Composition synergists for the stabilization of polyolefins

 

(57) Abstract:

Describes the composition of synergists for the stabilization of polyolefins, comprising three(2,4-ditertbutyl)FOSFA and a collection of other phosphites, characterized in that as the population it contains three(2-tertbutylphenyl)FOSFA, three(4-tertbutylphenyl)FOSFA, di(4-tertbutylphenyl)(2,6-ditertbutyl)FOSFA and di(4-tertbutylphenyl)(2,4,6-tetrachlorophenyl)postit in the following ratio of ingredients, wt. %: three(2,4-ditertbutyl)postit 90,0 - 94,5, three(2-tertbutylphenyl)postit 2,5 - 3,8, three(4-tertbutylphenyl)postit 2,8 - 5,5, di(4-tertbutylphenyl)(2,6-ditertbutyl)postit of 0.1 - 0.4, di(4-tertbutylphenyl)(2,4,6-tetrachlorophenyl)postit 0.1 to 0.3. The technical result is an increase synergies in the process of stabilization of polyolefins. 3 table.

The present invention relates to the stabilization of polymeric materials and can be implemented in the chemical industry. To increase synergies in the process of stabilizing polyolefin compositions used synergists for the stabilization of polyolefins.

Known composition synergists for the stabilization of polyolefins containing three(2,4-ditertbutyl)fo is soma low synergistic effect in the stabilization of polyolefins.

Also known composition synergists for the stabilization of polyolefins containing any postit General formula (RO)3P, in particular three(2,4-ditertbutyl)FOSFA, and a set of (one or more) of phosphites of the General formula

< / BR>
R is alkyl, aryl, aralkyl, R1- Allen, arankele (ed.the certificate of the USSR N 493485 MKI3C 07 F (1975)). The disadvantage of this known arrangement, which on the totality of symptoms and the achieved technical result closest to declare our object and is therefore selected as a prototype, is relatively low synergistic effect in the stabilization of polyolefins.

The aim of the present invention is to increase synergies in the process of stabilization of polyolefins.

The declared objective is achieved by the fact that the known composition of synergists for the stabilization of polyolefins, comprising three(2,4-ditertbutyl)FOSFA and set of other phosphites, as this set contains three(2-tertbutylphenyl)FOSFA, three(4-tertbutylphenyl)FOSFA, di(4-tertbutylphenyl)(2,6-ditertbutyl)FOSFA and di(4-tertbutylphenyl)(2,4,6-tetrachlorophenyl)postit in the following ratio of ingredients, wt.%:

Three(2,4-ditretbutyl the 4-tertbutylphenyl)(2,6-ditertbutyl)postit - 0.1 -0.4

Di(4-tertbutylphenyl)(2,4,6-tetrachlorophenyl)postit - 0.1 -0.3

The use of such compositions synergistic effect of the stabilization of polyolefins is greatly increased.

Previously, the composition of synergists for the stabilization of polyolefins with the above set of features in the literature are not described. Marked the moment gives us every reason to believe that declare our object is inherent in the first criterial element of the invention in the patent legislation of the Russian Federation - novelty. In addition, knowledge of the properties of the composition of the prototype and characteristics amendments (namely the introduction as a set of phosphites three(2-tertbutylphenyl)phosphite, three(4-tertbutylphenyl)phosphite, di(4-tertbutylphenyl)(2,6-ditertbutyl)phosphite and di(4-tertbutylphenyl)(2,4,6-tetrachloroethylthio) is not possible a priori to predict the above-noted positive effects - increased synergistic effect in the stabilization of various polyolefins, and this in turn means, what is the essence of the proposed us object explicitly known at the present level of the art does not. Just what allows us to conclude that samsemilia us the composition is quite simple in composition, easily manufactured by a well-developed technology of those reagents which are produced now by the domestic industry, and is currently under implementation in large-scale production. This means that we declare our object falls under the third criterion characteristic of the invention and industrial applicability.

Declare on the subject of the invention composition synergists for the stabilization of polyolefins is illustrated by the following examples.

Example 1 (preparation of the claimed composition synergists).

By mixing in random order are the following composition source of phenols, wt.%:

2,4-ditertbutyl - 90.0

2-tertbutylphenol - 2.0

4-tertbutylphenol - 3.0

2,6-ditertbutyl - 2.0

2,4,6-tetrachlorophenol - 3.0

100 g of this mixture of phenols, 50 ml of n-heptane and 0.3 g of pyridine, which acts as a catalyst (ed. mon. The USSR 172328 (1968)), is heated with thorough stirring to 50oC, after which the mixture is injected dropwise 21.3 g (13.6 ml) trichloride phosphorus. Upon completion of the described procedure, the reaction system was kept at this temperature for 1 hour and then contacting the mixture with isopropanol and mix thoroughly. The residue is filtered off, washed and dried at room temperature. Thus obtained target product is a mixture of three(2,4-ditertbutyl)-, tri(2-tertbutylphenyl)-, tri(4-tertbutylphenyl)-, di(4-tertbutylphenyl)((2,6-ditertbutyl)- and di(4-tertbutylphenyl)(2,4,6-tetrachlorophenyl)has been further analyzed by liquid chromatography. Data analysis, wt.%:

Three(2,4-ditertbutyl)postit - 91.5

Three(2-tertbutylphenyl)postit - 3.8

Three(4-tertbutylphenyl)postit - 4.1

Di(4-tertbutylphenyl)(2,6-ditertbutyl)postit - 0.4

Di(4-tertbutylphenyl)(2,4,6-tetrachlorophenyl)postit - 0.2

Example 2.

Prepare the composition of the synergists of the composition specified in example 1, after which experience it on a synergistic effect in the stabilization of polyethylene. This 100 wt. parts low pressure polyethylene is mixed with 0.1 wt. part of the obtained composition synergists and 0.1 wt. part of the antioxidant ester 4-hydroxy-3,5-directrories acid and pentaerythritol ("venosan-23") in a high-speed mixer at room temperature for 10 minutes the mixture is ekstragiruyut on single-worm extruder with a ratio of the length of the worm to the diameter CAH determine such parameters, as the induction period of oxidation (, h), elongation at break (%) and the melt flow index after five extrusion (PTR5). Determination of induction period of oxidation performed on the side of the unit with 200oC and a pressure of 250 mm RT.article according to a known method (K. P. Piotrowski, H. N. Tarasova Aging and stabilization of synthetic rubber and vulcanization agents. M.: Chemistry, 1980). Elongation at break was determined according to GOST 11268-80 on installing RMI-60 at a temperature (20.0+0.5)oC and the moving speed of the rolling clamp 50 mm/min. and a melt flow Index was determined according to GOST 11645-73 on extrusion plastometer with the nozzle diameter of 2.095 mm at a temperature of (190.0+0.5)oC, load 5.0 kg after exposure of the material in the unit for 4-5 minutes

Test data for the specified cases are presented in table. 1.

Example 3.

Perform as example 2, but as the composition of the synergistic use the mixture, which according to chromatographic analysis has the following composition, wt.%:

Three(2,4-ditertbutyl)postit - 90.0

Three(2-tertbutylphenyl)postit - 3.8

Three(4-tertbutylphenyl)postit - 5.5

Di(4-tertbutylphenyl)(2,6-ditertbutyl is given according to the General scheme of example 2, but for testing use composition synergists, which according to that analysis has the following composition, wt.%:

Three(2,4-ditertbutyl)postit - 92.5

Three(2-tertbutylphenyl)postit - 3.5

Three(4-tertbutylphenyl)postit - 3.6

Di(4-tertbutylphenyl)(2,6-ditertbutyl)postit - 0.2

Di(4-tertbutylphenyl)(2,4,6-tetrachlorophenyl)postit - 0.2

Example 5.

Carry out the type of example 2, but for testing use composition synergists, which according to that analysis has the following composition, wt.%:

Three(2,4-ditertbutyl)postit - 94.5

Three(2-tertbutylphenyl)postit - 2.5

Three(4-tertbutylphenyl)postit - 2.8

Di(4-tertbutylphenyl)(2,6-ditertbutyl)postit - 0.1

Di(4-tertbutylphenyl)(2,4,6-tetrachlorophenyl)postit - 0.1

Example 6 (comparative).

Perform as described in example 2, using as the composition of the synergistic mixture composition, wt.%:

Three(2,4-ditertbutyl)postit - 85.0

Three(2-tertbutylphenyl)postit - 10.5

Three(4-tertbutylphenyl)postit - 4.0

Di(4-tertbutylphenyl)(2,6-ditertbutyl)postit - 0.3

Di(4-tertbutylphenyl)(2,4,6-tetrachlorophenyl)postit - 0.2

Example 7 (comparative).

Carried out as described in example 2, shenil)postit - 0.5

Three(4-tertbutylphenyl)postit - 0.6

Di(4-tertbutylphenyl)(2,6-ditertbutyl)postit - 0.2

Di(4-tertbutylphenyl)(2,4,6-tetrachlorophenyl)postit - 0.2

Example 8 (comparative).

Implement the type of example 2 with the composition of the synergistic composition, wt.%:

Three(2,4-ditertbutyl)postit - 94.0

Three(2-tertbutylphenyl)postit - 2.4

Three(4-tertbutylphenyl)postit - 2.4

Di(4-tertbutylphenyl)(2,6-ditertbutyl)postit - 0.7

Di(4-tertbutylphenyl)(2,4,6-tetrachlorophenyl)postit - 0.5

Example 9 (comparative).

Perform as example 2, but as the composition of the synergistic use of the mixture composition, wt.%:

Three(2,4-ditertbutyl)postit - 86.0

Three(2-tertbutylphenyl)postit - 5.0

Three(4-tertbutylphenyl)postit - 7.0

Di(4-tertbutylphenyl)(2,6-ditertbutyl)postit - 1.0

Di(4-tertbutylphenyl)(2,4,6-tetrachlorophenyl)postit - 1.0

Example 10 (the prototype).

Perform according to the General scheme of example 2, but as the song synergists take the mixture composition, wt.%:

Three-naphthyl)postit - 75.0

n-Oktilovom ether 4,4'-dimethyl-6,6'-ditretbutyl-2,2'-methylene-biphenylphosphine acid - 25,0

and 100 wt. parts of polyethylene take 0.1 wt. parts of the uke is CLASS="ptx2">

Perform according to the General scheme of example 2, but as the song synergists take the mixture composition, wt.%:

Three-naphthyl)postit - 50.0

n-Oktilovom ether 4,4'-dimethyl-6,6'-ditretbutyl-2,2'-methylene-biphenylphosphine acid - 50.0

Example 12 (comparative, the prototype).

Perform as described in example 2 technology, but as the composition of the synergistic use of the mixture composition, wt.%:

Three(2,4-ditertbutyl)postit - 75.0

n-Oktilovom ether 4,4'-dimethyl-6,6'-ditretbutyl-2,2'-methylene-biphenylphosphine acid - 25.0

The test results for the specified case is also presented in table. 1.

Example 13.

Prepare the composition of the synergists of the composition specified in example 2, after which experience it on a synergistic effect in the stabilization of polypropylene. This 100 wt. parts of polypropylene mixed with 0.1 wt. part of the obtained composition synergists and 0.1 wt. part of the antioxidant "venosan-23" in a high-speed mixer at room temperature for 10 minutes the mixture is ekstragiruyut on single-worm extruder with a ratio of the length of the worm to the diameter of 20:1 at 180-200oC. the granules at a temperature of 210-215oC pressed plates is at break (%) and melt flow index after five extrusion (PTR5) as described in example 2 scheme. Test data for selected cases are shown in table. 2.

Example 14.

Perform General technological scheme of example 13, but using composition synergists specified in example 3.

Example 15.

Carried out as example 13, but using composition synergists, the composition of which is given in example 4.

Example 16.

Carried out according to the scheme of example 13, using the specified in example 5, the composition of synergists.

Example 17 (comparative).

Perform the type of example 13, and the composition of the synergistic use specified in example 6 set.

Example 18 (comparative).

Carried out as example 13, but with the use of a composition, the composition specified in example 7.

Example 19 (comparative).

Perform General technological scheme of example 13, but using composition synergists specified in example 8.

Example 20 (comparative).

Carried out according to the scheme of example 13, using the specified in example 9 composition synergists.

Example 21 (the prototype).

Carried out like example 13, using the comp is isout scheme of example 13 with the use specified in example 11 composition of synergists.

Example 23 (comparative, the prototype).

Implement the scheme of example 13 with the use indicated in example 12 composition synergists.

Example 24.

Prepare the composition of the synergists of the composition specified in example 2, after which experience it on a synergistic effect in the stabilization of poly(4-methylpentene-2). This 100 wt. parts of poly(4-methylpentene-2) is mixed with 0.1 wt. part of the obtained composition synergists and 0.1 wt. part of the antioxidant venosan-23 in a high-speed mixer at room temperature for 10 minutes the mixture is ekstragiruyut on single-worm extruder with a ratio of the length of the worm to the diameter of 20:1 at 180-200oC. the granules at a temperature of 220-240oC pressed plate of thickness 1 mm and then determine the induction period of oxidation (, h), elongation at break (%) and the melt flow index after five extrusion (PTR5) specified in example 2 scheme. Test data for selected cases are shown in table. 3.

Example 25.

Perform General technological scheme of example 24, but using composition synergists specified in example 3.

Example 26.

< is 4.

Example 27.

Carried out according to the scheme of example 24, using the specified in example 5, the composition of synergists.

Example 28 (comparative).

Perform the type of example 24, but as the composition of the synergistic use specified in example 6 set.

Example 29 (comparative).

Carried out as example 24, but using the composition, the composition specified in example 7.

Example 30 (comparative).

Perform General technological scheme of example 24, but using composition synergists specified in example 8.

Example 31 (comparative).

Carried out according to the scheme of example 24, using the specified in example 9 composition synergists.

Example 32 (the prototype).

Carried out as example 24, using the composition of synergists specified in example 10.

Example 33 (comparative, the prototype).

Implement the scheme of example 24 with the application specified in example 11 composition of synergists.

Example 34 (comparative, the prototype).

Implement the scheme of example 24 with the use indicated in example 12 composition synergists.

As you can see in table. 1-3 La song-prototype (it is noted a significant increase in induction period of oxidation and melt flow index). Herewith declare our content limits composing the composition ingredients are essential and beyond them a synergistic effect is significantly attenuated and the purpose of the invention is not achieved (compare examples 2-5 and 6-9, 13-16, and 17-20, 24-27, and 28-31, respectively, for each of the named table. 1-3 types of polyolefins). Note that similar results were obtained by us and other polyolefins (polyethylene, copolymer of polyethylene and polypropylene, polyisobutylene and other).

Composition synergists for the stabilization of polyolefins, comprising three(2,4-ditertbutyl)FOSFA and set of other phosphites, characterized in that as the population it contains three(2-tertbutylphenyl)FOSFA, three(4-tertbutylphenyl)FOSFA, di(4-tertbutylphenyl) (2,6-ditertbutyl)FOSFA and di(4-tertbutylphenyl) (2,4,6-tetrachlorophenyl)postit in the following ratio of ingredients, wt.%:

Three(2,4-ditertbutyl)postit - 90,0 - 94,5

Three(2-tertbutylphenyl)postit - 2,5 - 3,8

Three(4-tertbutylphenyl)postit - 2,8 - 5,5

Di(4-tertbutylphenyl) (2,6-ditertbutyl)postit - 0,1 - 0,4

Di(4-tertbutylphenyl) (2,4,6-tetrachlorophenyl)postit - 0.1 to 0.3

 

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