SU508217A3 - Polyolefin Composition - Google Patents

Description

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in which, P and P are pivot or ornma are Ofiyr from the other and mean an alkyl group with 1-12 carbon atoms or a monocyclic ring structure with 512 carbon atoms:, H is an integer 1-3:

if n is 1, from - an alkyl group with 12O. preferably 1-18, in particular 6-18, carbon atoms or the benzyl group:

if n is 2, RJ is an alkylene group with 1-2O, preferably 1-16, in particular JCTH 2-12. carbon atoms, g xyly to lenovo group, or alkyl substituted IB. I .. xylylene or its alkyl substituted group of the general formula - 7 is hydrogen in which P is an alkyl group with 1-5 carbon atoms if Pd is 1,3,5-mesitylene or 2,4,6-alkyl-substituted mesitylene group, where alkyl substituents contain 1-5 carbon atoms, in the amount of 0.005-5% by weight of polym.,. :; . . . ; - / The term alkyl or alkylene, both started Wd, means an alkyl or alkylene group with 1 to 2O carbon atoms, for example methyl, ethyl, propyl, iso propyl, butyl, pentyl, isopentyl, hexyl, octyl, dodecyl, tetradeyl, hexadecyl , octadecan, eicosyl, methylene, ethylene, propylene, butylene, octylene, dodecylen, octadocylene or eicosylene. P, RIO and monocyclic substituents of Rj and Pg, there may be lower alkyl groups with 1-5 carbon atoms, namely methyl, ethyl, propyl, butyl and peytyl, o Compounds of formula 1 are recommended to be added in an amount of about 0.005 -5%, preferably 0, O12% by weight of polymer. Derivatives of piperazine disks of coagulantly Formula 1 can be used in combination with others with etostabilizers, such as, for example, 2- {2-oxyphenyl benzotropylase, 2-hydroxybenzophenols, nickel complexes, and benzoates. The stabilizers prepared according to claim 2) of the invention are recommended to protect polyolefins from the harmful effects of light. Stabilized polymers are used for the same materials as plastics, especially as films and fibers. The obtained compounds can be introduced into the polymer composition during the processing, for example, during hot rolling, followed by extruding, pressing, extruding into strands, fibers, threads, beads, etc. In the case of obtaining polymer from liquid monomer (e.g. styrene) The stabilizer may be dispersed or dissolved in the monomer before polymerization or vulcanization. The proposed stabilizers can be used in compositions containing other additives, such as plasticizers, pigments, fillers, paints, glass or fugue fibers, thermal antioxidants, etc. In most cases, it is advisable to add a sufficient amount of thermal antioxidants to the plastic composition plastics from thermal and oxidative destruction; An antioxidant needs as much as a light stabilizer, i.e. approximately p 005-5 wt.%, preferably 0.01-2 wt.% . As antioxidants, phosphorous esters are used, for example, triphenylphosphite and dibutylphosphite, and also alkyl arylphosphites, for example, dibutylphenylphosphite. The best results are achieved by additionally introducing thermal antioxidants from the class of space-hindered phenols. Example 1, Exposure on artificial light. A, Manufacture of samples. Unstabilized polypropylene powder is mixed with additives. The mixed material is rolled for 5 minutes on rollers at 182 ° C. Rolled sheet B mold is pressed into a film with a thickness of 5 mm at a temperature of 220 C and under a pressure of 1.25 kg / cm2 with water cooling in the mold. B. Test Method. The test is carried out in a device consisting of fluorescent fluorescent lamps and black lamps on the basis of the model of Atma Cua "a tw /", which consists of 4 tubes of alternating fluorescent day lamps and black lamps {20) Samples - films 55 mm are placed on holders with dimensions 75 :: 50 mm with holes 6x25 mm and then on a rotating drum at a distance of 5 mm from the lamps of the described fixture. The time (in hours) of the manifestation of 0.5 units of absorption to rbonyl, which are determined by an infrared spectrophotometer, is measured. The formation of functional carbonyl groups in a polymer is proportional to the degree of deterioration of its properties under the influence of ultraviolet rays. The test results are shown in Table. 1, with the amount of sample given in weight pro (enta based on the weight of the polymer.

The keacaca from the tested samples, as well as the cops, the control sample contains 0.2% di-and-octadecyl {3,5-di-tert.-butyl-F-okoibeneel: -phosphate, which is pro-oxidative to prevent oxidative destruction of polypropylene. Other substituted fuzyl antioxidants can be used instead of the di-X-octadeyl- (3,5-d-tert., -6utyl-4-oxybenzyl) -f6sfonate used in these compositions, Sh p and me 2,

A. Stabilized linear polyethylene is manufactured by introducing 05 wt.% | 4-ba13yl-2 into it | 2.6,6 tetramethyl-3,5-diketo piperazine. As a result of the ultraviolet radiation of the stabilized composition, the stabilized composition becomes less fragile and brittle than the comp (Zits without the specified stabilizer.

B. Stabilized crystalline, polystyrene is obtained by introducing 0.1 into it.

Ta bl g c a 1

; weight, 4,4 - (2,4,6-trimethyl-cC, L mezityl den) -triss-2,2,6,6-tetramethyl, 3.5 dpi-piperazine Under the influence of ultra-violet rays, the stabilized composite becomes less fragile and brittle than the unstabilized composition. , Frozen High impact polystyrene resin containing

The flO elastomer, for example, butadiene styrene, is stabilized against the loss of elasticity properties under ultraviolet rays by the introduction of 0.3 wt.% 15-octadecyl-7, 15 Dyasadaspiroc 5,1.5.3) hexadecane-14116-et. The unstabilized resin is dissolved in chloroform and a stabilizer is added, after which the mixture is applied to glass slabs and the solvent is evaporated to obtain a uniform film, which, after drying, can be removed and cut off after further pressing for 7 minutes at 16 3 ° C and a pressure of 14 kg / cm2, as a result of which a uniform of thickness (25 mm) is obtained. Sheets are cut into pouches with a size of approximately 100x12.5 mm. Some of these bands are measured with a percentage of elongation in the Instron tensile testing device, C) the steel part of the bands is placed in the device described in Example 1B, measuring the time duration up to 5O% - reduction of elongation. The stabilized poly styrene resin retains its elastic properties for a longer period than the non-stabilized one. Similar results are achieved by using, instead of the indicated stabilizer equivalent, the amount of one of the following stabilizers; 0.1 wt% 15, 15 (.4,6-trimethyl - ct, wasp, ist -chmesitylidene) tris-, 15-diazabIoHirO- (5.1,5,3} -hexadecane-14. 1e-di: -.. ,,. about ..; .., O, 2 BeCi% 15, 15 - "d-octamethyl-. -bis- 7,15-dnasadispiro-4, 1,5,3) -hexa decane 14,1e-dyona); 1 wt.% 15 1-methyl-7,15-tadazadispiro- {5 .1; b, 3) -hexadecan-14,16-DIO; O, 1 wt.% 4-H-octadecyl-2.2, b, 6-tetramethyl 3.5 iketopic azine; O, 1 wt.% 4,4, 5 b-tetramethyl. And -); silyl azdenyl-bis- {2.2,6,6-tetramethyl | -3, 5-diketopiperazine); ... O, 5 wt.% 4.4 - (,) ktametilen) -bis -, - (2,2,6,6-tetramethyl-3,5-diketopiperazine 1 wt.% 4-n-yuktil-2,2,6,6-tetrame1 il-3, 5-iketopiperazine; p, 5 wt.% 23-L-octadecyl-11,23-diazadispiro- (9.1.9,3) -tetracosan-22.24-dione: 0.5 wt.% 4-benzyl 2; 6-aimethyl -2,6-dipive1,5-3,5 diketopiperazine; 0,5 v0c.% 4-octyl-2,2,6, e-trans-3-3 .5-diketparaziyaa. In each of the specified compositions it is also possible to introduce protivoxidants, such kiv, for example, as di-a-yuktadecyl-is - (3-Trpbt-butyl-4-oxy-5-methylbenzyl) -malonate, 2.4-bis- (4-hydroxy-3,5-di-tr et. -6utylphenoxy) -6- (n. -octyl1-ethylthio) -1,3,5-triaziH, 2,4, -bis- (3,5-DI-tert.-butyloxyphznosi) -6- (t-oxy1) -1,3.5-triazine, di-ug-octadecyl-3,5-di-tert.- € util-4-hydroxybenzylphosphon; Octadecid-3- (31 5-n-t-tert.-. butyl-4-oxyphenip) gpropionat. Example 4 Exposure to light in the open. Additives in the liquid state and in the specified amounts are mixed into a powdered polypropylene, powdered sewed for 5 minutes in a C planetary gear mixer, then the dried mixture is dried in a vacuum in a vacuum furnace under a 750 mm vacuum of a water column. . :. . -: /:.,:}: .- ..,, - Polypropylene powder, containing these additives, are mixed in an extruder at 232 C. The obtained granules sprinkle the melt at -. 26 ° C to monofilament with a denier of 15 using a filter with diaphragms of 1O mm for the spinning of monofilament. Monovolocal is cooled by air and oryoztiruyut in the ratio of 4-1 between hot and cold rollers and wound them on the reel. The monofilament is placed on a wooden framework for the duration of the exposure and is subjected to natural conditions. The specimens are periodically removed and subjected to a tensile test when tested with a psychiatric tensile test using the InSerf firm. To determine if the monofilaments are 50% -% smO, a decrease in tensile strength is determined. In tab. Table 2 summarizes the test results, which demonstrate the number of kilrlangleys (cells) to achieve a reduction in tensile strength. (Langley, "DN" and ", and measuring energy and ultr; rafiol and the spectral region).

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 KeoKJUbiA from samples, as well as the control sample, contains 10.5% of the antioxidant di-octadecyl- (3,5-di-tert-butyl-4g-oxybenzyl) -profonate and O, 1% calcium stearate as a buffer.

5O8217

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Ф орм ул а and 3 о б р е т в н

A composition based on a polyolefin and a stabilizing additive is distinguished by the fact that, in order to increase the light stabilization effect, a compound of the following formula was introduced as a stabilizing additive

/ L,;

 with j o /

and and

KI Kg

where J and Ra are equal or different from each other and mean an alkyl group with 1-12 carbon atoms or a monocyclic structure with 5-12 carbon atoms;

 - integer 1-3;

if there is a 1-alkyl group with 1-2 O carbon atoms or a benzyl group;

if to 2, Kj is an alkylene group with 1-2O carbon atoms, and, is α-xylylene or its alkyl substituted group of the general formula I

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where 4 is a y-hydrogen or alkyl group with 1-5 carbon atoms;

if k 3, Rj is -1,3,5-mei-etileno or 2,4,6-alkyl-substituted mesitylene group, where the alkyl substituents contain 1-5 carbon atoms,

in the amount of 0.005-5% by weight of the polymer.