Stabilising mixture for high chlorine resistance

FIELD: chemistry.

SUBSTANCE: addition of a stabilising amount of a mixture to high density polyethylene, where the said mixture contains 4,4'-bis(α,α-dimethylbenzyl)diphenylamine and sterically hindered phenol, enables to increase resistance to decomposition caused by chlorinated water.

EFFECT: pipes made from such a stabilising composition are suitable for conveying hot water, particularly chlorinated water.

6 cl, 3 ex

 

The LEVEL of TECHNOLOGY

The technical field to which the invention relates

The present invention relates to a stabilizing mixture for polymeric thermoplastic resin. More specifically, the present invention relates to a stabilizing mixture for polymeric thermoplastic resin, which can improve the resistance to degradation caused by chlorinated water.

Description of the prior art

In engineering it is known that the hot water pipe, made of plastic, is subjected to premature mechanical damage due to crack growth caused by mechanical stress. The visible result of this damage is leaking water in the pipe caused by the formation of cracks or pin holes. In addition, it is known that premature damage of the plastic may occur as a result of extraction with hot water antioxidants/stabilizers present in the plastic. In addition, it is well known that once washed antioxidants as a result of extraction, plastic loses its protection, and is due to undergo mechanical damage due to thermal oxidative degradation.

In the U.S. chlorine added to drinking water for disinfection. However, the presence of chlorine resulted in about the Leme, associated with the stability of the plastic tubes, which transport water. Moreover, this problem has necessitated the use of standard test methods with which to measure the sustainability of plastic water pipes to chlorine.

A few years ago plastic pipe for water supply system made of polybutene-1, appeared in stores in the USA. In this water supply system for joining pipes used connecting parts of acetal resin. Soon after its introduction began to come complaints from places of its use of premature damage. This was due to the fact that the connecting parts of acetal resin contributed to the formation of water leaks. On the background of numerous lawsuits, manufacturers and distributors of pipeline began the study of the causes mechanical damage to the connecting parts of acetal resin. In General, it was concluded that Polyacetal not resistant to the harmful effects of chlorine. (See Broutman, L. J. et al., ANTEC 1999, 3366, and Lewis, P. R., ANTEC 2000, 3125).

Modern interest in plastic water pipes focused on polyethylene of high and medium density. In his custom made version of the ultimate use of polyethylene is used in pipes for hot water. Standard plastic plumbing the second pipe is used as a pipe plumbing and drainage, and sewage. Pipe polyethylene-based can sometimes contain soot.

In connection with the practice of applying water systems polybutene-1 the problem with the resistance of polyethylene to chlorinated water. In this regard, ASTM (American society for testing materials) to solve this problem was developed relevant standard test method for polyethylene and crosslinked polyethylene (ASTM Standard Test Methods F and F 2263 2023).

In General, it is known that hot water by itself can reduce the content of any stabilizers in plastic tubes (see publication Kramer, E. et al., Kunststoffe 73:11 (1983), which describes the study of the aging characteristics of the hot water pipes made of polybutene-1 and cross-linked polyethylene; publication Juskeviciute, S. et al., Mater. Vses. Simp. Vopr. Proizvod. Primen. Trub. Detalei Truboprovodov Polietilena (1966) 134, which describes the extraction of antioxidants water from films of high-pressure polyethylene; and the publication Pfahler, G. et al., Kunststoffe 78:142 (1988), related to the characterization of several extraction of phenolic antioxidants from compositions of polypropylene and high density polyethylene).

The publication also reported that the presence of chlorine in the water can accelerate damage to the plastic (See. Hassinen, J. et al., Polym. Degrad. & Stab. 84:261 (2004); Gill, T.S. et al., Proceedings of the Plastic Pipes X Conference, Gothenburg, 1998; Tanaka, A. et al., Proeedings of the Plastic Pipes X Conference, Gothenburg; 1998; Ifwarson, M. et al., Proceedings of the Plastic Pipes X Conference, Gothenburg; 1998; and Dear, J.P. et al., Polymers &Polymer Composites 9:1 (2001)).

In U.S. Patent 6541547 reveal moldings of polyolefin, which is stable in continuous contact with the extracting medium, and which include as stabilizers selected mixture containing the organic postit or phosphonic, and a specially selected group sterically obstructed phenols, or a certain group of sterically obstructed amines. In addition, it is specified that the selected three-component mixture comprising postit or phosphonic, phenolic antioxidant and a group sterically obstructed amines, particularly suitable as a stabilizer for moldings of polyolefin, which are in permanent contact with extracting medium.

The content of the above publications in their entirety are given here for information.

The INVENTION

There is a continuing need to increase the sustainability of plastic water pipes to the harmful effects of chlorine on the plastic from which the manufactured pipe. The present invention relates to a stabilizing mixture comprising the stabilizer of an aromatic amine and a sterically hindered phenol, for polymeric thermoplastic resins that improve the resistance to decomposition, the mod is UEMOA chlorinated water.

In another aspect, the present invention relates to compositions comprising a thermoplastic resin and a stabilizer comprising a stabilizer mixture of the aromatic amine with sterically difficult phenol.

More specifically, the present invention relates to a method of increasing the stability of thermoplastic resin in the presence of water, comprising adding to the said resin a stabilizing amount of a mixture of:

(A) at least one antioxidant of the aromatic amine; and

(B) at least one antioxidant of the sterically constrained phenol.

In another aspect, the present invention relates to a pipe for conveying water, which is made from compositions comprising thermoplastic resin and a stabilizing amount of a mixture of:

(A) at least one antioxidant of the aromatic amine; and

(B) at least one antioxidant of the sterically constrained phenol.

DESCRIPTION of the PREFERRED OPTION (OPTIONS)For carrying out the INVENTION

As noted above, in the technique it is known that the presence of a stabilizing mixture comprising fosfatnyi the stabilizer and the stabilizer of the sterically constrained phenol, can improve the stability of a thermoplastic material such as polyethylene, to the extracting medium, such as water, hot I water and chlorinated water.

It was found that, when the antioxidant of the secondary aromatic amine spend substitution on fosfatnyi component, the resulting amino-phenol mixture provides excellent protection from HDPE present and degrades the action of chlorine. This increased resistance provided by the mixture containing the stabilizer of the aromatic amine and steric obstruction of phenol was tested both in the absence and in the presence of soot.

Antioxidants from aromatic amine, which is used in the implementation of the present invention, can be substituted by a hydrocarbon diarylamino, such as antioxidants from aryl-, alkyl-, alkaryl and aralkyl-substituted diphenylamine. A non-limiting list available to the industry substituted hydrocarbon of diphenylamino includes diphenylamine, replaced by actiom, nannilam and heptyl, and diphenylamine, substituted para-substituted styrene or α-methylstyrene. Diphenylamine, substituted sulfur-containing hydrocarbon, such as n-(p-toluensulfonyl)-diphenylamine, are also considered part of this class.

Substituted by a hydrocarbon diarylamino, which are used in the implementation of this invention can be represented by the General formula

Ar-NH-Ar',

where Ar and Ar' are independently selected aryl radicals, at least one of which is predpochtitelno substituted, at least one alkyl radical. Aryl radicals can be, for example, phenyl, biphenyl, terphenyl, naphthyl, antril, tenantry and other similar radicals. Alkyl Deputy (deputies) can be, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, their isomers and other similar substituents. Preferred substituted hydrocarbon by diarylamino are those that are disclosed in U.S. patents 3452056 and 3505225, the contents of which are mentioned here for information. Preferred substituted hydrocarbon diarylamino can be represented by the following General formula:

where

R1selected from the group consisting of phenyl and p-College radicals;

R2and R3independently selected from the group consisting of methyl, phenyl and p-College radicals;

R4selected from the group consisting of methyl, phenyl, p-College and neopentylene radicals;

R5selected from the group consisting of methyl, phenyl, p-College and 2-phenylazopyridine radicals; and,

R6is a methyl radical.

where R1- R5independently selected from the radicals shown in formula I, and R7selected from the group consisting of methyl, peninnah and p-College radicals;

X is a radical selected from the group consisting of methyl, ethyl, C3-C10-Deut-alkyl, α,α-dimethylbenzyl, α-methylbenzyl, chlorine, bromine, carboxyl and salts of carboxylic acids with metals, where the metal is chosen from the group consisting of zinc, cadmium, Nickel, lead, tin, magnesium and copper; and,

Y is a radical selected from the group consisting of hydrogen, methyl, ethyl, C3-C10-Deut-alkyl, chlorine and bromine.

where

R1selected from the group consisting of phenyl or p-College radicals;

R2and R3independently selected from the group consisting of methyl, phenyl and p-College radicals;

R4is a radical selected from the group consisting of hydrogen, C3-C10primary, secondary and tertiary alkyl, C3-C10alkoxyl, which may be linear or branched chain; and

X and Y are radicals independently selected from the group comprising hydrogen, methyl, ethyl, C3-C10-Deut-alkyl, chlorine and bromine.

where

R9selected from the group consisting of phenyl or p-College radicals;

R10is a radical selected from the group consisting of methyl, phenyl, p-tolil and 2-phenylazomethine; and

R11is a radical selected is from the group includes methyl, phenyl and p-tolyl.

where

R12selected from the group consisting of phenyl or p-College radicals;

R13selected from the group consisting of methyl, phenyl and p-College radicals;

R14selected from the group consisting of methyl, phenyl, p-College and 2-2-familiabuilder radicals; and

R15selected from the group consisting of hydrogen, α,α-dimethylbenzyl, α-methylbenzylamino, triphenyl-methyl and α,α-p-trimethylbenzene radicals. Typical chemical reagents used in the invention are the following:

TYPE I
R1R2R3R4R5R6
PhenylMethylMethylPhenylMethylMethyl
PhenylPhenylM is Teal PhenylPhenylMethyl
PhenylPhenylPhenylNeopentylMethylMethyl

TYPE II
R1R2R3R4R5R7XY
PhenylMethylMethylPhenylMethylMethylα,α-dimethyl-benzylHydrogen
PhenylMethylMethylPhenylMethylMethylBromineBromine
PhenylMethylMethylPhenylMethylMethylCarboxylHydrogen
PhenylMethylMethylPhenylMethylMethylNickel carboxylateHydrogen
PhenylMethylMethylPhenylMethylMethyl2-ButylHydrogen
PhenylMethylMethylPhenylMethylMethyl2-OctylHydrogen
PhenylPhenylPhenylPhenylPhenylPhenyl 2-HexylHydrogen

TYPE III
R1R2R3R4XY
PhenylMethylMethylIsopropoxyHydrogenHydrogen
PhenylMethylMethylHydrogen2-OctylHydrogen
PhenylPhenylPhenylHydrogen2-HexylHydrogen

TYPE IV

R9is phenyl and R10and R11are the stands.

The second class of amine antioxidants include interaction products diarylamino and aliphatic ketone. Products vzaimode istia of diarylamino and aliphatic ketone, as used herein, are disclosed in U.S. patents 1906935; 1975167; 2002642; and 2562802. Without going into details, these products are obtained by the interaction of diarylamino, preferably of diphenylamine, which can, if necessary, to have one or more substituents on any aryl group, aliphatic ketone, preferably acetone, in the presence of an appropriate catalyst. In addition to diphenylamine, other suitable diarylamino reagents include dinitramine; p-nitrodiphenylamine; 2,4-dinitrodiphenylamine; p-aminodiphenylamine; p-hydroxydiphenylamine; and other similar reagents. In addition to the acetone, other suitable ketone reagents include methyl ethyl ketone, diethylketone, monochloroacetone, dichloroacetone and other similar reagents.

The preferred product of the interaction of diarylamino-aliphatic ketone receive the condensation reaction of diphenylamine and acetone (NAUGARD A, Crompton Corp.), for example, in accordance with the terms described in U.S. patent 2562802. Industrial product supply in the form of light-yellow-brown-green powder or in the form of a greenish brown scales, and it has a melting point in the range of from 85° to 95°C.

A third class of suitable amines include N,N' substituted hydrocarbon p-phenylendiamine. Hydrocarbon Deputy may be alkyl or aryl is a group, which may be substituted or unsubstituted. It is assumed that when used herein, the term "alkyl", unless specifically indicated otherwise, includes cycloalkyl. Typical materials are:

N-phenyl-N'-cyclohexyl-p-phenylenediamine;

N-phenyl-N'-terbutyl-p-phenylenediamine;

N-phenyl-N'-isopropyl-p-phenylenediamine;

N-phenyl-N'-(1,3-dimethylbutyl)-p-phenylenediamine;

N,N'-bis-(1,4-dimethylpentyl)-p-phenylenediamine;

N,N'-diphenyl-p-phenylenediamine;

mixed diaryl-p-N,N'-bis-(1-ethyl-3-methylpentyl)-p-phenylenediamine; and

N,N'-bis-(1-methylheptan)-p-phenylenediamine.

The last class of amine antioxidants include materials based on quinoline, especially, polymerized 1,2-dihydro-2,2,4-trimethylquinoline. Typical materials include polymerized 2,2,4-trimethyl-1,2-dihydroquinoline; 6-dodecyl-2,2,4-trimethyl-1,2-dihydroquinoline; 6 ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline and other similar materials.

Examples of suitable sterically obstructed phenols include 2,4-dimethyl-6-op; 2,6-di-tert-butyl-4-METHYLPHENOL (i.e., bottled hydroxytoluene); 2,6-di-tert-butyl-4-ethylphenol; 2,6-di-tert-butyl-4-n-butylphenol; 2,2'-Methylenebis(4-methyl-6-tert-butylphenol); 2,2'-Methylenebis(4-ethyl-6-tert-butylphenol); 2,4-dimethyl-6-tert-butylphenol; 4-hydroxymethyl-2,6-di-tert-butylphenol; n-octadecyl-beta(3,5-di-tert-butyl-4-hydroxyphenyl)propionate;2,6-dioctadecyl-4-METHYLPHENOL; 2,4,6-trimethylphenol; 2,4,6-triisopropylphenyl; 2,4,6-tri-tert-butylphenol; 2-tert-butyl-4,6-dimethylphenol; 2,6-methyl-4-decodecolor; Tris(3,5-di-tert-butyl-4-hydroxyisoleucine and Tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane.

Other suitable antioxidants include 3,5-di-tert-butyl-4-hydroxyhydrocinnamate; octadecyl-3,5-di-tert-butyl-4-hydroxyhydrocinnamate (NAUGARD 76, Crompton Corp.; IRGANOX 1076, Ciba-Geigy); tetrakis{methylene(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)}methane (IRGANOX 1010, Ciba-Geigy); 1,2-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)hydrazine (IRGANOX MD 1024,Ciba-Geigy); 1,3,5-Tris(3,5-di-tert-butyl-4-hydroxybenzyl)-s-triazine-2,4,6 (1H,3H,5H)Trion (IRGANOX 3114,Ciba-Geigy); 2,2'-oxalidales-{ethyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)}propionate (NAUGARD XL-1, Crompton Corp.); 1,3,5-Tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-s-triazine-2,4,6-(1H,3H,5H)Trion (CYANOX 1790, American Cyanamid Co.); 1,3,5-trimethyl-2,4,6-Tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene (ETHANOX 330, Ethyl Corp.); triavir 3,5-di-tert-butyl-4-hydroxyvitamin acid 1,3,5-Tris(2-hydroxyethyl)-5-triazine-2,4,6(1H,3H,5H)-Trion, and glycol ether bis(3,3-bis(4-hydroxy-3-tert-butylphenyl)butane acid).

In addition, other sterically difficult phenols, which are used in the implementation of the present invention are polyphenols, which contain three or more substituted phenolic groups, such as tetrakis{methylene(3,5-di-tert-butyl-4-hydroxyatrazine the Amat)}methane (IRGANOX 1010, Ciba-Geigy) and 1,3,5-trimethyl-2,4,6-Tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene (ETHANOX 330, Ethyl Corp.).

In particular, a mixture comprising 4,4'-bis(α,α-dimethylbenzyl)- diphenylamine and tetrakis[methylene(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)]methane, provided the characteristics that exceed the specifications of the control mixture of Tris(2,4-di-tert-butylphenyl)phosphite and tetrakis[methylene(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)]methane.

The preferred composition is a composition comprising a mixture of 4,4'-bis(α,α-dimethylbenzyl)of diphenylamine and tetrakis[methylene (3,5-di-tert-butyl-4-hydroxyhydrocinnamate)]methane.

Preferably, the mass ratio of the two components was 1:1, although it can be used and the relationship in the range of from 1:9 to 9:1.

Thermoplastic resins which can be stabilized by the compounds of the present invention include, but are not limited to, polyolefins. Such polyolefins are usually obtained by polymerization of ethylene, propylene and/or other alpha-olefins. In the case of ethylene, the polyolefin may be, for example, high density polyethylene (HDPE), low density polyethylene (LDPE) or linear low density polyethylene (LLDPE). Can also be used successfully polypropylene homopolymer, and copolymers and ternary copolymers containing ethylene, propylene and/or the others who LLF-olefins, and/or unpaired dieny, as well as mixtures of these polymers.

Thus, such polyolefin materials can, if necessary, to enable or polypropylene copolymer, which contains most of propylene, combined with a lower part (usually less than 50 wt.%, more typically from about 0.1 to 10 wt.%) the second monomer, which may include ethylene or4-C6Monomeric material.

Preferred copolymers of ethylene may include a large portion of ethylene and a lower part (usually less than 50 wt.%, preferably from about 0.1 to 10 wt.%) With3-C18the monomer.

HDPE, i.e. high density polyethylene is most preferred as thermoplastic resin, stabilized by mixtures of the present invention.

In thermoplastic resin used in the implementation of the present invention may be incorporated particulate filler including silica-containing fillers, carbon black and other fillers. Such filler materials include, but without limiting to these, metal oxides, such as silicon dioxide (paragenetically and precipitated), titanium dioxide, aluminosilicate and alumina, clay and talc, carbon black, and mixtures of the above substances, and other similar materials. Preferred is carbon black.

Thus, the hen a trial sample for testing (this) HDPE stable mixture of aromatic amine and sterically constrained phenol, was immersed in hot chlorinated water, it gave a higher resistance to the harmful effects of chlorine than the corresponding test sample for testing, containing the control mixture-based phosphite. This operational advantage characterized the induction time of oxidation.

Secondly, when a test sample for tests containing soot HDPE, stable mixture of aromatic amine and sterically constrained phenol, was immersed in hot chlorinated water, he gave an even higher resistance to the harmful effects of chlorine than the corresponding containing soot sample for testing, containing the control mixture-based phosphite. This operational advantage again characterized the induction time of oxidation.

In addition, increased resistance to mixture comprising the stabilizer of the aromatic amine and sterically constrained phenol, optionally tested in one only hot water in the absence of chlorine.

Thus, when a test sample for testing HDPE, stable mixture of aromatic amine and sterically constrained phenol, was dipped in water with a temperature of 60°C, it provided a higher stabilizing effect than in the case of the corresponding test sample for testing contains the control mixture-based phosphite measured using an induction time of oxidation.

Further, when a test sample for tests containing soot HDPE, stable mixture of aromatic amine and sterically constrained phenol, was dipped in water with a temperature of 60°C, it gave a higher stabilization than in the case of the corresponding containing soot test sample for testing, containing the control mixture-based phosphite measured using an induction time of oxidation.

Advantages and important characteristic features of the present invention will be more apparent from the following examples.

EXAMPLES

Differential scanning calorimetry

Differential scanning calorimetry was performed using a Mettler instrument 820 supplied software Mettler Star version 7.01. Test samples that do not contain carbon black, were analyzed in aluminum crucibles. Test samples containing soot, were analyzed in a copper crucible. The induction time of oxidation (IVO) was measured by heating in nitrogen atmosphere corresponding crucible containing a circular disk made of a test sample for testing to 200°C. At this point, while maintaining a temperature of 200°C, created an atmosphere of oxygen. IVO was recorded as the time the I, elapsed before the appearance of the curve. Higher values IVO indicate a higher level of protection and/or a lower degree of washout stabilizer.

Preparation of test sample for test and experiment on aging

Test samples for testing were prepared first by mixing powder of high density polyethylene, having a density of about 0,944 g/cm3with appropriate additives (additives) in the water absorption capacity and anticipation of Brabender at 200°C/50 rpm for 15 minutes. The resulting pellet is then used to obtain samples for testing, having a thickness of 10 mils, using a molding process. For experiments on aging appropriate sample for testing was placed in a vessel filled with either deionized water or a solution of chlorinated water, prepared according to the method of example 1, below. The vessel was then placed in an oven with circulating hot air, the temperature of which was set to 60°C.

EXAMPLE 1

Preparation of the test solution of chlorinated water

Four ml of commercially available bleach Clorox, having the concentration of active sodium hypochlorite 5.25%, and added in a volumetric flask with a volume of 2 L. Flask was then filled with deionized water to the mark. The resulting solution contained approximately 100 h/m is n active sodium hypochlorite.

EXAMPLE 2

The stabilizing effect of the mixture, including

aromatic amine and sterically hindered phenol in HDPE

IVO (min) @ 200°C
The composition of a test sample for testingCodeNot accounted for-certifiedAfter one week of aging at 60°C
Deion-
sirolan-
Naya water
Chlorinated water
HDPE+0,125% PHOS-1+ 0,125% PAO-1Control 11051063
HDPE+0,125% AM-1+0,125% PAO-1And13211425

PHOS-1 refers to Tris(2,4-di-tert-butylphenyl)FOSFA.

PAO-1 means tetrakis[methylene(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)]methane.

AM-1 means 4,4'-bis(α,α-dimethylbenzyl)diphenylamine.

The results of this test show that the mixture code A, which was prepared from stabilizing smesitelno aromatic amine and sterically constrained phenol, gave excellent characteristics as compared with a composition based phosphite (Control 1). This performance advantage was observed for hot water (without chlorine), and to hot chlorinated water.

EXAMPLE 3

The stabilizing effect of the mixture comprising an aromatic amine and a sterically hindered phenol in HDPE in the presence of soot

IVO (min) @ 200°C
The composition of a test sample for testingCodeNot accounted for-certifiedAfter one week of aging at 60°C
Deion-
sirolan-
Naya water
Chlorinated water
HDPE+0,125% PHOS-1+0,125% PAO-1+2,25% sootControl 273615
HDPE+0,125% AM-1+0,125% PAO-1+2,25% sootIn999821

For containing the carbon black compositions of the results of this test showed that Cosmas code B, which was made with a stabilizing mixture of a secondary aromatic amine and sterically constrained phenol, gave excellent characteristics as compared with a composition based phosphite, Control 2. An operational advantage was noted for hot water, and hot chlorinated water. Whereas many alterations and modifications which may be made without deviating from the principles underlying the invention, to understand the scope of protection, which gives the invention, reference should be made to the accompanying claims.

1. The method of increasing the stability of high density polyethylene in the presence of hot water, comprising adding to the specified polyethylene stabilizing amount of a mixture consisting of:
(A) 4,4'-bis(α,α-dimethylbenzyl)diphenylamine; and
(B) at least one sterically constrained phenol.

2. The method according to claim 1, in which water is chlorinated.

3. The method according to claim 1, where the sterically hindered phenol selected from the group comprising 2,4-dimethyl-6-op; 2,6-di-tert-butyl-4-METHYLPHENOL (i.e., bottled hydroxytoluene); 2,6-di-tert-butyl-4-ethylphenol; 2,6-di-tert-butyl-4-n-butylphenol; 2,2'-Methylenebis(4-methyl-6-tert-butylphenol); 2,2'-Methylenebis(4-ethyl-6-tert-butylphenol); 2,4-dimethyl-6-tert-butylphenol; 4-hydroxymethyl-2,6-di-tert-butylphenol; n-octadecyl-b is the(3,5-di-tert-butyl-4-hydroxyphenyl)propionate; 2,6-dioctadecyl-4-METHYLPHENOL; 2,4,6-trimethylphenol; 2,4,6-triisopropylphenyl; 2,4,6-tri-tert-butylphenol; 2-tert-butyl-4,6-dimethylphenol; 2,6-methyl-4-decodecolor; Tris(3,5-di-tert-butyl-4-hydroxyisoleucine; Tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane; 3,5-di-tert-butyl-4-hydroxyhydrocinnamate; octadecyl-3,5-di-tert-butyl-4-hydroxyhydrocinnamate; tetrakis {methylene(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)}methane; 1,2-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)hydrazine; 1,3,5-Tris(3,5-di-tert-butyl-4-hydroxybenzyl)-s-triazine-2,4,6(1H,3H,5H)Trion; 2,2'-oxalidales-{ethyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl)}propionate; 1,3,5-Tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-s-triazine-2,4,6-(1H,3H,5H)Trion; 1,3,5-trimethyl-2,4,6-Tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene; tiefer,5-di-tert-butyl-4-hydroxyvitamin acid 1,3,5-Tris(2-hydroxyethyl)-5-triazine-2,4,6(1H,3H,5H)-Trion, and glycol ether bis(3,3-bis(4-hydroxy-3-tert-butylphenyl)butane acid).

4. Pipe hot water, characterized in that it is made from compositions comprising high density polyethylene and a stabilizing amount of a mixture consisting of:
(A) 4,4'-bis(α,α-dimethylbenzyl)diphenylamine; and
(B) at least one sterically constrained phenol.

5. The pipe according to claim 4, where the water is chlorinated.

6. The pipe according to claim 4, where the sterically hindered phenol you the wounds from the group comprising 2,4-dimethyl-6-op; 2,6-di-tert-butyl-4-METHYLPHENOL (i.e., bottled hydroxytoluene); 2,6-di-tert-butyl-4-ethylphenol; 2,6-di-tert-butyl-4-n-butylphenol; 2,2'-Methylenebis(4-methyl-6-tert-butylphenol); 2,2'-Methylenebis(4-ethyl-6-tert-butylphenol); 2,4-dimethyl-6-tert-butylphenol; 4-hydroxymethyl-2,6-di-tert-butylphenol; n-octadecyl-beta(3,5-di-tert-butyl-4-hydroxyphenyl)propionate; 2,6-dioctadecyl-4-METHYLPHENOL; 2,4,6-trimethylphenol; 2,4,6-triisopropylphenyl; 2,4,6-tri-tert-butylphenol; 2-tert-butyl-4,6-dimethylphenol; 2,6-methyl-4-decodecolor; Tris(3,5-di-tert-butyl-4-hydroxyisoleucine; Tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane; 3,5-di-tert-butyl-4-hydroxyhydrocinnamate; octadecyl-3,5-di-tert-butyl-4-hydroxyhydrocinnamate; tetrakis {methylene(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)} methane; 1,2-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)hydrazine; 1,3,5-Tris(3,5-di-tert-butyl-4-hydroxybenzyl)-s-triazine-2,4,6(1H,3H,5H)Trion; 2,2'-oxalidales-{ethyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)}propionate; 1,3,5-Tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-s-triazine-2,4,6-(1H,3H,5H)Trion; 1,3,5-trimethyl-2,4,6-Tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene; tiefer 3,5-di-tert - butyl-4-hydroxyvitamin acid 1,3,5-Tris(2-hydroxyethyl)-5-triazine-2,4,6(1H,3H,5H)-Trion, and glycol ether bis(3,3-bis(4-hydroxy-3-tert-butylphenyl)butane acid).



 

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Polyethylene tubes // 2394052

FIELD: chemistry.

SUBSTANCE: method involves preparation of a mixture containing 5-50 wt % filler and 95-50 wt % low density polyethylene and 0-3 wt % of one or more stabilisers.The obtained mixture and high density polyethylene containing at least one low-molecular component which is a copolymer of ethylene and C3-C10 α-olefin are mixed in a molten mass until the end product is obtained at drop point of 165-185°C. The obtained composition for making tubes contains 1-20 wt % filler in terms of mass of the composition.

EFFECT: composition has better balance of properties and can be extruded with sufficiently high efficiency at optimal low melt temperature.

19 cl, 3 tbl, 7 ex

FIELD: technological processes.

SUBSTANCE: inventions relate to pipe of flaky composite material and method of its manufacturing. Method for manufacturing of pipe includes winding of inner glass plastic layer onto mandrel, bonding of intermediate foam plastic layer and winding of ribs and outer layer of glass plastic. In intermediate foam plastic layer there are circular grooves arranged for location of ribs. Ribs and outer layer is wound in a single technological operation by bundle of cross threads. Bundles are equipped with longitudinal threads, using method of cross-fibred longitudinal-transverse winding. At the same time longitudinal threads are bent as bundle changes from winding of external layer to winding of ribs and back with filling of each groove by mentioned bundle till ribs are formed.

EFFECT: improved manufacturability and reliability of glass plastic pipes operation.

2 cl, 4 dwg

Pressed shell // 2387910

FIELD: machine building.

SUBSTANCE: invention refers to pipe fabrication. The pressed shell containing layers of roll woven cloth with binding is made with circular layers of woven material in form of separate strips of length not less, than length of shell and width equal to perimetre of the latter with overlap.

EFFECT: increased reliability and expanded process functionality of pressed shell.

2 cl, 2 dwg

FIELD: transport.

SUBSTANCE: meshed cover in the form of rotation body from composite materials includes spiral and circular ribs comprised of layers repeated throughout the cover wall thickness of the systems of crossing spiral and circular strips. Inclined strip passages between circular strips are equally offset relative to each other in circumferential and spiral directions and are made in the form of one family of congruent continuous circular zigzag-shaped spirals located along circular surfaces, which is common to circular surfaces of layers of the systems of crossing spiral and circular strips. Tops of zigzags are adjacent to circular strips of circular ribs crossing in the gap between them with spiral strips or spiral and circular strips of spiral and circular ribs correspondingly so that circular zigzag-shaped ribs are formed and mainly arranged on cover ends.

EFFECT: increasing rigidity, improving reliability and decreasing the weight of the design.

4 cl, 4 dwg

FIELD: construction.

SUBSTANCE: invention is related to method for manufacturing of pipeline. Method provides for filling of space between ends of pipe composite layers by winding of fibrous material impregnated with binder, and attachment of composite layers is provided via winding of additional layers of fibrous material impregnated with binder on them and onto fibrous material with further polymerisation.

EFFECT: expansion of assembly resources and improved reliability after welding of pipe polymer layers.

1 dwg

FIELD: construction.

SUBSTANCE: invention is related to the field of pipes from plastic masses. In method of combined pipe manufacturing, including arrangement of sealing thermoplastic layer on technological mandrel, winding of fibrous material with binder and polymerisation, sealing layer is arranged by winding of extruded thermoplastic tape onto mandrel with overlap and simultaneous heating of joint of the latter in process of winding, then layer of woven cellular fibrous material is wound with partial penetration into uncooled sealing layer, and fibrous material with binder is laid over this layer with further polymerisation.

EFFECT: improved reliability.

3 dwg

FIELD: construction.

SUBSTANCE: invention is related to the field of pipes production from composite materials. In method for production of pipe, including installation of polymer pipe on mandrel, arrangement of primer layer on it, winding of fibrous material with binder and polymerisation, after installation of polymer pipe onto mandrel its surface layer is heated till yield state, and primer layer is arranged on it by means of woven cellular material winding on it, and then fibrous material is wound with binder and polymerised.

EFFECT: improved reliability.

1 dwg

FIELD: aircraft engineering.

SUBSTANCE: proposed air duct can feed air in the temperature range of minus 55°C to plus 85°C and at load with pressure difference relative to aircraft cabin inside pressure not exceeding ±500 GPa. Air duct outer or inner side is furnished with multi-layer reinforcing coat. Every layer has a number of coils formed by at least one continuous fiber. Coils of layers arranged one above another are wound in opposite directions to form the coat cellular structure. Air duct is made from foamed or dense plastic material. Aforesaid continuous fibers are enclosed by matrix made from either thermosetting plastic or thermoplastic polymer. Distance between said coils or angle of inclination between them and air duct lengthwise axis varies along said axis to change coils density along air duct lengthwise axis depending upon local requirements to air duct mechanical strain.

EFFECT: air duct reduced weight and increased strength.

12 cl, 8 dwg

FIELD: chemistry.

SUBSTANCE: method involves mixing at least one halogen-butyl elastomer of at least one mineral filler-silica and/or clay and at least one phosphine modifier - triphenyl phosphine. The filled elastomer is vulcanised with sulphur and/or zinc oxide. Filled halogen-butyl elastomers, obtained using the disclosed method, have higher filler dispersion.

EFFECT: increased hardness and tensile strength of the composition.

10 cl, 1 dwg, 2 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a thermoplastic elastomeric composition and preparation method thereof and can be used as a fluid impermeable layer in pneumatic tyres and tubes. The composition contains a halogenated isobutylene-containing elastomer and a nylon resin, having melting point between 170°C and 230°C. Said elastomer in form of vulcanised or partially vulcanised particles through dynamic vulcanisation is contained in form of a dispersed phase in a continuous phase of nylon in amount greater than 60 vol. % of overall content of elastomer and resin. Said period of time for dynamic vulcanisation is equal to or less than the defined holding time of the mixer. The method involves steps for mixing the elastomer with a vulcanising system thereof with fractional addition thereof into the nylon resin. The step for dynamic vulcanisation of the fractionally added amount of elastomer in the presence of a vulcanised composition from the previous step is repeated several times necessary to obtain total amount of halogenated elastomer in the said composition.

EFFECT: invention enables to achieve excellent longevity and elasticity properties with excellent air-tightness.

20 cl, 1 dwg, 5 tbl

FIELD: process engineering.

SUBSTANCE: invention relates to vulcanised multilayer structures, for example automotive tires. Proposed structure comprises at least two layers and at least one jointing layer. First of two layers inhibits fluid penetration. Second layer comprises at least one rubber with high content of diene. Jointing layer consists of the following mix: (1) 50-90 wt % of at least one halogenated isobutylene-containing elastomer; (2) 5-50 wt % of at least one elastomer with high content of diene; (3) 20-50 wt % of at least one filler; (4) 0-30 wt % of at least one process oil, and (5) 0.2-15 parts per 100 parts of rubber of vulcanising system for elastomer.Rubber and elastomer with high content of diene contain at least 50 mol % of diene monomer. Layer that inhibits fluid penetration comprises polymer composition with air permeability factor equal to 25x10-12 cu cm·cm/cm2 s cm Hg (at 30°C) or less, and Young module equal to 1 - 500 MPa. Said polymer composition comprises: (A) at least, 10 wt % of total weight of composition of at least one thermoplastic synthetic polymer component with air permeability factor equal to 25x10-12 cu cm-cm/cm2 s cm Hg (at 30°C), and Young module exceeding 500 MPa. Thermoplastic synthetic polymer component is selected from the group consisting of resins: polyamide, polyester, polynitrile, polymethacrylate, polyvinyl, imide polymers of cellulose and fluorinated polymers. Polymer composition comprises also (B) at least, 10 wt % of total weight of composition of at least one thermoplastic synthetic polymer component with air permeability factor exceeding 25x10-12 cu cm·cm/cm2 s cm Hg (at 30°C), and Young module not exceeding 500 MPa. Component (B) is dispersed in vulcanised or partially vulcanised state ad a discrete phase in the matrix of component (A) of polymer composition.

EFFECT: reduced permeability for air and better adhesion.

23 cl, 1 dwg, 5 tbl

FIELD: process engineering.

SUBSTANCE: invention relates to multilayer microporous polyethylene membrane and storage battery made thereof. Proposed membrane has at least two microporous layers. One layer (a) of polyethylene resin A contains high-density polyethylene A with 0.2 and more end vinyl groups per 10 000 carbon atoms defined by IR-spectroscopy. Second microporous layer (b) of polyethylene resin B contains high-density polyethylene A with smaller than 0.2 end vinyl groups per 10 000 carbon atoms defined by IR-spectroscopy. Said membrane is produced by two methods. First method comprises simultaneous extrusion of solutions of polyethylene resins A and B through spinneret, cooling of extrudate, removing of solvent and laminating. Second method comprises extrusion of said solutions through different spinnerets. Said membrane is used to produce storage battery separator.

EFFECT: well-balanced characteristics of melting and cutting-off, good forming property of film and separator and anti-oxidation properties.

4 cl, 1 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: composition contains a mixture of a low molecular weight polyethylene component and a high molecular weight polyethylene component and a binding agent containing at least 0.0025 wt % polysulphonyl azide. The mixture has sine peak on the lamella thickness distribution (LTD) curve.

EFFECT: prolonged wear resistance of pipes under gas or water pressure, resistance to cracking under stress associated with environmental factors, resistance to slow formation of cracks, to fast crack propagation and to creep under internal stress.

64 cl, 3 dwg, 24 tbl, 6 ex

FIELD: chemistry.

SUBSTANCE: moulding method involves heating thermoplastic material higher than melting point, forcing the obtained melt through a die at 10-100°C higher than melting point of the thermoplastic material and cooling the product to temperature lower than melting point. The composition of thermoplastic material includes a thermoplastic polymer and a complex additive for improving moulding. The complex additive used is a reactive composition containing at least one polyether polyol and at least one thickening component selected from a group comprising polybasic organic acids, anhydrides of polybasic organic acids, fatty acids containing 8-18 carbon atoms, as well as mixtures thereof.

EFFECT: method cuts on induction time, increases rate of flawless moulding thermoplastic material, reduces power consumption and moulding temperature, lowers pressure in the equipment when moulding high molecular weight polymers, simplifies and lowers the cost of moulding articles from thermoplastic polymer materials.

12 cl, 11 dwg, 14 ex

FIELD: chemistry.

SUBSTANCE: moulding method involves heating thermoplastic material higher than melting point, forcing the obtained melt through a die at 10-100°C higher than melting point of the thermoplastic material and cooling the product to temperature lower than melting point. The composition of thermoplastic material includes a thermoplastic polymer and a complex additive for improving moulding. The complex additive used is a reactive composition containing at least one polyether polyol and at least one thickening component selected from a group comprising polybasic organic acids, anhydrides of polybasic organic acids, fatty acids containing 8-18 carbon atoms, as well as mixtures thereof.

EFFECT: method cuts on induction time, increases rate of flawless moulding thermoplastic material, reduces power consumption and moulding temperature, lowers pressure in the equipment when moulding high molecular weight polymers, simplifies and lowers the cost of moulding articles from thermoplastic polymer materials.

12 cl, 11 dwg, 14 ex

FIELD: textile, paper.

SUBSTANCE: heat-shielding material is made of a shaped layer of aramid fibre of non-woven structure with diametre of fibre from 1 to 10 nm, laid between two layers of rubber mix on the basis of ethylene-propylene rubber with further curing in item composition.

EFFECT: invention makes it possible through usage of new nanofibre filler to solve the problem of its recycling on completion of item life cycle.

1 dwg, 1 tbl

FIELD: chemistry.

SUBSTANCE: material is made from synthetic thermoplastic polymer, filler in form of nanoparticles selected from natural or synthetic phyllosilicates or silica clay and dispersant. The dispersant is obtained through free-radical polymerisation.

EFFECT: materials have high value of modulus of elasticity and also meet technical requirements for surface hardness and accuracy of size of nanocomposites.

17 cl, 5 tbl, 5 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing composite nanomaterials for antifrictional purposes. The materials can be used in systems working under high deformation loads and in friction assemblies. The method involves mechanical activation of powder filler in form of sheet silicate in a ball mill in high-speed mode. Further, the powder filler is then mixed with powdered ultra-high molecular weight polyethylene for 10-60 minutes in a high-energy mill combined with mechanical activation.

EFFECT: obtained mixture is starting material from which articles with improved tribological characteristics, high mechanical strength and elasticity are moulded.

2 cl, 9 dwg, 2 tbl, 1 ex

Polymer composition // 2395542

FIELD: chemistry.

SUBSTANCE: invention relates to polymer compositions, particularly to rubber mixtures for making tyre treads and can be used in the tyre industry. The polymer composition contains the following components, in pts. wt: polybutadiene rubber SKD 20-30, polyisoprene rubber SKI-3 70-80, zinc oxide 4-5, technical carbon N339 50-55, oleic acid 1.5-2.0, sulphur 1.5-2.2, sulfenamide T 1.0-1.5, diaphene PP 1.0-1.5, Pikar hydrocarbon resin 2-3, oil PN-6s 10-15, Omsk-10 wax 1.5-2.0, acetonanyl N 1.5-2.0, santogard PVI 0.1-0.15, 3-15 mm long pieces of waste hybrid saturated cords 1.5-20.0.

EFFECT: increased extension elongation, bouncing elasticity and lower brittleness temperature.

2 cl, 4 tbl

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