SE187665C1 - - Google Patents

Description

Inventors: AC Hecker and S. Cohen Priority Asked for May 10, 1961 (USA) The present invention relates to new stabilizer compositions for polyvinyl chloride resins and to a process for producing a polyvinyl chloride resin composition having improved color and better temperature stability. prepared resin composition.

U.S. Pat. No. 2,564,646 proposes the stabilization of polyvinyl chloride resins by means of a heavy metal salt of a higher fatty acid, and in this stabilizing agent also an organic phosphite or a strongly blocked alkyl. phenol, which acts as an antifouling agent, which inhibits precipitation of metal halide from the stabilizer resin composition as grams in the material. U.S. Pat. No. 2,716,092 proposes an improved stabilizer which consists of a combination of such heavy metal salts of higher fatty acids and polyvalent metal salts of carbonate substituted phenols. Many of these types of compositions are currently widely used to stabilize polyvinyl chloride resins against discoloration during processing and against shallow cuts due to the separation of constituents in the resin. However, the compositions based on the organic phosphite have been more widely used than the compositions based on a combination of metal salt of a higher fatty acid and a strongly blocked phenol, because the phenol, although it improves the high temperature stability, gives a noticeable, yellowish shift. This is not always disadvantageous, but in some cases such color shades can not be accepted.

It has now been discovered, however, that polyhydric alcohols having a certain structure have the property of reducing or completely inhibiting the yellowing produced by the phenol in these compositions, and of further increasing the stabilization obtained with a certain amount of phenol and fatty acid salt. The polyols used in accordance with the invention have the structure: CH 2 OH R 2 -C 14 2 -C-CH 2 OH CFI 2 OH, in which R represents vate or an organic radical from the group of alkyl, alkoxy, hydroxyalkylate alkoxyhydroxyalkyl groups, which. ha 1-30 kolr. atoms.

Examples of R-radicals arc methyl, ethyl, isopropyl, butyl, tertiary butyl, secondary butyl, isobutyl, amyl, isoamyl, hexyl, isohexyl, heptyl, octyl, 2-ethylhexyl, isooctyl, decyl, octadecyl, methoxy, ethoxy, hydroxypropyl, hydroxyethyl, oxy, hydroxyethyl, butoxy, propoxy, pentaerythrityloxy and hydroxineopentyloxy.

Typical glycols are dipentaerythritol, trime, tylolpropane, trimethylolmethane, trimethylolethane and trimethylolbutane. The methylenetrimethylol configuration is very important for the activity of these compounds. For example, pentaerythritol, glycerol and ethylene glycol are unsatisfactory, and combine with mannitol and sorbitol. however, this feature of the structure is not kthrt.

Along with these polyols, there is also a metal salt stabilizer for the polyvinyl chloride resins of the type described above: in U.S. Pat. No. 2,564,646 and other patents relating thereto. : MetallSaliS * 41Arer ._ 2— - the ring agent is a salt of a polyvalent metal and a monocarboxylic, free nitrogen atom free, organic acid, which has 6-18 carbon atoms. Aliphatic, aromatic, alicyclic and oxygen-containing heterocyclic monocarboxylic acids are active as a class. The acids may be optionally substituted with such groups as halogen, sulfur and hydroxyl. The oxygen-containing heterocyclic acids contain oxygen and carbon in the ring, and examples of such acids are alkyl-substituted furanecarboxylic acids. Examples of the acids which may be mentioned are: caproic acid, capric acid, 2-ethyl-caproic acid, lauric acid, chlorocaproic acid, hydroxycapric acid, stearic acid, hydroxystearic acid, palmitic acid, oleic acid, myristic acid, dodecylthioetherpropionic acid C12H-2H-benzoic acid; , phenylacetic acid, isobutylbenzoic acid, the monoethyl ester of phthalic acid, ethylenebenzoic acid, isopropylbenzoic acid, castor oleic acid, pt-butylbenzoic acid, n-hexylbenzoic acid, salicylic acid, naphthoic acid, 1-naphthaleneacetic acid, orthobenzoylbenzoic acid hydrophenic acid, fraphenylphenobenzoic acid. These acids are used in the form of their metal salts, especially the alkaline earth metal salts, for example the magnesium, barium, strontium and calcium salts and the zinc, cadmium, lead and tin salts. These salts can be sprayed by conventional reactions, for example by mixing the acid, acid chloride or anhydride with the corresponding oxide or hydroxide of the metal in a liquid solvent and, if necessary, then heating until the salt formation is complete. The barium, cadmium and zinc compounds are withdrawn.

The second essential component of the stabilizer composition of the invention is a carbon monosubstituted phenol containing at least one phenolic hydroxyl group and 1-30 carbon atoms per phenolic hydroxyl group. The phenol contains one or more phenolic hydroxyl groups and may contain one or more phenolic nuclei. In addition, the phenolic nuclei may have an oxy- or thioether substituent.

In addition, the phenol may have one or more alkyl, aryl or cycloalkyl substituents or a second ring, which is condensed clamed, as in the naphthols, and which has one or more carbon atoms app to the total number of carbon atoms per phenolic hydroxyl group. Generally, the phenols have at most about 18 carbon atoms in which at any time alkyl, aryl, cycloalkyl, alicyclidene or alkylene group. The phenols may have 1-5 substituent radicals per the phenols.

Examples of phenols are ortho-, meta- and paracresol, ortho-, meta- and para-phenylphenol, ortho-, meta- and para-xylenols, the carvenols, spumetric xylenol, thymol, ortho-, meta- and para-nonylphenol, ortho , meta- and para-dodecylphenol and ortho-, meta- and para-octylphenol, para-ok Lylresorcinol, para-dodecylresorcinol, para-octadecylcatechin, para-isooctylphloroglucinol, p-isohexylcatechin, 2,6-ditorcinol-2-ditorcinol-2 , 6-diisopropylphloroglucinol, methylene-bis- (2,6, ditert-hutylphenol), 2,2-bis- (4-hydroxyphertyl) -propane, methylene-bis- (pcresol), 4,4'-thiobisphenol, 4, -1'-oxobis- (3-methyl-6-isopropylphenol), 4,4'-thio-bis- (3-methyl-6-tert-butylphenol), 2,2'-oxobis- (4-dodecylphenol) , 2,2`-thiobis- (4-methyl-6-tert-butylphenol), 2,6-diisooctylresorcinol, 4,4'-n-butylidene-bis- (2-t-butyl-5-methylphenol), 4,4'-hensylidene-bis- (2-t-butyl-5-methylphenol), 2,2'-methylene-bis- (4-methyl-6-1 '-methylcyclohexylphenol), 4,4'-cyclohexylidene- bis- (2-t-butylphenol), 2,6-bis- (2'-hydroxy-3'-t-butyl-5'-methylbenzyl) -4-methyl-pheno 1,4-octylpyrogallic acid and 3,5-ditert-butylcatechin, α- and fl-naphthol and mono- and di-tert-butyl-substituted α- and finaphthols.

The basic stabilizers according to the invention consist of the combination of the metal salt stabilizer, substituted phenol and polyol. These components can also be used with other stabilizers, which are normally used for polyvinyl chloride resins.

Effective stabilizers are also organic compounds which contain at least one epoxy group. These compounds can be used to supplement the basic stabilizers. The amount used can be 0-100 parts by weight per 100 parts of resin, depending on the desired effect, because many epoxy compounds are also plasticizers for polyvinyl chloride resins.

A total of 0.5-10 parts by weight of the stabilizers can be used for 100 parts by weight of the resin. Larger amounts of stabilizer composition can be used, but no better results are usually obtained, and therefore such larger amounts are uneconomical and reprehensible. Of this amount, 5-60 °, polyol () is 5-60 phenol and 90-35% metal salt.

The invention is applicable to any polyvinyl chloride resin. The term "polyvinyl chloride" is intended to include not only polyvinyl chloride homopolymers but also copolymers which contain a major proportion of vinyl chloride and a minor proportion of other copolymerizable monomers, for example, copolymers of vinyl chloride and vinyl acetate, copolymers of vinyl chloride, vinyl chloride and vinyl chloride; copolymers of vinyl chloride and styrene, and the term polyvinyl chloride is intended to include mixtures of a predominant amount of polyvinyl chloride and a minor amount of other synthetic resins, for example chlorinated polyethylene or a copolymer of acrylonitrile, butadiene and styrene.

Usually eLL plasticizers are mixed in, for example dioctyl italate, dioctyl sebacate and tricresyl phosphate.

Particularly useful plasticizers are the higher epoxy esters, which have 22-150 carbon atoms. Such esters are originally said to have had a fatigue in the alcohol or acid portion of the molecule, which fatigue is taken up by the formation of the epoxy group.

A small amount, usually at most 1, of a mold release agent can be mixed into the oven. Typical mold release agents are higher, aliphatic acids having 12 to 24 carbon atoms, for example stearic acid, lauric acid, palmitic acid and myristic acid, mineral lubricating oils, polyvinyl stearate, polyethylene and paraffin wax.

The preparation of the stabilized composition is carried out easily in the usual way. The selected stabilizer composition is usually mixed with the plasticizer, and this mixture is then mixed at a temperature at which the mixing is fluid and thorough mixing is omitted, with the polyvinyl chloride resin using, for example, a plastic mixing roll which rolls the plasticizer and the stabilizer in the resin mill. 120-180 ° C for a sufficient Capture time to form a homogeneous sheet, usually 5 minutes. Since the mass is uniform, it is deposited in the usual way.

The following examples are intended to illustrate the invention and describe preferred examples of the invention.

Example 1.

A series of mixtures was prepared which had the following composition: Plastic composition Weight parts Geon 101 Ep (homopolymer of polyvinyl chloride) 100 Dioctyl phthalate Stabilizer composition, given in Table I1, The dioctyl phthalate and the stabilizers, among others. and this mixture was then mixed with the polyvinyl chloride. The mixture was heated in a two-roll mill to 180 ° C, and the mixture was then tested in an oven at 180 ° C to test the heat stability. The discoloration was noted and is listed in Table I.

Table 1.

Color.

Sample number Stabilizer Heating time A Barium laurate 1, Cadmium laurate 1, Barium laurate 0.7 Cadmium laurate 0.7p-nonylphenol 1, Trimethylolpropane 1, Originally Clear Clear Clear Shift in light yellow Clear After 15 min Brown Clear Clear Brown Brown After 30 min Brown Gray with black edges Clear with some light yellow discoloration Dark brown Brown After 45 min Deeper brown Black Yellow flaelcar Dark brown Dark brown After 60 min Dark brown Black Dark yellow flakes Dark brown Dark brown After 75 min Dark brown Black Black Dark brown Dark brown After 90 min Very dark brown Black Black Dark brown After 105 min Black Black Black Black Dark brown After 120 min Black Black Black Black Black Fan.

Sample number Stabilizer Heating time p-nonylphenol 0.7 Trimethylolpropane 0.7Barium laurate 0.70 Cadmium laurate 0.70 p-nonylphenol 0.1 Barium laurate 0.6 Cadmium laurate 0.6 Trimethylolpropane 0.3 Barium laurate 0, Cadmium laurate 0, Trimethyl 0, Trimethyl 3 p-nonylphenol 0.1 Originally Shift in light yellow Shift in light yellow Clear Ready After 15 min Deep amber color Shift in light yellow Clear Ready After 30 min Dark brown Shift in light yellow Clear Ready After 45 min Dark brown Shift in light yellow Light yellow Clear After 60 min Dark brown deeper yellow Light yellow Clear After 7min Dark brown Shift in deeper yellow Dark yellow flakes Clear After 90 min Black Shift in deeper Black with gala Weak, yellow mismatched yellow fldckar staining After 105 min Black Shift in deeper yellow Black Weak, yellow discoloration After 120 min Black Shift in deeper yellow Black Weak, yellow discoloration 4— - The results show that barium laurate alone (sample A). and cadmium laurate alone (sample B) are completely ineffective as stabilizers. Barium laurate and cadmium laurate together (sample C) gay a certain, small improvement, but this lasted only 30 minutes during the warm-up, which joke is sufficient. Completely unsatisfactory are p-nonylrenal (sample D) and trimethylolpropane (sample E), which do not have any stabilizing effect even for 15 minutes of heating. The combination of pnonylphenol and trimethylolpropane (sample F) was not better than the two components separately. The combination of barium laurate, cadmium laurate and p-nonylphenol (sample G) was quite effective in terms of heat stabilization, but the p-nonylphenol originally introduced a shift in the hole, which for some purposes is inadequate. Trimethylolpropane, barium laurate and cadmium laurate together (sample H) gay ° good stabilization, but this lasted only 1 hour on heating.

The combination of barium laurate, cadmium laurate, trimethylolpropane and p-nonylphenol (sample I) was completely effective. The trimethylolpropane prevented the initial shift to yellow, which is introduced by the p-nonylphenol (compared to sample G), and good stabilization was achieved. Even after 120 minutes of heating, a light yellow discoloration was observed, and this color was definitely better than the color in sample G at the end of this heating period. The results thus clearly show the distinctive feature of the trimethylolpropane in the stabilizing compositions of the invention.

Example 2.

A series of polyvinyl chloride resin compositions were prepared which both had the following composition: Plastic Composition Light Parts Geon 101 Fp (Homopulyines of polyvinyl chloride) 100 Dioctyl phthalate Mixed isooctyl ester of tall oil fatty acids The mixture was heated in a two-roll mill to 180 ° C and then tested in an oven at 180 ° C to ensure heat stability. The discoloration was noted and is listed in Table II.

Table II.

Color.

Sample number Stabilization Medal Heating time Cadmium stearate 1.0 Zinc stearate 1.0 2,6-ditert.-hutyl-p-cresol 0, Trimethylolethane 0, Cadmium-tert.-butyl benzoate 2.0 p-tert-butylphenol 0, Trimethylolethane 0 , Barium laurate 0.6 Cadmium benzoate 0.6 Bisphenol A 0, Dipentaerythritol 0.3 Originally Clear Clear Clear After 15 min Shift in light yellow Clear Li us yellow After 30 min Yellow Shift in light yellow Light yellow After 45 min Yellow Strong yellow Light yellow After 60 min Strong gut Yellow Light yellow After 75 min Strong yellow Yellow with black edges Light yellow Or 90 min Deep yellow Yellow with blackLight edges Strong yellow after 105 min Deep yellow Yellow with black edges Strong yellow After 120 min Yellow with black edges Black Strong yellow The above test show the effectiveness of the stabilizer compositions according to the invention. Sample L was heated for an additional 1 hour, and at the end of this time the sample was the same color as at 120 minutes.

Example 3.

Example 1 was repeated using the resin Vinylite VYHH, a copolymer of 87 °, vinyl chloride and 13% vinyl acetate. Equivalent results were obtained.

Example 4.

Example 2 was repeated using the resin "Vinylite VYHH", a copolymer of 87% vinyl chloride and 13% vinyl acetate. Equivalent results were obtained.

Claims (4)

Patent claim: A stabilizer for polyvinyl chloride resin, which stabilizer is capable of improving the resistance of the resin to discoloration when heated at 180 ° C, characterized in that it consists of a hydrocarbon-substituted phenol having 1 to 30 carbon atoms per phenolic hydroxyl group, of a salt of a polyvalent metal and a monocarboxylic, Iran nitrogen atom free, organic acid, sum having 6-18 carbon atoms, and of a polyol having the structure CH, OH R — CH2 - C — C1120H CH, OH - - in which R represents vate or a organic radical from the group of alkyl, alkoxy, hydroxyalkyl and alkoxyhydroxyalkyl groups having 1-30 carbon atoms. Stabilizer according to claim 1, characterized in that the polyol is trimethylolpropane. Stabilizer according to claim 1, characterized in that the polyol is dipentaerythritol. Stabilizer according to claim 1, characterized in that the polyol is trimethylolethane. Stabilizer according to claim 1, characterized in that the phenol is para, para'-isopropylidene diphenol. Stabilizer according to claim 1, kanneteeknat & Jay, wherein the polyvalent metal salt is a mixture of at least two metal salts. Stabilizer according to claim 6, characterized in that the polyvalent metal salts arc a mixture of barium and cadmium salts. Stabilizer according to claim 6, characterized in that the polyvalent metal salts are mixed barium and cadmium laurates. 9. Stabilizer according to claim 6, characterized in that the polyvalent metal salts are mixed barium laurate and cadmium benzoate. 10. Set to produce a polyvinyl chloride resin composition having improved resistance to discoloration when heated at 180 ° C, characterized in that a polyvinyl chloride resin is mixed with a stabilizer according to any one of claims 1-9. According to patent claim 11, characterized in that the epoxy compound is an epoxy ester 13. Set according to claim 10, characterized in that the polyvinyl chloride resin consists of a polyvinyl chloride 10. characterized in that the polyvinyl chloride resin is composed of a copolymer of vinyl chloride and vinyl acetate 15. Resin composition prepared in the manner according to any of the patents 10-1 4. Request publications: