den aliphatiska kedjan.