CS239596B1 - High water and oil resistant high performance polymers - Google Patents

Abstract

The subject of this invention are plasticized polymers highly resistant to water and petroleum materials, especially based on homopolymers and/or copolymers of vinyl chloride, suitable a) for the production of polyurethanes based on by-products from a large-tonnage petrochemical process. They consist of 39 to 94 wt. d. of starting polymer and/or copolymer material, 5 to 60 wt. d. of polymer plasticizer, prepared by the action of diols to polyols on distillation residues from the production of cyclohexanone or cyclohexanol by oxidation of cyclohexane and auxiliary substances

Description

3 4 239396

The invention relates to spawning. water-resistant polymers and petroleum materials, mainly based on homopolymers and / or copolymers of vinyl chloride, with the presence of auxiliary substances, also suitable for the production of by-product polyurethanes from a heavy petrochemical process.

In the manufacture of spun polymers. mainly polyvinyl chloride, many types of chemical compounds are used as softeners, which have the requisite desiccation with the plasticized polymer and satisfy the desired properties. In addition to the necessary features, the availability and price of the softener is also important. Particularly valuable for the plastics industry are the polymeric types of softeners, since they incorporate homo-molecular materials better, do not evaporate as monomeric softeners, and do not impart odor to the products. Providing the final product with a long-lasting durability and ultimately the high quality of the final products. Conventional polymeric softeners include polymeric hydrocarbons (polyisobutylaluminum) which can be applied especially to chlorocarbon, polystyrene and partly to polyvinyl chloride and copolymers thereof. Furthermore, they are low molecular weight homopolymers and copolymers of butadiene and acrylonitrile which soften the copolymers of vinyl chloride and polyvinyl chloride (U.S. Pat. No. 2,552,904, French Pat. Chem., 26, 152, (1952)], a co-polymer of vinyl acetate with olefins (V. Brit.pat. 666 530; U.S. Pat. No. 2,657,188), etc. A significant group of polymeric surfactants are polymeric softeners which can be prepared by esterification of polyhydric alcohols with monocarboxylic acids, e.g. esterification of triethylene glycol and polyglycols with caprylic acids, capronic acids (U.S. Pat. No. 2,554,259; V. Brit. or by esterification of polyvalent alcohols with dicarboxylic acids as well as with monocarboxylic acid C7 to Ca (French Pat. 1 078 377) or butanediol and ethylene glycol adipic acid (U.S. Pat. No. 209,664). there are also combinations of polyester surfactants with other copolymers, such as polypropylene sebacate and copolymer of butadiene with acrylonitrile (V). Briton. pat. 640 558). Although these types of sizing agents have excellent technical properties and high purity requirements for starting materials.

SUMMARY OF THE INVENTION The subject matter of the present invention is a water-based, high-water-resistant, petroleum-based material, in particular homopolymers and / or copolymers of vinyl chloride in the presence of auxiliary liquids consisting of 39 to 94 wt. d. starting polymeric and / or copolymer material, 5 to 60 wt. d. a polymeric zinc builder prepared by the action of diols to polyols on distillation residues from the production of cyclohexane or cyclohexanol by oxidation of cyclohexane. The advantage of the softened polymers of the present invention is the significant technical and economical recovery of the technical readily available polyester polyols, based on the cyclohexanone and cyclohexanol production by oxidation of cyclohoxane and the possibility of extending the production of polymeric lubricants. The films prepared according to the present invention possess the necessary technical properties as foils soaked with other high quality commercial polymeric softeners, such as high dimensional stability and stability, and water and organic solvent resistance.

Especially polyesterpolyols prepared by the esterification described in, for example, U.S. Pat. No. 229,429 or by modifying the manufacturing process of the polymeric wetting agent of the Czech Republic, Author's Certificate No. 230 443 and (PV) may be used as the plasticizer 11a to prepare the softened polymers of the present invention. 4768-83). The base raw materials for the production of polyester polyols are the by-products isolated as distillation residue from the distillation, respectively. rectification of cyclohexanone and cyclohexanol, an oxidate generally prepared by catalytic oxidation of cyclohexane, consisting mainly of a mixture of monocarboxylic acids, hydroxyacids and ketoacids, esters and polyesters of said acids, optionally cyclohexanone and cyclohexanol. In addition, internal ester esters of lactones are present in monomeric form, but also in dimers and higher oligomers. the two by-products can be used in the preparation of the polyester polyols in the flood state, by the chemical ones, by the physico-chemical chemistry or by the phyto-phosphate compound. The addition of dicarbonyl acetate (alone or in admixture) and monoalkidylic acid is suitable to change the properties of the polyosterojyol as a wetting agent.

Component! for polyesterillation, optionally estersification, and partial reesterification, the esters of hydroxyl groups and the addition of divalent and / or alcohols such as glycols, t-methylolpropane, glycerol, pentaerythritol and the like can be used. reesterification catalysts. Further details and advantages of the invention are apparent from the following examples. Example 1

Polyesterpolyol (D-10) is prepared by esterification of 6,250 g of residues from the preparation of cyclohexanone and cyclohexanol by oxidation of cyclohexane with an acid number of 269 mg KOH / g and 239596 5 1062.5 g of diethylene glycol at a temperature of 200 ° C in the presence of 4.35 g of tetrabutyl titanate. Values followed: hydroxyl number = - 73.2 mg ΚθΗ / g; acid number 5.0 mgKOH / g; saponification number 374.4 mg KOH / g 6 a, viscosity 8.3 Pas / 25 ° C. From the obtained polyesterpolyol, mixtures of PVC, softeners and additives are prepared by conventional methods in a conventional manner using a conventional method: 1

Suspension polyvinyl chloride to a value of 70 650 g Polyesterpolyol 150 g Dioctyl phthalate (DOP) 150 g TiO2 - Stabilizer 20 g Epoxybutyl ester 25 g Lubricant (glidant) 5 g Foils prepared from this mixture overlapping properties: 1 thermal stability at 180 CC 120 strength in thrust - MPa 23,0 elongation -% 342 modulus 100% - MPa 13,3 resistivity - N / mm 41 hardness ° Sh A - ° Sh 81 brittleness temperature - ° C - 14 migration to PE -% 5,9 EXAMPLE 2 The polyester polyol (D-42) is prepared by esterification of 1500 g of residues from the production of cyclohexanone and cyclohexanol by oxidation of cyclohexane as specified in Example 1, 216 grams of diethylene glycol and: 12 grams of glycerol at 220 ° C in the presence of 1.1 g of tetrabutyl titanate and in a stream of nitrogen as a suspension 1 Suspended polyvinyl chloride to a value of 70 650 g polyesterpolyol D-42 150 g dioctyl phthalate (DOP) 150 g TiO 2 - stabilizer 20 g epoxybutyl ester 25 g lubricant 5 g 2 3 640 g 650 g 150 g - 150 g 300 g 10 g - 20 g 20 g 25 g 25 g 5 g 5 gi 1 mm thick 2 3 120 150 23,0 20,6 348 348 13.1 10.2 44.5 34.4 '81.5 7: 8 —14 —31 4.8 12.7 0.38 0.05 Water Pitch. It has the following properties: hydroxyl number 51.3 mg KOH / g; acid number 2.3 mg KOH / g, saponification number 402 mg KOH / g; viscosity 11.9 Pas / 25 ° C. From the polyester polyol obtained, mixtures of PVC, wetting agents and additives are prepared according to the procedure described in Example 1 for the test of damping properties. 2 3 610 g 610 g 150 g - 150 g 300 g 40 g 40 g 20 g 20 g 25 g 25 g 5 g. 5 g

Claims (2)

239596 7 8 1 mm pressed sheets have the following characteristics: 1 2 3 thermal stability at 180 ° C - min 120 * 180 * 180 'tensile strength - MPa 22,5 22,1 19,4 ductility -% 334,0 332 360 module 100% - MPa 13,7 12,9 9,3 resistivity resistance 39,5 43,1 33,9 — N / mm hardness ° Sh A - ° Sh 83 83 75,5 brittleness temperature - ° C —15 -15 -34 migration to PE -% 8.5 6.6 13.7 aqueous extract -% 0.31 1 0.42 0.1 Example 3 The polyester polyol has the following values: hydroxyl number 46.8 mg KOH / G; Acid number Polyesterpolyol (D-43) was prepared to give 2.3 mg KOH / g; saponification number by esterification of 1500 g of distillation residue 390 mg KOH / g; viscosity 9.8 Pas / 25 ° C. of the obtained polyesterpolyol, titanate and 120 g of xylene are prepared as a water scavenger in the presence of 1.1 g of tetrabutyl test for scrubbing properties. blends and foils according to the following formulas: 1 2 3 Suspension polyvinylchloride 70 610 '650 610 polyesterpolyol D-43 150 150 - dioctylphthalate (DOP) 150 150 300 TiO 2 40 - 40 stabilizer 20 20 20 epoxybutyl ester 25 25 25 wax E 3 3 3 stearin 2 2 2 Films made of these will give the following properties: 1 2 3 Thermal stability at 180 ° C 180 '120 * 180 * Tensile strength - MPa 22,1 22,6 19,4 Elongation -% 340 326 360 Module 100% 12.4 13.9 9.3 additional tear resistance - N / mm 40.0 38.4 33.9 hardness ° Sh - ° Sh 80 84 75.5 brittleness temperature - ° C —16 -14 —34 migration to PE - % 7,8 7,8 13,7 Water leachate -% 0,32 0,31 0,10 SURFACE FLOWS Highly resistant to water and oil materials, especially homopolymers and / or copolymer vinyl chloride in the presence of auxiliary liquids. characterized in that they consist of 39 to 94 wt. d. a starting polymeric and / or copolymeric material, 5 to 60 wt. d. polymeric softener prepared by the action of diols to polyols on distillation residues from the production of cyclohexanone or cyclohexanol by oxidation of cyclohexane. Severografla, n. P ,, závod 7, Most Price 2,40 Kčs