DE2652458A1 - HEAT STABILIZER FOR HOMOPOLYMERISATE AND COPOLYMERISATE BASED ON VINYL CHLORIDE - Google Patents

Description

Heat stabilizer for homopolymers and copolymers

the basis of vinyl chloride

(Addition to patent ............ patent application P 26 00 516.3)

The subject of the main patent is the use of a combination consisting of two components for the heat stabilization of polymers based on vinyl chloride, with the aid of which the yellowing and thermal degradation of the polymers at temperatures up to 230 ^° C. is prevented. This stabilizer combination is used as follows, based on the polymer:

a) 0.1 to 5% by weight of one or more organic metal salts, such as are usually used as stabilizers for vinyl chloride polymers used as well

b) 0.05 to 5% by weight of one or more organic β-diketone compounds the general formula

R ₁ -CO- CHR ₂ - CO - R ₃

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in which R ₁ and R_ are the same or different and each represent a linear or branched alkyl or alkenyl group with up to 30 carbon atoms, an aralkyl group with 7 to 36 carbon atoms, an aryl group or cycloaliphatic group with less than 14 carbon atoms, which optionally contain carbon Contains carbon double bonds, this group being optionally substituted by halogen atoms and the aryl or cycloaliphatic groups being substituted by methyl or ethyl groups and also by the presence of one or more groupings

-O-, -C-O, -CO-

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can be modified in the aliphatic chain or in the R ₁ and R-. together also denote an alkylene group with 2 to 5 carbon atoms, which optionally also contains an oxygen _{or nitrogen atom and one of the two substituents R 1} or R _{3 can} also be a hydrogen atom; where in all R ₁ and R ₃ neither an ethylenically or aromatically unsaturated bond nor a carbonyl bond emanate from the carbon atom bonded to a carbonyl group; and R _{3 is} a hydrogen atom, an alkyl or alkenyl group optionally modified in the chain by groups -0-, -CO, -CO f (with up to

0
to 30 carbon atoms or a group of the formula -CO-R., where R. stands for an alkyl group, with 1 to 30 carbon atoms or stands for an aryl group if neither R ₁ nor R _{3 is} aromatic,

CO - R ₁

or a group of the formula -R ₁ . - CH ^,

^ CO - R ₃ .

where R- is an alkylene group having 1 to 6 carbon atoms.

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The invention now relates to stabilized molding compositions ^ ΛίΡ er & t ^ Ba. sis of vinyl chloride polymers which, based on the polymer, contain:
Next

a) 0.1 to 5% by weight of one or more for stabilization common organic metal salts of vinyl chloride polymers

b) 0.05 to 5% by weight of one or more organic compounds the general formula

CO - CH - CO - R "

in which R _{1 is} a divalent group of the following meaning; straight-chain or branched alkylene or alkenylene group with up to 36 carbon atoms,

Aralkylene group with 7 to 36 carbon atoms, arylene or cycloalkylene group with less than 14 carbon atoms, the cycloalkylene group optionally containing carbon-carbon double bonds and the groups listed are optionally substituted with halogen atoms or, in the case of the aryl or cycloaliphatic groups, with methyl or ethyl groups. The groups can also be modified in the carbon chain by one or more groups -0-, -CO- _{r --CO-}

11

be; _{R 2} also denotes a linear or branched alkyl or alkenyl group with up to 36 carbon atoms, an aralkyl group with 7 to 36 carbon atoms, an aryl group or cycloaliphatic group with fewer than 14 carbon atoms, which optionally also contains carbon-carbon double bonds. These groups can optionally be substituted with halogen atoms or, in the case of the aryl or cycloaliphatic groups, with methyl or ethyl groups. They can also be modified in the aliphatic chain by one or more groups -0-, -CO-, -CO-.

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ORIGiNAL INSPECTED

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■ "" rt * ■ "

These ß-diketones are usually with the help of classic Synthesis methods prepared as described by R. Adams et al in "Organic Reactions" 1954, Vol. VIII, p.59 ff. Specific synthetic methods are described by M.J. Kramers in "Rec, Trav. Chem. Pays-Bas "16 (1897) p. 116; by G.T. Morgan and E. Holmes in J. Chem. Soc. 127 (1925) p. 2891, by R, Robinson and E. Seijο in "J.Chem.Soc." (1941) p. 582 and by Claisen in "Reports" 20 (1887), p. 2188.

A common method is that in the presence of sodium, sodium amide, sodium hydride or sodium ethylate an ester with a cyclanone (cydoalkanone) or a ß-tetralone (Tetraion = oxo-1,2,3,4-tetrahydronaphthalene)

Polyvinyl chloride compositions within the meaning of the description are the various Compounds containing a homopolymer or a copolymer of vinyl chloride and various common additives, such as they are usually used to facilitate processability or to achieve special properties of the molded body will.

All homopolymers of vinyl chloride can be used, regardless of whether they are vinyl chloride or not of whether they are carried out by bulk polymerization, suspension polymerization, dispersion polymerization or in still other ways and Manner and regardless of their intrinsic viscosity.

Numerous copolymers of vinyl chloride can be heat-stabilized by the same means as indicated for the homopolymers will. These include the copolymerization of vinyl chloride with other monomers, which is a polymerizable ethylenic Contain double bonds, such as ethylene, acrylic ester, styrene, vinyl ester, Maleic acid or maleic anhydride and maleic acid ester obtained polymers.

The copolymers usually contain 50% by weight of vinyl chloride units. The process according to the invention is particularly suitable for those copolymers which contain at least 80% by weight of vinyl chloride units contain and as a further monomer unit vinyl acetate or vinylidene chloride units,

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- gr -

The homopolymers and copolymers based on vinyl chloride can be rigid or soft or flexible masses. If rigid polymers are used, these agents can be used can be added, which improve their impact resistance, as well as pigments and / or fillers, lubricants, etc. in addition to the Resin and stabilizers. If soft or flexible polymers are used, they contain a plasticizer (primary and / or secondary plasticizers), pigments and / or fillers, lubricants, etc. in addition to the resin and the stabilizers.

Lubricants, antioxidants, light or UV stabilizers can also be added.

The organic metal salts used as stabilizers are essentially salts of calcium, barium, zinc, lead or Cadmium with saturated or unsaturated, optionally substituted aliphatic organic acids or fatty acids. The common salts include the acetates, diacetates, stearates, oleates, laurates, palmitates, benzoates, and hydroxystearates and 2-ethylhexanoate,.

They are generally used in pairs, for example calcium / zinc * -or- barium / cadmium salts in amounts of 0.1 to 5 wt .-%, based on the polymer, according to the invention co-used organic compounds are used in amounts of 0 to 05 _f 5% by weight, preferably 0.1 to 1% by weight, are used, each based on the weight of the polymer,

The stabilizers according to the invention can contain further organic Compounds are added which are known for their stabilizing effect, for example pentaerythritol or trihydroxyethyl isocyanurate,

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The stabilizers provided according to the invention can simultaneously be incorporated into the polymers with the other additives and auxiliaries. You can also start with each other or mixed with certain other additives. They then form a stabilizer mixture that can be used at a later date is incorporated into the polyvinyl chloride in question. All common methods in this field are suitable for Preparation of the mixture of the components, the homogenization of the mass on a mixer or kneader is particularly advantageous,

The molding compositions according to the invention can be with the help of all edit and process known working methods for polyvinyl chloride or vinyl chloride copolymers, for example casting, Extrusion, extrusion blow molding, calendering, deformation by rotation, etc. The combination of an organic stabilizer and a pair of stabilizing metal compounds delays the appearance of yellowing during the entire manufacturing process and enables the production of transparent, homogeneous and non-exuding finished products.

The invention is explained in more detail in the following examples, Example 1

In a 1000 ml flask with a stirrer, heating or cooling jacket, ascending The cooler and enema ampoule were presented:

100 g technical grade methyl stearate containing methyl palmitate as an impurity,

40.5 g of 50% sodium hydride suspension in oil 400 ml of toluene.

The contents of the flask were heated to 75 to 80 ° C. You left on it 61 g of alpha-tetralone run in within two hours 45 minutes and held the whole four hours at 85 ° C,

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It was allowed to cool and acidified by adding 230 g of a mixture 80 parts by weight of glacial acetic acid, 50 parts by weight of water and 100 parts by weight of ice.

The toluene layer, kept at about 40 ° C., was separated from the aqueous Phase separated and washed three times with 150 ml of lukewarm water. The toluene was then distilled off at atmospheric pressure. The brown residue melted at about 60 ° C; Yield 160.9g.

The residue was recrystallized from ethanol; 60 g of a white solid with a melting point of about 52 ° C. were obtained from stearyl tetralone and palmityl tetralone,

Molecular weight determination by mass spectrometry revealed two spades at 384 and 412. In addition, the structure of the two obtained ß-diketones confirmed by the NMR spectrum.

Examples 2 to 6

A molding compound A was produced which was particularly suitable for the production of bottles by the blow molding process.

The following were placed in a cylindrical ball roller mill:

1000 g PVC powder with viscosity number 80 (French standard NFT 51 013) obtained by suspension polymerization, Trade name Lucovyl RS 8000

Copolymer of butadiene, styrene and methyl methacrylate as a means of improving impact resistance

Wax based on rosin ester as a lubricant or lubricant

Calcium stearate
Zinc stearate
epoxidized soybean oil
organic aryl phosphate

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100 G 10 G 10 G 7th G 30th G 3 G

The roller mill was run for 15 hours.

In six powder jars of 250 ml each with some porcelain balls contained, 56 g of this mass were given each time, as well as:

0.3 g stearyl tetralone according to Example 1 or

0.15 g of 2-acetyl tetralone with melting point 56 to 57 ° C., according to the example VIII of US-PS 2,158,071 and

0.10 g smelling liquid 2-acetylcyclohexanone with Bp 110 to 115 ° C, manufactured according to J.Am.Chem. Soc 67, (1945) pp. 1510-1511 or,

0.15 g of 2-benzoyl-cyclohexanone with Ep 88 ° C, prepared according to F.W. Swamer and C, H. Hauser in J. Am. Chem, Soc. 68 (1946) p. 2647 or

0.15 g of 2-acetylcyclohexanedione-13.

The various batches were left in the roller mill for 15 hours run and thus received the homogeneous molding compounds B, C, D, E and F; the sixth powder glass contained the molding compound used for comparison A without the addition of organic stabilizers,

2.5 mm thick plates were produced from these molding compositions on a roller mill heated to 180 ° C. and from these Cut out rectangular test pieces 10 χ 20 mm in size and kept in a ventilated oven at 180 ° C for different lengths of time. Thereupon the discoloration of the test specimens after the Gardner scale determined using a Lovibond comparative disk. The following results were obtained:

Time in min 0 7th 14th 21 Discoloration after
Gardner Molding compound A 8th 8th 8th - 9 Molding compound B 1 1 1 ■ 1.5 Molding compound C 1.5 1.5 1.5 1.5 Molding compound D 1.5 1.5 1.5 2 Molding compound E 1.5 2 2 4th Molding compound F 1.5 2 4th 6th

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The comparison shows that the test specimens made from molding compound B with the organic stabilizer provided according to the invention discolored much less easily during their manufacture and exhibited better heat stability than the test specimens produced with the stabilizers according to the state of the art.

Claim ;

Claims (1)

Claim Use of a mixture of a) carboxylic acid salts of divalent metals and b) a diketone as a heat stabilizer for vinyl chloride homopolymers or copolymers in an amount of 0.1 to 5 wt .-% a) and 0.05 to 5 Ge \ i, - % b), each based on the polymer according to the patent (Patent application P 26 00 516.3-43), thereby characterized in that component b) of the general formula CO - CH - CO - Rp I I ι η ι corresponds, in which R ,, a linear or branched alkylene or an alkenylene group of up to 36 carbon atoms, an aralkylene group of 7 to 36 carbon atoms, an arylene group or a cyclοalkylene group with fewer than 14 carbon atoms, which optionally contains carbon-carbon double bonds, these groups optionally with halogen atoms and the aryl or cycloaliphatic groups are also substituted with methyl or ethyl groups and the groups listed also by the presence of one or more of the following groups -0-, -C-O-, -CO- 0 in the aliphatic chain can be modified, and in the R2 a linear or branched alkyl or alkenyl group having up to 36 carbon atoms, an aralkyl group having 7 to 36 carbon atoms, an aryl group, or a cycloalkyl ^ group with less than 14 carbon atoms, which optionally Contains carbon-carbon double bonds, 709848/0685 is, these groups optionally with halogen atoms and the aryl or cycloaliphatic groups also with Methyl or ethyl groups are substituted and the groups listed are also substituted by the presence of an or several of the following groupings -0-, -C-O-, -CO- in 0 of the aliphatic chain can be modified. 70 9 848/0685