SU859398A1 - Polymeric composition - Google Patents

Description

(54) POLYMER COMPOSITION

The invention relates to polymeric compositions based on polypropylene and stabilizers for light and thermo-oxidative degradation and can be used in the manufacture of products for various purposes (film fibers, raffi, sheets, etc.). The stabilized polypropylene compositions are known, including various benzotriazole derivatives as light stabilizers, for example 2- (2 -oxy-5-methylphenyl) -benzotriazole (Tinuvin P), 5-chloro-2- (2 -oxy-5-methyl-3-tert-butylphenyl) ) -benzotriazole (Tinuvin 326), 5-chloro-2- (2 -oxy-3,5-di-tertbutylphenyl) -b, JH-isotriazol (Tinuvin 327) 1. Stabilized polypropylene compositions are also known that include phenolic compounds as thermostabilizer, for example 2 , 2-methylene bis- (4-methyl-b-tert-butylphenol) (Visalkofen B.P.), 4,4-thiobis- (3-methyl-6 -tbutylphenol) (Thioalkofen BM), 1, 1,3-tris- (4 -oxy -2-methyl-5-tertbutylphenyl) -butane (Trisalkofen Pb), pentaerythritol ester p) - (375-ditertbutyl-4-hydroxyphenyl - propionic acid (Irganox 1010) 2. The disadvantage of benzotriazole derivatives in the light stabilization of polymers is their relatively low light stabilizing efficiency, the absence of heat stabilizing efficiency, volatility and coloring effect on polymers. In the domestic industry there is also no available raw material for obtaining these products (p-cresol). Phenolic-type heat stabilizers well protect polymers from thermo-oxidative aging, but do not provide the necessary light resistance. Closest to the present invention is a polymer composition based on polypropylene a, soda {9) calcium stearate and, in the amount of a light stabilizer, a product based on aminotriacetonamine and dichloroethane: N, N-6HC- (2,2,6,6-tetramethylpiperidyl) -ethite lentiamine ( C-245) 3. The disadvantage of this light stabilizer is the complexity of its production technology and insufficient efficiency. The purpose of the invention is to increase the light and heat resistance and obtain compositions based on polypropylene.

To achieve this goal, a polypropylene-based composition containing calcium stearate and a stabilizing additive, as the latter, contains phosphorus-containing triacetonamine derivatives of the general structural formula

% f nz) pr (p)

CHj

-10 7

where Ar is CgH5, -C

 or 2;

 or 2

bis- (2,2,6,6-tetramethamide) - {b-naphthylphosphorous (AT-3)

HjC CHS

9 chusng

He CH-KN-P

HF

ASNg SNZ SNZ

2,2,6,6-tetramethylpiperidyl amide diphenylphosphoric acid (AT-4)

in the following ratio of components, wt.%

Polypropylene 98.8-99.8

Calcium stearate 0.1-0.2

Stabilizing

additive0,1-1

The proposed stabilizers are white crystalline powders. They are obtained on the basis of available raw materials (acetone, al (miak, aryl phosphoric acid chlorides).

The proposed stabilizers can be introduced into the polymers by any known means, for example, in the form of a powder or solution.

The amount of stabilizers added is O., 1-1.0 wt.% Based on the weight of the polymer, mostly 0.2-0.5 wt.%, And depends on the properties and type of the products obtained and on the conditions of their operation.

The proposed stabilized polymeric compositions contain stearate, calcium in an amount of 0% by weight of the polymer, which is used to neutralize the remaining acid residues and to plasticize the polymer.

The polymer compositions may additionally contain phenolic or amine-type antioxidants, ultraviolet light absorbers, phosphite stabilizers, agents for the formation of crystallization centers, lubricants, antistatic agents, flame retardants, pigments, carbon black, asbestos, etc.

In terms of their light-stabilizing efficiency, stabilizers are superior to benzotriazole derivatives, benzophenone and C-245 stabilizer, and they produce high-light and weather-resistant light colored or completely unstained colored or color-resistant colored products (yarns, fibers, films, sheets, raffy, etc. .).

Example 1. A mixture of powdered polypropylene (PP) with stabilizers AT-3, AT-4, AT-6 in the amounts listed in Table 1, and polypropylene with stabilizers Tinuvin 326 and C-245 is prepared for comparison.

From the prepared mixture, films with a thickness of 0.1 mm are pressed, which are then subjected to Xenotest-150 artificial weathering apparatus (temperature on the sample surface is 35 ° C, relative humidity is 60%) and heat aging in an air thermostat (film is placed in the middle of the cabinet in a suspended states). The light and heat resistance of the films is determined by the time of the test before destruction, the onset of brittleness.

The results of determining the light and heat resistance of polypropylene films with various stabilizers are shown in Table 1.

From the data presented in Table 1, it can be seen that the products AT-3, AT-4 and AT-6 exhibit a greater light and thermal stabilization efficiency compared with Tinuvin 326 and C-245, respectively.

Example 2. Powdered polypropylene (100 g), calcium stearate (StSa). (0.2 g) to stabilizers:. Tinuvin 326, C-245, AT-3, AT-4, Lti AT-6 in the amounts listed in Table 2 are mixed in a paddle mixer for 30 minutes. The resulting mixture is extruded at 210-220s, crushed to granules and pressed shoulders, 0.1 mm thick at 210t2 ° C.

The films are subjected to accelerated aging in the Xenotest-1200 artificial pigment apparatus. Light resistance according to the polymer compositions in the form of films is evaluated by the accumulation rate in films of carbonyl groups using an IR spectrometer. Table 2 shows the data on the kinetics of accumulation in the polymer of carbonyl groups (relative units) during the light-oxidative aging process. From the data of Table 2, it follows that the stabilizers AT-4, AT-3 and AT-b in polypropylene compositions, are superior in efficiency to the well-known products Tinuvin 326 and C-245, taken in the same dosages (0.3 and 0.5% by weight of the polymer). Example 3. Granules are prepared from powdered polypropylene and additives of stabilizers listed in Table 3. The granules are molded (at 250 ° C) on a laboratory stand with monofilament, which is then subjected to light-oxidative aging in the Xenotex-1200 artificial aging apparatus and thermo-oxidative aging in a heating cabinet at 150 ° C. Aging time is recorded until the sample collapses (the beginning of breakage, fragility). Table 3 shows the light and thermal resistance of monofilaments (8 tex) on the basis of polypropylene with various stabilizers. Phenozan 23 - pentaerythryl-tetrak-3- (3,5-ditert6util-4-hydroxyphenylpropionate). The data show that AT-4, AT-3 and AT-b in the presence of phenol antioxidant Fenozan 23, according to a complex of indicators, provide compositions based on polypropylene with a much higher light and heat resistance than the products Tinuvin-326 and C-245. in the same dosage. In addition, the thread threaded with AT-3, AT-4, and AT-B is colorless, while the thread with Tinouvin 326 has a pale yellow color. Example 4. From powdered polypropylene and stabilizers AT-3, AT-4, C-245, Tinuvin 326 receive granules, as in example 2. From the granules on a laboratory bench when molded monofilament, which is cast to light-oxidizing aging in the device ISEGOST 10761-64 and thermo-oxidative aging in a heating cabinet at 150 ° C. Aging time is recorded until the specimen is destroyed (beginning of breakage, fragility). Table 4 shows the light and heat resistance of monofilaments based on polypropylene with various stabilizers. From the data of Table 4 it follows that the threads stabilized with compounds AT-3 and AT-4 have higher light and heat resistance indices compared with the threads stabilized with compounds C-245 and Tinuvin326. In addition, Tinuvin-326 gives the threads a light yellow tint, while the stabilizers we offer do not paint the polymer. Example 5. A mixture of the composition specified in Table 5 is prepared from 10 kg of powdered polypropylene and various stabilizers. The mixture is extruded at 2 ° C-24 ° C and ground to a granule on a chipper. From the obtained granules form monofilament with a diameter of 0.2 mm on the unit of the company Reifenhauser. Monofilament is tested for light and heat resistance, as in Example 4. The light fastness of the thread is judged by maintaining strength as a percentage of the initial one after 40 days of irradiation in an IP device. Table 5 shows the light and heat resistance of monofilaments with a diameter of f, 2 mm based on polypropylene with various stabilizers. From the data of Table 5 it follows that after 40 days of irradiation, the threads stabilized with the composition based on AT-4 retain 100% strength, while the threads with the composition based on Tinuvin-326 are destroyed after 30 days, and the threads based on C - 245 retain - maintain 92% strength. The heat resistance of yarns with a stabilizing composition based on AT-4 also exceeds that of yarns stabilized with compositions based on C-245 and Tinuvin-326. Thus, both on films and filaments, polypropylene compositions with stabilizers AT-3, AT-4 and AT-6 have a higher light-heat resistance than similar compositions with the known stabilizers Tinuvin-326 and C-245. In addition, the advantage of these compositions is their colorlessness, which allows them to be used in any assortments of buildings and unstained buildings.

without stabilizer153

0.1% Tinuvina326 167

+ 0.3% Tinuvin 326 200

+ 0.5% Tinuvina326 241

+. 1.0% Tinuvina326 238

+ 0.1+ C-245281.

+ .0.3% C-245325

+ 0.5% C-245610

+ 1.0% C-245495

. + 0.1% AT-3324

+ 0.3% AT-3360

+ 0.5% AT-3620

+ 1.0% AT-3600

+ 0.1% AT-4456

+ 0.3% AT-4495

+ 0.5% AT-4650

-I- 1.0% AT-4665

+ 0.1% AT-6358

+ 0.3% AT-6370

+ 0.5% AT-6660

+ 1.0% AT-6692

Note All compositions contain stearate.

calcium as a plasticizer in an amount of 0.1% by weight of the polymer,

Table 1

6

eight

eight

eight

9

13

18

21

23

21

26

29

31

32

40

44

49

22

25

27

32 Composition

PP unstabilized

PP + StSa 0.2%)

 Tinuvin 326 (0.3%) 1.0 5.0 5.5

PP + St Sa (0.2%) - "

+ Tinuvin 326 (0.5%) 1.0 4.9 5.3 PP + St Ca (0.2%) + + C-245 (0.3%) PP - St Ca (0.2%) + + C-245 (0.5%) PP + St Ca (0.2%) - “+ AT-3 (0.2%) 19P + St Ca (0.2%) + + AT-3 (0, 5%) PP + St Ca (0.2%) + -I-AT-4 (0.3%) PP + Civ Ca (0.2%) + + AT-4 (0.5%) PP + St Ca (0.2%) + + AT-6 (0.3%) PP + St Ca (0.2%) + + AT-6 (0.5%)

Films are destroyed

PP + Tinuvin 326To, 5%) +

+ Phenozan 23 (0.2%) + + St Ca (0.2%).

PP + Tinuvin 326 (0.1%) +

+ Phenozan 23 (0.1%) +

+ Sa Sa (0.1%)

PP + C-245 (0.5%) + Phenozan 23 (0.2%) + + St Ca (0.2%)

PP + C-245 (0.1%) + + Phenozan 23 (O, 1%) + + Art. Ca (0.1%)

Table 2 About

1.0 12.0 1.0 2,12,22,3 1,0 2,02,12,1 1,0 2,22,23,0 1,0 2,02,22,9 1,01, 01.01.1 1.0 1.01, 11.1 1.0 2.22.83.1 1.0 2.42.72.9

Table 3

180

145

94

115

Sixths1 to 690

200

- -

E5v

134 Aging time, h, in the presence of carbonyl groups 34,75,05,3 1,11,52,55 l 1,11,11,72,65,0 3,73,94,04,54,8 2,93,03,23,84 , 6

PP + AT-3 (0.5%) +

+ Phenozan 23 (0.2%) + + St Ca (0.2%)

PP + AT-3 (P, 1%) +

+ Phenoean 23 (0.1%) + + St Ca (0.1%)

PP + AT-4 (0.5%) +

+ Phenozan 23 (0.2%) + + St Ca (0.2%)

PP + AT-4 (0.1%) +

+ Phenozan 23 (0.1%) Ca (0.1%)

PP + AT-6 (0.5%) +

+ Phenozan 23 (0.2%) + + St Ca (0.2%)

PP + AT-6 (0.1%) +

+ Phenozan 23 (0.1%) + + St Ca (0.1%)

. U and the composition includes a stearate note. In an amount of 0.1% by weight

Continuation of the table ..

one

230

712

| I.

167

577

 I 1

256

720

583

211

I I-,

248

700

   -

203

517

 .

Table

polymer

1 PP + Tinuvin 326 (0.3%) + +. Fenozac-23 (0.2%)

2 PP + C-245 (0.3%) +

+ Phenozan-23 (0.2%)

3 PP + AT-4 (0.3%) +

Claims (3)

+ Phenoean-23 (0.2%) Note The claims of the invention are a polymer composition containing polypropylene, which stabilizes the additive and calcium stearate, in order to improve the light and heat resistance, as well as the preparation of an uncolored composition, as a stabilizing additive, oia contains a derivative of triacetonamine of the general formula J (Ar-o-) n-Wra- (g) nH, o / cf. Ar -, T a b i u c 5 Light- 30 (collapses) yellow240 Colorless- 92 at 215 100 252 in to n compositions includes stearate in the amount of 0.2% by weight or 2; 1 or 2, with the following ratio of components, wt.%: Polypropylene 98.8-99.8 Stabilizing additive. 0.1-1.0 Calcium stearate 0.1-0.2 Sources of information taken into account during the examination 1. Stabilizers, accelerators, vulcanization agents, pore-forming agents abroad. Directory. Tambov, Izdvo Tambovska Pravda, 1972, p.53. 2. Chemical additives to polymers. Reference book, M, Himi, 1973, p., 45, 3. The author's certificate of the USSR 605411, class, C 08 L 23/12, 1977 (prototype),