Polyamide resin-based composition and moulded product

FIELD: chemistry.

SUBSTANCE: invention relates to composition based on polyamide resin for manufacturing moulded products. Composition contains polyamide, consisting of diamine units, containing units of 1,3-bis(aminomethyl)cyclohexane and units of dicarboxylic acid, including units of adipic and/or sebacic acid, (B) compounds of aromatic secondary amine, (C) organic sulphur-based compound and (D) phenolic oxidant. Weight ratio of components (B)/(C) in said composition constitutes from 0.5 to 10 and weigh ratio (D)/(C) in composition constitutes from 0.5 to 10. Polyamide resin-based composition is characterised by the fact that it has oxygen permeability coefficient not higher than 1.5 cubic cm·mm/m2.day·atm at temperature 23°C and relative humidity 75%. Moulded product, in particular hose or pipe is also described.

EFFECT: increased resistance to thermal ageing with preservation of gas-barrier properties of polyamides and products manufactured from them.

14 cl, 1 tbl, 16 ex

 

The technical field to which the invention relates

The present invention relates to compositions based on polyamide resins having excellent resistance to heat aging and gazoballonnyj properties, and to a molded product that includes it.

The level of technology

Given the fact that polyamide resins have excellent characteristics such as strength, hardness, resistance to solvents, formability, etc., are used as materials for injection molding of articles such as car parts or products for the electrical and electronics industries, etc., or as packaging materials for food products, soft drinks, chemicals, electronic parts, or so on, above all, polyamides containing m-xylene group in the main polymer chain, are characterized by high stiffness and also have excellent barrier properties against various gases or chemicals, or so forth, and therefore, they are widely used as materials for injection molding or packaging materials.

However, since polyamides containing m-xylene group in the main polymer chain, in the position of benzylmethyl structural rings easily forms a radical, they have low heat resistance or resistance to heat aging is about compared to polyamides, as nylon-6, etc., For this reason, there are areas where the polyamides containing m-xylene group, can hardly be applied as molded materials, considering the harsh environment or conditions of use, such as high-temperature environment, and so on

In recent years, for these reasons, it was difficult to use polyamides containing m-xylene group in the main polymer chain, in areas such as parts of vehicles, etc. that require gazoballonnyj properties and resistance to heat aging, although the possibility of applying polyamides studied.

Therefore, attempts were made to improve the heat resistance or resistance to heat aging polyamides. For example, patent document 1 discloses heat-resistant polyamide consisting of a polyamide containing m-xylene group in the main polymer chain, copper, halide, hindered phenol and/or hindered amine and organo-phosphorus compound. However, this method is a method suitable for obtaining an extruded fiber, but it proved unsatisfactory for improving the resistance to thermal aging of the molded articles obtained by injection molding, or extrusion molded articles intended for use as parts of vehicles, etc.

To the ome, for example, patent document 2 proposes a method in which in the case of tin processing of polyamide containing m-xylene group in the main polymer chain, at least one element selected from the softener, stabilizer based on organophosphorus compounds, difficult phenolic compounds and difficult amine compounds are added in amounts of 0.005 to 0.5 parts by weight, preventing the gelation of the polyamide. However, this method is a technology to prevent gelation during the molding process, but this proved unsatisfactory technology to increase resistance, heat aging after forming.

In addition, for example, patent document 3 describes as a material for molding precision products is an example in which the connection based on the aromatic secondary amine is introduced into the polyamide resin as depletability. However, this technology is a technology suitable for nylon 66, but is not considered its applicability to polyamides having different polymer structure.

In light of the above, in particular, regarding the above-mentioned polyamides having excellent gazoballonnyj properties, the current level is characterized by the absence of technical solutions, notoriuosly would increase their resistance to heat aging while maintaining gazoballonnyj properties.

The list of documents prior

PATENT DOCUMENTS

Patent document 1: JP-A-10-130497

Patent document 2: JP-A-2001-164109

Patent document 3: JP-A-2006-28327

Summary of the invention

Problems to be solved by the invention of

The aim of the present invention is to develop a composition based on polyamide resin, which would solve the problems described above and which would be a great gazoballonnyj properties and resistance to heat aging, and molded articles that include it.

Part of the solution

The authors of the present invention conducted extensive and in-depth research. In the result, it was found that the above problem is solved by a composition based on polyamide resin comprising (A) a polyamide composed of links of a diamine containing 1,3-bis(aminomethyl)cyclohexane link and link dicarboxylic acid, and at least, and (C) the connection on the basis of an aromatic secondary amine, and (D) an antioxidant, based on the phenol, a composition based on polyamide resin has a coefficient of oxygen permeability is not more than 1.5 CC·mm/m2· day·ATM. at 23°C and a relative humidity RH of 75%.

The effect of the invention

Composition based on polyamide resin of the present invention is excellent is from the point of view gazoballonnyj properties and resistance to thermal aging. Molded product comprising it can be used for automobile parts and so on, which are required gazoballonnyj properties and resistance to heat aging, and its industrial value is very high.

Ways of carrying out the invention

Composition based on polyamide resin

Composition based on polyamide resin of the present invention includes (A) a polyamide composed of links of a diamine containing 1,3-bis(aminomethyl)cyclohexane link and link dicarboxylic acid in its structure, and at least two (In) connection on the basis of the aromatic secondary amine and (D) an antioxidant, based on the phenol, a composition based on polyamide resin has a coefficient of oxygen permeability is not more than 1.5 CC·mm/m2·day·ATM at 23°C and a relative humidity RH of 75%. In this regard, in the present invention, 1,3-bis(aminomethyl)cyclohexane link refers to a component link comprising 1,3-bis(aminomethyl)cyclohexane, which is the starting material. In addition, "diamino link" refers to a component link, formed the source material on the basis of the diamino component polyamide, and "link dicarboxylic acid" refers to a component link, formed the source material based on the dicarboxylic acid polyamide. Prepact the tion, composition based on polyamide resin additionally contains (C) an organic compound on the basis of sulfur.

The polyamide (A) used in the present invention is a polyamide containing 1,3-bis(aminomethyl)cyclohexane link in its structure. The polyamide (A) has excellent getbasename properties and also excellent getbasename properties at high humidity. In addition, given that 1,3-bis(aminomethyl)cyclohexane link does not have the provisions of methylene benzene ring in its structure, it provides excellent resistance to heat aging. As the polyamide (A), for example, examples of polyamides, obtained by polycondensation diamino component containing 1,3-bis(aminomethyl)cyclohexane component and dicarboxylic acids of any type, etc., the polyamide may be homopolymer or copolymer. Discuss the polyamide has a high level gazoballonnyj properties and is favorable for heat resistance, resistance to heat aging and the ability to processing methods of forming. The polyamide (A) may be used separately or as a mixture of several resins.

In the present invention, the content of 1,3-bis(aminomethyl)cyclohexanone links in diamino link is preferably 30% by mol or more before occhialino 50% by mol or more, even more preferably 70% by mol or more, particularly preferably 80% by mol or more, and most preferably 90% by mol or more.

When the content of 1,3-bis(aminomethyl)cyclohexanone links in diamino link is 30% by mol or more, resistance to heat aging, gazoballonnyj properties and gazoballonnyj properties at high humidity of the polyamide (A) can be positive.

As an example, diamino component that is different from 1,3-bis(aminomethyl)cyclohexane, which can be used to obtain a polyamide (A) can lead aliphatic diamines, such as tetramethylaniline, pentamethylene, 2-methylpentylamine, hexamethylenediamine were, heptamethylnonane, octamethylene, monomethylaniline, decamethylenediamine, documentrenderer, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine and etc.; alicyclic diamines such as 1,4-bis(aminomethyl)cyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, bis(4-aminocyclohexane)methane, 2,2-bis(4-aminocyclohexane)propane, bis(aminomethyl)decalin, bis(aminomethyl)tricyclodecane and so on; aromatic diamines containing rings, such as bis(4-AMINOPHENYL)new simple ether, p-phenylenediamine, m-xylylenediamine, p-xylylenediamine, bis(aminomethyl)naphthalene, etc.,; and so on, But should not be considered the ü, what is the present invention limited to.

In the polyamide (A) of the present invention, the content of the element α,ω-linear aliphatic dicarboxylic acid containing from 4 to 20 carbon atoms in the chain dicarboxylic acid is preferably 50 mol.% or more, more preferably 70 mol.% or more, more preferably 80 mol.% or more and particularly preferably 90 mol.% or more.

By adjusting the content of parts of α,ω-linear aliphatic dicarboxylic acid containing from 4 to 20 carbon atoms in the chain dicarboxylic acid, up to 50 mol.% or more, you can improve gazoballonnyj properties and gazoballonnyj properties at high humidity of the polyamide (A).

As an example of a component of dicarboxylic acids that can be used to obtain a polyamide (A) can lead to α,ω-linear aliphatic dicarboxylic acid containing from 4 to 20 carbon atoms, such as succinic acid, glutaric acid, Emelyanova acid, subernova acid, azelaic acid, adipic acid, sabotinova acid, undecanoate acid, dodekanisa dikelola and so on; aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, 2,6-natalijagolosova acid and so forth; and so on, But we should not assume, what is the present invention limited

In addition, particularly preferred of the above-mentioned α,ω-linear aliphatic dicarboxylic acids containing from 4 to 20 carbon atoms, is adipic acid and sabotinova acid.

In addition to the diamino component and a component based on the dicarboxylic acid, lactam, such as ε-caprolactam, laurolactam, etc., or aliphatic aminocarbonyl acid, such as aminocaproic acid, aminoundecanoic acid, etc. can also be used as a copolymerization component within the interval, where the positive effects of the present invention is not particularly limited.

In addition, from the above-mentioned materials as polyamide (A), which can be preferably used in the present invention, as examples, polyamides, obtained by polycondensation diamino component containing 30 mol.% or more 1,3-bis(aminomethyl)cyclohexane, component and dicarboxylic acid containing 50 mol.% or more α,ω-linear aliphatic dicarboxylic acid having from 4 to 20 carbon atoms. As a polyamide, for example, can be called a polyamide obtained by polycondensation of a diamine containing mainly 1,3-bis(aminomethyl)cyclohexane, and adipic acid (hereinafter called "polyamide (a)); a polyamide obtained polycondensed the Oia diamine, containing mainly 1,3-bis(aminomethyl)cyclohexane, and sabatinovka acid (hereinafter referred to as "polyamide (b)"); a polyamide obtained by polycondensation of a diamine containing mainly 1,3-bis(aminomethyl)cyclohexane, adipic acid and sabatinovka acid (hereinafter referred to as "polyamide (C)); and so on Here used above is meant by the term "mainly" content of 50 mol.% or more of the total diamine.

In addition, as an example, the above-mentioned polyamide (a) can result in a polyamide obtained by polycondensation of 1,3-bis(aminomethyl)cyclohexane and adipic acid; and as the polyamide (b), an example of the polyamide obtained by the polycondensation of 1,3-bis(aminomethyl)cyclohexane and sabatinovka acid.

In the polyamide (C), obtained by polycondensation mainly 1,3-bis(aminomethyl)cyclohexane, adipic acid and sabatinovka acid, using adipic acid and sabatinovka acid as a component of dicarboxylic acid, its melting point, heat resistance, gazoballonnyj properties and crystallinity can be adjusted arbitrarily, and therefore it is preferred. When it is supposed to reduce the crystallinity, or when the system give amorphous state, the ratio of the mixture is of adipic acid and sabatinovka acid (molar ratio (sabotinova acid)/(adipic acid)) is preferably from 80/20 to 30/70, and more preferably from 70/30 to 40/60. When important gazoballonnyj properties, from the point of view of the above relations blending effect can be achieved by reducing the share of sabatinovka acid in the mixture. In particular, the mixing ratio preferably does not exceed more than 50/50, more preferably not more than 40/60, and even more preferably not more than 30/70. When is more important than the heat, from the point of view of the above relations blending effect can be achieved by reducing the share of sabatinovka acid in the mixture. In particular, the mixing ratio is preferably not more than 60/40, more preferably not more than 40/60, and even more preferably not more than 30/70.

In addition, as examples of the polyamide (A), which can be preferably used in the present invention, can be called a mixture of the above-mentioned polyamide (a) and polyamide (b). Mixing the above-mentioned polyamide (a) and the polyamide (b), can be arbitrarily adjust the heat and gazoballonnyj properties while maintaining the crystallinity. In the case of preferential attention to gatbering properties, from the point of view of a mixed polyamide (a) and polyamide (b),(mass ratio (polyamide (b)/(PA (a)), effectively reduce the proportion of the polyamide (b) in the mixture. In particular, the ratio of mixing is preferably a value not greater than 50/50, more predpochtitel is but not more than 40/60, and even more preferably not more than 30/70.

In addition, there is scope for which you want crystallinity; and the scope for which you want a low crystallinity or amorphous nature, depending on the field of application of the molded product. For this field of use can appropriately adjust the crystallinity, changing the mixing ratio of dicarboxylic acid ((sabotinova acid)/(adipic acid), or the ratio of mixture of polyamides (polyamide (b)/(PA (a)), as discussed above.

Furthermore, the addition of parts of 1,4-bis(aminomethyl)cyclohexane in the link of 1,3-bis(aminomethyl)cyclohexane as diamino link you can increase the resistance by increasing the melting temperature or glass transition temperature of the polyamide (A). Since the content of parts of 1,4-bis(aminomethyl)cyclohexane adjudged to be in an interval not exceeding 70 mol.% diamino link, by entering them in an arbitrary proportion, you can adjust the heat.

The polyamide (A) is not particularly limited to the method of its production, and it can be obtained by using the traditional method and the conditions of polymerization. A small amount of monoamine or monobasic carboxylic acids may be added as a molecular weight regulator at the time of polycondensation of the polyamide. For example, the polyamide (A) receive ways the Ohm, in which the nylon salt consisting of 1,3-bis(aminomethyl)cyclohexane and adipic acid, is exposed to high temperature at high pressure in the presence of water and polimerizuet in the molten state with the removal of added water and water of condensation. The polyamide (A) also get the way in which 1,3-bis(aminomethyl)cyclohexane add directly to adipic acid in the molten state, and the mixture is subjected to polycondensation at atmospheric pressure. In this case, to maintain the reaction system in a uniform molten state in the adipic acid is continuously added 1,3-bis(aminomethyl)cyclohexane and allow to flow polycondensation, simultaneously affecting the reaction system elevated temperatures, so that the reaction temperature does not decrease below the melting temperature of the resulting oligoimide and polyamide.

In addition, the polyamide (A) can be obtained by performing the polymerization in the solid phase, when carrying out the heat treatment in the solid state phase after polymerization of the melt. The polyamide (A) is not particularly limited way to obtain it, and it can be obtained by using the traditional method and polymerization conditions.

Srednedlinny molecular weight (Mn) of the polyamide (a) which is preferably from 18000 to 70,000, and more preferably from 20,000 to 50,000 from the point of view of values, in terms of PMMA (polymethylmethacrylate) when measured by the GPC method (gel chromatography). When srednedlinny molecular weight (Mn) falls within the range from 18000 to 70,000, it is possible to achieve favorable performance of the heat resistance and the ability to recycle the molding.

The glass transition temperature (Tg) of the polyamide (a) is preferably from 80 to 120°C., more preferably from 85 to 120°C. and even more preferably from 90 to 120°C. When the glass transition temperature (Tg) falls in the interval from 80 to 120°C, achieved a favorable amount of resistance.

Meanwhile, the glass transition temperature can be measured using DSC (differential scanning calorimetry). For example, measurements can be conducted by screening approximately 5 mg of sample and heating it at a temperature of from room temperature up to 300°C, provided the temperature rises at a rate of 10°C/min when using the device DSC-60 manufactured by Shimadzu Corporation. As the atmospheric gas may be flowing nitrogen at 30 ml/min For the temperature of vitrification accept the so-called temperature at the midpoint (Tgm). Meanwhile, as is well known, Tgm is the temperature at the midpoint on a slope of the DSC characterizing the phase transition between the base lines in zostelovane condition and supercooled state (in scolastica state).

The polyamide (a) may be added a compound of phosphorus with the aim of improving stability during processing at the time of molding of the melt or to prevent staining of polyamide (A). As phosphorus compounds suitable use of phosphorus compounds containing alkali metal or alkaline earth metal, and their examples include salts of phosphoric acid, salts hypophosphorous acid and salts of phosphorous acid alkali metals or alkaline earth metals such as sodium, magnesium, calcium, etc., In particular, those polyamides which used salt of an alkali metal or alkaline earth metal hypophosphorous acid, find primary use, because they have been particularly successful, the effect of preventing coloration of the polyamide. The concentration of phosphorus in the polyamide is preferably from 1 to 1000 million hours, more preferably from 1 to 500 million hours, more preferably from 1 to 350 million hours and particularly preferably from 1 to 200 million hours per phosphorus atom.

Composition based on polyamide resin of the present invention contains (C) a compound of the aromatic secondary amine and/or (D) a phenolic antioxidant as a constituent component(s) other than the polyamide (A). Of the compounds of the aromatic secondary amine (C) preferred are the I connection having phenylnaphthylamine structure, and compounds having dinitramine structure; and compounds having diphenylamino structure, and compounds having phenylnaphthylamine structure are more preferable.

In particular, examples of compounds having diphenylamine structure, such as N-phenyl-1-naphtylamine, p,p'-dialkyldiphenyl (the number of carbon atoms in the alkyl group is from 8 to 14), actinidiae diphenylamine, 4,4'-bis(α,α-dimethylbenzyl)diphenylamine, p-(p-toluensulfonyl)diphenylamine, N,N'-di-2-naphthyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, N-phenyl-N'-isopropyl-p-phenylenediamine, N-phenyl-N'-(1,3-dimethylbutyl)-p-phenylenediamine, N-phenyl-N'-(3-methacryloyloxy-2-hydroxypropyl)-p-phenylenediamine, etc.; compounds having phenylnaphthylamine structure, such as N-phenyl-1-naphtylamine, N,N'-di-2-naphthyl-p-phenylenediamine, etc.; compounds having dinitramine structure, such as 2,2'-dinitramine, 1,2'-dinitramine, 1,1'-dinitramine and so forth; and mixtures thereof. But we should not assume that this invention is limited. Of them 4,4'-bis(α,α-dimethylbenzyl)diphenylamine, N,N'-di-2-naphthyl-p-phenylenediamine and N,N'-diphenyl-p-phenylenediamine are more preferred, and N,N'-di-2-naphthyl-p-phenylenediamine and 4,4'-bis(α,α-dimethylbenzyl)diphenylamine are particularly preferred.

As above, the aforementioned phenolic antioxidant (D), an example of 2,2'-Methylenebis(4-methyl-6-t-butylphenol), 4,4'-butylidene(6-t-butyl-3-METHYLPHENOL), 4,4'-THIOBIS(6-t-butyl-3-METHYLPHENOL), 3,9-bis[2-[3-(3-t-butyl-4-hydroxy-5-were)propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane, bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], triethylene glycol, 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,4-bis(n-octylthio-6-(4-hydroxy-3,5-di-t-butylaniline)-1,3,5-triazine, pentaerythrityl·tetrakis[3-(3,5-di-t-butyl}-4-hydroxyphenyl)propionate], 2,2-thiodiethanol[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxyhydrocinnamate), 3,5-di-t-butyl-4-hydroxymethylphosphonate-diethyl ether complex, 1,3,5-trimethyl-2,4,6-Tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, Tris(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate, 2,4-bis[(octylthio)methyl]-o-cresol, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, etc., But we should not assume that this invention is limited. Of them 3,9-bis[2-[3-(3-t-butyl-4-hydroxy-5-were)propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane and N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxyhydrocinnamate) are preferred.

Mix the amount of such compounds aromatic secondary amine (s) and/or phenolic antioxidant (D) is preferably from 0.01 to 5 parts by m the SSE, more preferably from 0.1 to 2.0 parts by weight and particularly preferably from 0.2 to 1.0 parts by weight per 100 parts by weight of polyamide (A). When mixed number falls in the range from 0.01 to 5 parts by weight, the effect of increasing the resistance to heat aging and the appearance of the surface of the molded product is improved, and therefore it is preferred.

Preferably, the composition based on polyamide resin of the present invention additionally contains (C) an organic compound based on sulfur. Of organic compounds based on sulfur preferred are compounds based mercaptobenzothiazoles, based connection dithiocarbamates acid, compounds with thiourea and organic compounds on the basis of timeslot; and more preferred are compounds based mercaptobenzothiazoles and organic compounds on the basis of timeslot.

In particular, examples of such compounds on the basis of mercaptobenzothiazoles, 2-mercaptobenzimidazole, 2-mercaptobenzimidazole, metal salts of 2-mercaptobenzimidazole and so on; organic compounds based on timeslot, such as dilauryl-3,3'-thiodipropionate, Dimyristyl-3,3'-thiodipropionate, DISTEARYL-3,3'-thiodipropionate, pentaerythritol of arakis(3-laureltree the NAT), etc.; such compounds based on dithiocarbamates acid as metal salts pttc acid, metal salts dibutyldithiocarbamate acid and so forth; such compounds based on thiourea as 1,3-bis(dimethylaminopropyl)-2-thiourea, tributyltinoxide and so forth; and mixtures thereof. But we should not assume that this invention is limited. Them 2-mercaptobenzimidazole, 2-mercaptobenzimidazole, Dimyristyl-3,3'-thiodipropionate, DISTEARYL-3,3'-thiodipropionate and pentaerythritol tetrakis(3-lawrenceofarabia) are preferred; more preferred are pentaerythritol tetrakis(3-lawrenceofarabia), 2-mercaptobenzimidazole and Dimyristyl-3,3'-thiodipropionate; and especially preferred is pentaerythritol tetrakis(3-lawrenceofarabia).

Mix the amount of such organic compounds based on sulphur (S) is preferably from 0.01 to 5 parts by weight, more preferably from 0.1 to 2.0 parts by weight and particularly preferably from 0.2 to 1.0 parts by weight per 100 parts by weight of polyamide (A). When mixed number falls in the range from 0.01 to 5 parts by weight, the effect of increasing the resistance to heat aging and the appearance of the surface of the molded product is improved, and therefore it is preferred.

As the above-mentioned compounds based on aromatic secondary amine (V) and phenol-type antioxidant (D) may be used one type or two or more types. In addition, it is preferable that the connection on the basis of aromatic secondary amine (C) and/or phenolic antioxidant (D) and the organic compound on the basis of sulfur (S) was used in combination. When using organic compounds based on sulphur (S) in combination resistance to heat aging the composition based on polyamide resin becomes more favorable as compared with the case where only used the compound (C) based on the aromatic secondary amine and/or a phenolic antioxidant (D).

In particular, examples of suitable combinations of compounds based on aromatic secondary amine (C) and organic compounds based on sulphur (S) is the combination of both compounds (C) on the basis of an aromatic secondary amine, at least one element selected from 4,4'-bis(α,α-dimethylbenzyl)diphenylamine and N,N'-di-2-naphthyl-p-phenylenediamine; and as organic compounds based on sulphur (S), at least one element, selected from pentaerythritol tetrakis(3-lawrenceofarabia), 2-mercaptobenzimidazole and Dimyristyl-3,3'-thiodipropionate. In addition, with regard to the appropriate combination connection is tion on the basis of aromatic secondary amine (C) and organic compounds based on sulphur (S), you can give an example N,N'-di-2-naphthyl-p-phenylenediamine, as compounds based on aromatic secondary amine (V), and pentaerythritol tetrakis(3-lawrenceofarabia), as organic compounds based on sulphur (S).

In particular, as a suitable combination of phenolic antioxidant (D) and organic compounds based on sulphur (S), an example of the combination as a phenolic antioxidant (D) at least one element selected from 3,9-bis[2-[3-(3-t-butyl-4-hydroxy-5-methyl)phenyl)propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane and N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxyhydrocinnamate) and as organic compounds based on sulphur (S), at least one element selected from pentaerythritol tetrakis(3-lawrenceofarabia), 2-mercaptobenzimidazole and Dimyristyl-3,3'-thiodipropionate. As for the more appropriate combination of phenolic antioxidant (D) and organic compounds based on sulphur (S), you can give an example 3,9-bis[2-[3-(3-t-butyl-4-hydroxy-5-were)propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane as phenolic antioxidant (D), and pentaerythritol tetrakis(3-lawrenceofarabia), as organic compounds based on sulphur (C).

In addition, the content of the above compounds based on aromatic secondary amine (C) and er is ancescao compounds based on sulphur (C) (mass ratio (B)/(C)) in the composition based on polyamide resin of the present invention is preferably from 0.5 to 10.0, more preferably from 0.5 to 8.0. In addition, the content of the above-mentioned phenolic antioxidant (D) and organic compounds based on sulphur (C) (mass ratio (D)/(C)) in the composition based on polyamide resin of the present invention is preferably from 0.5 to 10.0. Moreover, in the case of compounds based on aromatic secondary amine (V) and phenol-type antioxidant (D) in combination with each other, the content of compounds based on aromatic secondary amine (B) phenolic antioxidant (D) and organic compounds based on sulphur (C) (mass ratio ((C)+(D))/(S)) in the composition based on polyamide resin is preferably from 0.5 to 10.0.

Adjusting the attitude of the contents so that they fall into the above ranges, it is possible to effectively improve the resistance to heat aging while maintaining barrier properties.

In addition, with a composition based on polyamide resin of the present invention can be mixed resin of one or more types, such as polyamide, different from the polyamide (A), koinopolitia, polyolefin, polyethyleneimine, polycarbonate, etc., within the interval in which the target parameter is not affected.

In addition, it may be the preferred way added floor is amide, different from the polyamide (A). More preferably, can be added aliphatic polyamide resin. Preferably used aliphatic polyamide resin as it is able to improve the physico-mechanical properties of molded products. As the aliphatic polyamide resin can be used nylon-6, nylon-66, nylon 11, nylon 12, nylon 46, nylon-610, nylon-612, nylon-666, etc. individually or several types.

Composition based on polyamide resin of the present invention may contain an inorganic filler. The use of inorganic filler increases the rigidity and dimensional stability of molded articles. The inorganic filler includes many fillers, which are fibrous, powdery, granular, flaky, tissue-like or solid form. Its examples include fiberglass, carbon fiber, graphite fiber, carbon black, calcium carbonate, talc, Catalpa, wollastonite, silicon dioxide, aluminum oxide, diatomaceous earth, clay, kaolin, mica, granulated glass, glass flakes, hollow glass, gypsum, iron oxide red, metallic fiber, titanium dioxide, whiskers of potassium titanate, whiskers of aluminum borate, magnesium oxide, calcium silicate, sodium aluminate, aluminum is NAT calcium, aluminum, aluminum oxide, aluminum hydroxide, copper, stainless steel, zinc oxide, whiskers metals, etc.

To a composition based on polyamide resin of the present invention can be added various additives such as a matting agent, a stabilizer pogodnosti, the absorber of ultraviolet rays, a crystallization nucleating agent, plasticizer, flame retardant, antistatic agent, stabilizer, color, protivorechivymi agent, a coloring agent, an agent to facilitate removal of articles from molds, etc., within the interval, which does not deteriorate the effects of the present invention.

It is required that the composition based on polyamide resin according to the present invention have a coefficient of oxygen permeability is not more than 1.5 CC·mm/m2·day·ATM at a temperature of 23°C and a relative humidity RH of 75%. When the permeability coefficient of oxygen falls within this interval, barrier properties to various gases, such as freon, carbon dioxide, hydrogen, alcohol, etc. are favorable. The permeability coefficient of oxygen is preferably not more than 1.2 CC·mm/m2·day·ATM, more preferably not more than 0.7 CC·mm/m2·day·ATM.

Molded product

Molded product comprising a composition based on polyamide resin in the present the invention, has as getbasename properties and resistance to heat aging, and can be used for various automobile parts, parts, electrical products, etc., and therefore is preferred. In particular, as molded articles comprising a composition based on polyamide resin can be preferably used hoses or hoses.

EXAMPLES

Below the present invention is described in more detail with reference to examples and comparative examples, but should not be considered that the present invention be limited by them. In this regard, in these examples, various measurements were carried out using the following test methods.

(1) Gazoballonnyj properties

The coefficient of oxygen permeability (CC·mm/m2·day·ATM) of a film was measured in an atmosphere at 23°C and a relative humidity RH of 75% or at a temperature of 23°C and a relative humidity of 90% RH in accordance with JIS K7126. For measurements used OX-TRAN 2/21, production Modern Controls Inc. This means that the lower the value, the more favorable are gazoballonnyj properties.

(2) Resistance to heat aging

First, the film was heated at 130°C for 72 hours using a hot air dryer. Then measured prochnost the e tensile properties of the film before and after heat treatment in accordance with JIS K7127, thereby determining the stress at break (MPa) (width of sample: 10 mm, distance between clamps: 50 mm, stretch speed: 50 mm/min, measure temperature: 23°C humidity measurement: 50% RH). In this regard, as for measurements used Strograph produced by Toyo Seiki Seisaku-sho, Ltd. The ratio of the stress at break before and after heat treatment was determined as an indicator of durability and indicator durability (%) was calculated by the following expression (1). This means that the higher the degree of conservation of strength, the better the resistance to heat aging.

The indicator durability (%)=[(Stress at break (MPa) of the film after heat treatment)/(Stress at break (MPa) of the film before heat treatment)]×100(1)

(3) the melting point and the glass transition temperature of polyamide

The melting point and the glass transition temperature was determined by the method of differential scanning calorimetry (DSC) using a calorimeter DSC-60, produced by Shimadzu Corporation. As for the measurement conditions, approximately 5 mg of sample was subjected to exposure to elevated temperature, growing at a rate of 10°C/min, and when the temperature is ostirala 300°C, the sample was rapidly cooled and re-heated at a rate of 10°C/min In this regard, the amorphous sample was measured as a sample obtained by boiling tablets and crystallization.

(4) Srednedlinny molecular mass

Srednekamennogo the molecular weight was determined in the units of the values obtained by the calibration curve for PMMA, using the measurement method on civil chromatograph HLC-8320GPC, produced by Tosoh Corporation. In this regard, TSKgel Super HM-H was used as a column for measurement; hexafluoroisopropanol (HFIP) containing 10 mmol/l trifenatate sodium, dissolved therein, was used as the solvent and the temperature of the measurements was set to 40°C. in Addition, received a standard curve by dissolving PMMA six molecular masses in HFIP and measurements of each solution.

EXAMPLE OBTAIN 1

The synthesis of the polyamide (A1)

After adipic acid (produced by Rhodia) was heated and melted at 170°C in the reactor, the water slowly, dropwise, with stirring, the contents were added 1,3-bis(aminomethyl)cyclohexane (manufactured by Mitsubishi Gas Chemical Company, Inc.) obtaining molar ratio to adipic acid 1/1, and simultaneously, the temperature was increased to 240°C. After completion pocataligo adding the reagent, the temperature was increased to 260°C. After the reaction, the contents were extracted in the form of threads and gr which was nuorvala in the granulator. The obtained granules were loaded into the drum and subjected to solid phase polymerization under reduced pressure, resulting in the polyamide (A) having a specified molecular weight. In this regard, as 1,3-bis(aminomethyl)cyclohexane used material, whose attitude CIS-form/TRANS-isomer was brought to 74/26 in units of molar ratio. The polyamide (A) had a melting point of 230°C, the glass transition temperature of 102°C and srednekamennogo molecular weight of 30000, and the permeability coefficient of oxygen is 0.2 CC·mm/m2·day·ATM.

EXAMPLE of GETTING 2

The synthesis of the polyamide (A2)

The polyamide (A2) was synthesized in the same manner as in the example of obtaining 1, except that sabotinova acid (THE brand, the production of Ito Oil Chemicals Co., Ltd.) used instead of adipic acid in the sample receiving 1. The polyamide (A2) had a melting point of 189°C, the glass transition temperature of 84°C, srednekamennogo molecular weight of 50,000 and a coefficient of oxygen permeability of 1.2 CC·mm/m2·day·ATM.

EXAMPLE for the preparation of 3

Synthesis of polyamide (A3)

Polyamide (A3) was synthesized in the same manner as in the example of obtaining 1, except that unlike the example of getting 1 as the dicarboxylic acid used mixed sabotinova acid and adipic acid, whose molar ratio stood at the head amounted 4/6 (mark ONE production Ito Oil Chemicals Co., Ltd.) instead sabatinovka acid. Polyamide (A3) had a melting point of 135°C., a glass transition temperature of 98°C, srednekamennogo molecular weight of 35,000 and a coefficient of oxygen permeability of 0.6 CC·mm/m2·day·ATM.

EXAMPLE 1

100 parts by mass of the polyamide (A1) and 0.05 parts by weight of N,N'-di-2-naphthyl-p-phenylenediamine (Nocrac White, produced by Ouchi Shinko Chemical Industrial Co., Ltd.) mixed in dry form and subjected to extrusion molding at dvuhserijnom extruder equipped with a screw having a diameter of 30 mm and a T-shaped extrusion head, resulting in a received film thickness of 100 microns.

By using the above film conducted an assessment of the above gazoballonnyj properties and resistance to thermal aging. The results of the measurements are presented in the table.

EXAMPLES 2-14

Films were obtained in the same manner as in example 1, except that a composition based on polyamide in example 1 was replaced with each of those that are described in the table, and then evaluated their properties in a similar way. The results of the measurements are presented in the table.

Comparative examples 1-2

Films were obtained in the same manner as in example 1, except that a composition based on polyamide in example 1 was replaced with each of those that are described in the table, and then carried out the assessment and the property in the same way. The results of the measurements are presented in the table.

EXAMPLE 15

Polyamide and additives used in example 2, and nylon-6 (produced by Ube Industries, Ltd., brand:V) was mixed in dry form in a mass ratio ((polyamide and additive)/(nylon-6)) 3/7 (the amount of the nylon 6 was 234,5 parts by weight per 100 parts by weight of polyamide resin (A1)) and was shaped on adenocarcinom extruder equipped with a screw having a diameter of 25 mm, and the extrusion head, resulting in the received tubular molded product with a thickness of 200 μm. Of the molded product was cut out of the sample for testing the tensile strength and it was heated at 130°C for 72 hours. The indicator of the durability of the sample after heat treatment was 105%. In addition, the tubular molded product was cut out of the sample plate and used it to measure the permeability of oxygen. The test results presented in the table.

In this regard, each of the abbreviations used in the table has the following values,

A1 - polyamide (A1) obtained in example obtain 1

A2 - polyamide (A2) obtained in example getting 2

A3 - polyamide (A3) obtained in the example of getting 3

B1 - N,N'-di-2-naphthyl-p-phenylenediamine (Nocrac White, produced by Ouchi Shinko Chemical Industrial Co., Ltd.)

B2 - 4,4'-bis(α,α-dimethylbenzyl)diphenylamine (Ncrac CD, produced by Ouchi Shinko Chemical Industrial Co., Ltd.)

C1 - tetrakis(3-lawrenceofarabia) pentaerythritol (Sumilizer TP-D, produced by Sumitomo Chemical Co., Ltd.)

C2 - 2-mercaptobenzimidazole (Sumilizer MB, produced by Sumitomo Chemical Co., Ltd.)

C3 - Dimyristyl-3,3'-thiodipropionate (Sumilizer TPM, produced by Sumitomo Chemical Co., Ltd.)

D1 - 3,9-bis[2-[3-(3-t-butyl-4-hydroxy-5-were)propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane (Sumilizer GA-80, produced by Sumitomo Chemical Co., Ltd.)

D2 - N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxyhydrocinnamate) (Irganox 1098, produced by Ciba-Geigy AG).

As shown in the above examples, a composition based on polyamide resins, comprising (A) polyamide containing the link of 1,3-bis(aminomethyl)cyclohexane, and (C) the connection on the basis of the aromatic secondary amine and/or (D) a phenolic antioxidant, all of which are distinctive features of the present invention, have a great getbasename properties and resistance to heat aging, while compositions based on polyamide resins that do not meet the specified conditions, have low resistance to heat aging.

1. Composition based on polyamide resin for the manufacture of molded articles comprising (A) polyamide comprising (a1) parts of a diamine containing parts of 1,3-bis(aminomethyl)cyclohexane and (A2) is Venev dicarboxylic acid, including parts of adipic and/or sabatinovka acid, (B) compounds aromatic secondary amine, (C) organic compound on the basis of sulfur, and (D) a phenolic antioxidant,
moreover, the content of compounds of the aromatic secondary amine (C) and organic compounds based on sulphur (C) (mass ratio (B)/(C)) in the specified composition is from 0.5 to 10.0, and the content of phenolic antioxidant (D) and organic compounds based on sulphur (C) (mass ratio (D)/(C)) in the composition is from 0.5 to 10.0, and
composition based on polyamide resin has a coefficient of oxygen permeability is not more than 1.5 CC·mm/m2·day·ATM at a temperature of 23°C and a relative humidity of 75%.

2. Composition based on polyamide resin under item 1, where the link diamine (a1) containing 30% by mol or more parts of 1,3-bis(aminomethyl)cyclohexane.

3. Composition based on polyamide resin under item 2, where the link diamine (a1) contains 50% by mol or more parts of 1,3-bis(aminomethyl)cyclohexane.

4. Composition based on polyamide resin under item 1, where the compound (C) an aromatic secondary amine is one or more elements selected from compounds having the structure of diphenylamine, compounds having the structure of phenylnaphthylamine, and compounds having the structure of dinitramine.

5. The composition is again a polyamide resin under item 4, where the compound (C) an aromatic secondary amine contains one or more elements selected from compounds with the structure of diphenylamine, and compounds with the structure of phenylnaphthylamine.

6. Composition based on polyamide resin under item 5, where the compound (C) an aromatic secondary amine is one or more elements selected from N-phenyl-1-naphtylamine, p,p'-dialkyldiphenyl (the number of carbon atoms in alkyl group: 8-14), artisterium of diphenylamine, 4,4'-bis(α,α-dimethylbenzyl)diphenylamine, p(-p-toluensulfonate)diphenylamine, N,N'-di-2-naphthyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, N-phenyl-N'-isopropyl-p-phenylenediamine, N-phenyl-N'-(1,3-dimethylbutyl)-p-phenylenediamine, N-phenyl-N'-(3-methacryloyloxy-2-hydroxypropyl)-p-phenylenediamine, 2,2'-dinitramine, 1,2'-dinitramine and 1,1'-dinitramine.

7. Composition based on polyamide resin under item 6, where the compound (C) an aromatic secondary amine contains at least any one of N,N'-di-2-naphthyl-p-phenylenediamine and 4,4'-bis(α,α-dimethylbenzyl)diphenylamine.

8. Composition based on polyamide resin under item 1, where the phenolic antioxidant contains at least any of 3,9-bis [2-[3-(3-tert-butyl-4-hydroxy-5-were)propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane and N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxyhydrocinnamate).

<> 9. Composition based on polyamide resin under item 1, where the organic sulfur compound (C) contains at least one or more elements selected from mercaptobenzimidazole-containing compounds, compounds based on dithiocarbamates acid, compounds based on thiourea and compounds based on organic timeslot.

10. Composition based on polyamide resin under item 9, where the organic sulfur compound (C) contains one or more elements selected from compounds based on mercaptobenzothiazoles and compounds based on organic timeslot.

11. Composition based on polyamide resin under item 10, where the organic sulfur compound (C) contains one or more elements selected of the group consisting of 2-mercaptobenzimidazole, 2-mercaptobenzimidazole, Dimyristyl-3,3'-thiodipropionate, DISTEARYL-3,3'-thiodipropionate and tetrakis(3-lawrenceofarabia) pentaerythritol.

12. Composition based on polyamide resin under item 11, where the organic sulfur compound (C) contains at least one of tetrakis(3-lawrenceofarabia) pentaerythritol, Dimyristyl-3,3'-thiodipropionate and 2-mercaptobenzimidazole.

13. Molded product comprising a composition based on polyamide resin under item 1.

14. Molded product under item 13, which is a hose or pipe.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: invention relates to pipe, possessing increased resistance to growth of pipe cracks and manufactured from polyethylene composition, as well as to application of phenol type stabiliser (C) and phenol type stabiliser (D) to increase resistance of pipes to slow crack growth. Pipe consists of polyethylene composition, which includes basic resin and phenol type stabilisers (C) and (D), which are different. Stabiliser (C) contains, at least, one ester group, and stabiliser (D) does not contain any ester group. Basic resin of polyethylene composition contains first ethylene homo- or copolymer (A) and second ethylene copolymer (B), with comonomer(s) for copolymer (B) and, possibly, copolymer (A) representing C3-C20 alpha-olefins.

EFFECT: pipes in accordance with invention have stability in testing whole cut for creep (FNCT), measured in accordance with ISO 16770:2004, at least, 5000 h.

11 cl, 1 tbl, 3 ex

Gas-main pipeline // 2532972

FIELD: transport.

SUBSTANCE: gas pipeline contains linear tube sections to transfer conveyed gas from entrance of the said section to its exit, herewith at least on the part of linear sections seamless pipe is installed having length equal to the length of this section and made of fibreglass plastic or carbon fibre-reinforced plastic. This pipe has inner diameter not less than 2500 mm.

EFFECT: increased productivity and durability of gas-main pipeline, lower construction costs.

6 cl, 2 dwg

Shell of composite // 2531108

FIELD: transport.

SUBSTANCE: shell of composite is intended for use in aircraft and aerospace engineering. Foam plastic ply is arranged between rings 1, 2 and shell and composed of basic parts 3 to make intersecting channels. Said channels accommodate rib-like cellular structure 4 extending to edge frames 5. The latter are made of the sets of solid circular plies 9, 10 arranged across unidirectional bundles and/or threads. The latter alternate with the set of plies of rib-like cellular structure 11. Note here that depth of the latter in the frame makes 0.4-0.6 of its width outside the frame. Circular plies arranged cross unidirectional bundles and/or threads can be made of woven and/or braided materials, e.g. glass, organic or carbon threads or combination thereof.

EFFECT: increased strength of shell.

17 cl, 2 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to method of obtaining cross-linked pipe and to cross-linked pipe, which contains cross-linked polymer composition, containing cross-linked ethylene polymer. method of manufacturing cross-linked pipe includes: (i) polymerisation of ethylene non-obligatorily with one or several comonomers (comonomer) in presence of Ziegler-Natta catalyst with obtaining ethylene polymer, which contains carbon-carbon double bonds; ethylene polymer has: (A) linkability, expressed through the level of gel content, equal, at least, 50 wt %, according to the measurement of disc-shaped sample of cross-linked ethylene polymer (ASTMD 2765-01, Method A, extraction in decalin); or/and (B) content of carbon-carbon double bonds in a number higher than 0.2 carbon-carbon double bond/1000 carbon atoms, according to the measurement by FTIR method; and (ii) obtaining polymer composition, including, at least, 50% wt % of ethylene polymer; (iii) formation of pipe from composition, obtained at stage (ii); (iv) cross-linking pipe, obtained at stage (iii). Ethylene polymer represents ethylene homopolymer or ethylene copolymer with one or several comonomers, and is selected from elastomers (POE), plastomers (OPO) or very low density ethylene copolymers of (VLDPE), which cover the density range from 855 to 909 kg/m3, linear low density ethylene copolymers (LLDPE), which have density in the range from 910 to 930 kg/m3 (ISO 1183), medium density ethylene copolymers (MDPE), which have density in the range from 931 to 945 kg/m3, or high density polyethylenes (HDPE), which are selected from homo- or copolymers of ethylene, and which have density higher than 946 kg/m3. Cross-linked pipe consists of cross-linked polymer composition. Polymer composition before cross-linking includes, at least, 50 wt % of ethylene polymer, where ethylene polymer is obtained by polymerisation of ethylene optionally together with one or several comonomers (comonomer) in presence of Ziegler-Natta catalyst, where ethylene polymer contains carbon-carbon double bonds in a number higher than 0.4 carbon-carbon double bond/1000 carbon atoms, according to the measurement by FTIR method, where ethylene polymer has linkability, expressed through the level of gel content, equal, at least, 50 wt %, according to the measurement for disc-shaped sample of cross-linked ethylene polymer (ASTMD 2765-01, Method A, extraction in decalin) and has MFR2 from 0.01 to 5.0 g/10 min, Mn/Mw from 0.1 to 20.0 g/10 min, and where ethylene polymer represents ethylene homopolymer or ethylene copolymer with one or several copolymers, and is selected from linear low density ethylene copolymers (LLDPE), which have density in the range from 910 to 930 kg/m3 (ISO 1183), medium density ethylene copolymers (MDPE), which have density in the range from 931 to 945 kg/m3, or high density polyethylenes (HDPE), which are selected from ethylene homo- or copolymers and which have density higher than 946 kg/m3.

EFFECT: improvement of material properties.

18 cl, 5 tbl

FIELD: weapons and ammunition.

SUBSTANCE: housing is provided with profile power layer (5) located between its outer (3) and inner (4) power layers and is attached to them. Profile power layer is made as a set of mated and fastened to each other longitudinal multiwalled profiles (7) with inner hollow and filled cavities. Longitudinal slot (2) is designed mainly through, it is oriented by housing radius and formed by unit (6) of rigid fixation of the slot form. Unit of rigid fixation is formed by corrugations made on the slot location and to the length of the slot. Corrugations include slot fixing corrugation (14) of inner power layer and corrugation (17) of higher rigidity of profile power layer. Corrugation of higher rigidity is made on one or two adjacent profiles and is reinforced from outside by longitudinal stiffener (19). Profiles cavities adjacent to the corrugation with its stiffener are filled with heat-insulation material. By the second version housing has longitudinal rectangular slot in guiding profile element provided with base, slot-forming and support surfaces. Guiding profile element is located in fixation unit embracing its support surface by slot-fixing corrugation.

EFFECT: improving maintenance reliability with required housing geometry being unchanged.

29 cl, 12 dwg

Multimodal polymer // 2496794

FIELD: chemistry.

SUBSTANCE: invention relates to cross-linked polyethylene, a method of producing cross-linked polyethylene, as well as cross-linked polyethylene and articles, preferably pipes, made therefrom. The cross-linked polyethylene contains a multimodal ethylene polymer with density lower than 950 kg/m3, which is obtained via polymerisation in the presence of a catalyst with one active centre and having STR21 from 2 to 15 g/10 min and shear thinning index PSV2.7/210 from 5 to 10.

EFFECT: providing a polymer composition with improved cross-linking capacity, eg with cross-linking degree of at least 70%, flexibility and good processability.

14 cl, 3 tbl, 1 ex

Multimodal polymer // 2491298

FIELD: chemistry.

SUBSTANCE: invention relates to cross-linked multimodal polyethylene. Described is cross-linked polyethylene, which includes multimodal ethylene polymer with density less than 950 kg/m3, obtained by polymerisation in presence of catalyst with one active centre. Polymer has MFR21 from 10 to 20 g/10 min. Index of viscosity reduction in shifting of TVR2.7/210 is at least 4. Also described is application of multimodal ethylene polymer in production of cross-linked pipe and method of multimodal ethylene polymer obtaining.

EFFECT: obtaining good workability and essential cross-linking in one and the same polymer.

15 cl, 3 tbl, 2 ex

FIELD: machine building.

SUBSTANCE: proposed method comprises plasma processing of inner sealing later inner surface, applying outer layer of composite material composed of reinforcement fibers and binder and hardening of binding composite material. Inner sealing layer represents tubular billet from polymer material. Plasma processing of tubular billet is carried out in cold plasma of abnormal glow discharge in air in flow mode at 2-10 Pa.

EFFECT: high operating properties at ease of manufacture.

5 cl, 5 tbl

FIELD: process engineering.

SUBSTANCE: invention relates to production of tubes and may be used in production of tubes from composite materials. Proposed compound comprises epoxy resin, hardener, reinforcing and friction-decreasing additives, reinforcing fillers, crystalline silicon dioxide with particle diameter varying from 7 to 40 nm in amount of 0.01-10 wt % of the binder.

EFFECT: higher rupture strength, lower wear.

1 ex

FIELD: machine building.

SUBSTANCE: heat-insulated flexible multi-layer polymer pipe not spreading flame includes central pipe, barrier layer, reinforcing layer, bonding layer, heat-insulating layer and water-proof layer, layer with antipyretic and antidotic agents made of polymer material on the base of polyolefin, protective shell made of galvanised flexible metal sleeve.

EFFECT: provision of non-spreading of flame and decomposition products of elements of its structure under the influence of high temperatures in case of fire hazard, provision of flexibility for performing installation and repair and renewal operations in hard-to-reach places, provision of resistance of its external surface to mechanical damages that can occur at operations with pipe in hard-to-reach places.

3 cl, 1 dwg

FIELD: mining.

SUBSTANCE: device for delivery of geophysical instruments to horizontal wells comprises umbilical cable layout of two umbilical cables of different diameter, arranged coaxially one in the other with a geophysical instrument at one end of one of the umbilical cables. The end of the umbilical cable of smaller diameter, inside the umbilical cable of the larger diameter has a piston coupled with the umbilical cable of the larger diameter. The umbilical cables are placed one inside the other along the entire length of the umbilical cable of the larger diameter in the initial mutual position. The device has a limiter of relative motion of the umbilical cables to the value not exceeding the length of the umbilical cable of the larger diameter. There is a pressure chamber with two coaxial holes in the opposite walls, the hole of the larger diameter is sealingly connected to the umbilical cable of the larger diameter, and the umbilical cable of the smaller diameter extends through the seal into the hole of the smaller diameter and through the hole of the larger diameter.

EFFECT: increasing reliability, improving smoothness of displacement of geophysical instrument.

4 cl, 1 dwg

FIELD: machine building.

SUBSTANCE: invention relates to high-pressure flexible sleeves used in piping systems. Outer surface of a longitudinal projection of the flange represents a combined rotation surface consisting of conical, cylindrical and curved elements. The conical element of surface of the longitudinal projection is a flattened cone, the base of which is located on the end face side of longitudinal projection of the flange; a sealing layer is arranged along inner diameter of the flange of the flexible hose in a cavity for laying of the sealing layer; a bead ring is made from synthetic high-strength low-tensile cord.

EFFECT: simpler design of a flexible hose flange and providing reliability of attachment of a power frame on the flange.

5 cl, 2 dwg

FIELD: machine building.

SUBSTANCE: pipe assembly containing an electroconductive corrugated pipe including coils of peaks and cavities, an electroconductive polymer cover located throughout the length of the above corrugated pipe; at that, polymer cover includes a fire-resistant substance and has a volumetric specific resistance that equals approximately to 7×104 Ohm·cm, minimum tensile strength that equals approximately to 10.3 MPa, and minimum elongation that equals approximately to 200%.

EFFECT: creation of a cover having fire-resistant properties.

6 cl, 1 dwg

Hybrid cable // 2451155

FIELD: electricity.

SUBSTANCE: hybrid cable comprises several pipes for a fluid medium, electrical wires and/or optical conductors, a filling material, which are assembled together into a twisted bundle by means of a packing operation. The hybrid cable also comprises a protection shell covering the pipes for the fluid medium, the wires/conductors and the filling material, and at least one load-carrying element installed in a cross-section of the hybrid cable. The pipes for the fluid medium, the wires/conductors, the filling material and at least one load-carrying element are laid in turns, i.e. with a continuously varying direction along the entire length or on a part of the hybrid cable length. At the same time the assembled bundle shall be held as substantially rigid in torsion with the help of the protection shell, possibly, with addition of a strong tape wound along the spiral line onto the bundle directly under the protection shell.

EFFECT: simple manufacturing of a large-length cable with the help of a mobile small-size equipment, resistance to stretching forces in process of the cable installation.

19 cl, 8 dwg

Power hybrid cable // 2451154

FIELD: electricity.

SUBSTANCE: power hybrid cable comprises several electric cables, possibly, electrical wires and/or optical conductors, a filling material assembled together into a twisted bundle by means of a packing operation. The power hybrid cable also comprises a protection shell and at least one load-carrying element installed in a cross-section of the power hybrid cable. Electric cables, possible wires/conductors, the filling material and at least one load-carrying element are laid in turns, i.e. with a continuously varying direction along the entire length or on a part of the power hybrid cable length. At the same time the assembled bundle shall be held as substantially rigid in torsion with the help of the protection shell, possibly, with addition of a strong tape wound along the spiral line onto the bundle directly under the protection shell.

EFFECT: simple manufacturing of a large-length cable with the help of a mobile small-size equipment.

17 cl, 6 dwg

FIELD: machine building.

SUBSTANCE: hose includes internal hose (10) at least with two sections (12, 13) connected to each other using at least two internal connection elements (16, 17; 30a, 30b; 72, 73) passing in transverse direction. Internal hose is flexible and includes flexible reinforced wall having inner diametre at least of 10 cm. External hose (11) enveloping internal hose contains water-proof elastomeric or composite material and includes at least two sections (20, 21) connected to each other by means of two external connection elements (24, 25). External hose has wall at least 2 cm thick, bending radius, at least 2 m and inner diametre of at least 20 cm. Internal hose is kept at some distance from external hose by means of a number of separating elements (28, 29) covering distance hi between outer wall of internal hose and oinner wall of external hose; at that, this distance is within 0.1 to 0.8 of inner diametre di0 of internal hose (10), and longitudinal position of a pair of internal connection elements (16, 17; 30a, 30b; 72, 73) is at the level of or close to longitudinal position of pair of external connection elements (24, 25). Internal connection elements (16, 17; 30a, 30b; 72, 73) cover distance hi between walls of internal and external hoses and include flange section (16, 17, 72, 73) of internal hose wall, two transverse support surfaces (34, 35) on external hose wall; at that, flange sections (16, 17, 72, 73) are connected in a detachable way between support surfaces (34, 35) to prevent relative axial movement between segments of internal and external hoses (12, 13; 20, 21) at the level of or close to longitudinal position of pair of external and internal connection elements, in which flange sections (72, 73) can be detached from internal hose wall and/or support surfaces (34, 35) can be detached from wall of external hose so that at removal of flange sections (72, 73) and/or support surfaces (34, 35) from gap between internal hose (10) and external hose (11), all parts of wall of internal hose (10) are located at some distance from external hose (11) wall.

EFFECT: hose is extended when used in marine conditions.

Floating pipeline // 2384785

FIELD: machine building.

SUBSTANCE: invention refers to pipeline hydro-transport and can be implemented at construction of pipeline transporting homogenous fluid and hydraulic mixtures. The floating pipeline consists of sections of pipes (2) made out of elastic material and connected with flanges. Each section of pipe (2) has several floats (4) of positive buoyancy in fluid; also the floats are equipped with compensators of lengthwise travel (5). Compensators of lengthwise travel (5) can be made in form of elements fabricated out of flexible material secured in side ears (6) of neighbour floats. End floats (7) of neighbour sections of pipes are connected with arresters of lengthwise travel in form of chains (8) secured in side ears. Chains (8) are supported with poles (10) attached to flanges of pipes. Support facilities for service lines, for example for electric cables, are made on the floats in form of upper ears (11); these facilities are furnished with devices for fastening service lines (14).

EFFECT: ensuring high flexibility at pipeline travel and increased reliability of service lines securing.

3 cl, 3 dwg

FIELD: construction industry.

SUBSTANCE: invention refers to corrugated tubes (including hoses) designed for transporting gases and gas liquid mixtures. The effect is achieved by two version of the invention. As per the first version, the specified effect is achieved by the fact that gas pipeline consists of at least one pair of corrugated pipe lengths, the ratio of corrugation pitches of which is within 0.3-0.9, and amplitude ratio - within 0.8-1.2; at that, each specified length of the pipe consists of at least one corrugation pitch. As per the second version, the specified result is achieved by the fact that gas pipeline consists of at least one corrugated pipe length with the corrugation profile formed by adding at least two periodic functions of the distance along the pipe axis; at that, ratio of periods of the above functions is within 0.3-0.9, and amplitude ratio - within 0.8-1.2.

EFFECT: reduction of noise and vibration, which appear owing to turbulence of internal medium flow in corrugated gas line without any loss of efficiency caused by decrease of transportation speed.

2 cl, 4 dwg

FIELD: transportation.

SUBSTANCE: in discharge floating pipe floats are arranged as a whole with hose and are installed along its whole length next to each other, at that internal diametre of torus is equal to diametre of hose external wall, besides, coaxially with hose and floats on their external sides, limiter of radial deformation is installed, made of fabric cloth shaped in jacket in the form of split cylinder with the possibility of its volume variation. In method, which includes assembly of multi-layer hose from rubber-fabric materials on cylindrical metal mandrel, press-fitting of billet prior to vulcanisation, vulcanisation and dismantling of discharge pipe, and on external wall of hose along its whole length next to each other, flat-folded rubber-fabric billets of floats are installed, which have nipples for passage of compressed air and arranged in the shape of torus with internal diametre equal to diametre of hose external wall, gaskets are installed in internal cavities of floats and between neighboring floats, at that limiter of radial deformations is installed coaxially with hose and floats on their external sides, press-fitting of hose with floats prior to vulcanisation is carried out by means of air injection via nozzles into floats installed between hose and limiter of radial deformations.

EFFECT: simplified assembly works and increased reliability of pipeline.

2 cl, 3 dwg

FIELD: technological processes.

SUBSTANCE: in method for manufacture of fire resistant hose armoured with metal braiding by means of coaxial fire resistant layer on it from siliceous textile soaked with solution of organosilicic rubber and polymerised to rubber-like condition, layer of siliceous textile in process sequence is applied between layers of metal braiding, afterwards it is soaked by hose submersion with plugged ends in solution of organosilicic rubber and polymerised, at that solution of organosilicic rubber used is solution of 100 mass parts of low molecular organosilicic rubber paste in 50 mass parts of benzene, and duration of soaking is assigned as 10 minutes.

EFFECT: higher efficiency of fire protection of fire resistant hose armored with metal braiding.

4 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to fire-resistant compositions of polyamide resin. Claimed is a fire-resistant composition of the polyamide resin, including a polyamide (A), which contains a unit, representing diamine and containing not less than 70 mol% of a unit, representing p-xylylenediamine, and a unit, representing dicarboxylic acid and containing not less than 70 mol% of a unit, representing a linear aliphatic dicarboxylic acid, which has from 6 to 18 carbon atoms; an organohalogen compound (B), which serves as fire-protective means; an inorganic compound (C), which serves as auxiliary fire-protective means; and an inorganic filling agent (D), where the polyamide (A) includes a polyamide, which has the concentration of phosphorus atoms, constituting from 50 to 1000 ppm, and a value YI, which by results of differential colorimetric analysis in accordance with JIS-K-7105, does not exceed 10, and the content of the organohalogen compound (B), the content of the inorganic compound (C) and the content of the inorganic filling agent (D) constitutes from 1 to 100 wt.p. from 0.5 to 50 wt.p. and from 0 to 100 wt.p., respectively, counted per 100 wt.p. of the polyamide (A). Also claimed is the moulded product from the said composition.

EFFECT: composition has excellent mouldability, mechanical properties, heat resistance and low water absorption.

15 cl, 4 tbl, 21 ex

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