Low-emission polyolefin composition containing vitamin e type stabiliser

FIELD: chemistry.

SUBSTANCE: tube is made from a polyolefin composition which contains a (co)polymer of ethylene or (co)polymer of propylene, a vitamin E type stabiliser of formula (I) , where R1, R2, R3, R4 and R5 independently denote H or unsubstituted or substituted aliphatic or aromatic hydrocarbon radicals which may contain heteroatoms, and a phenol stabiliser of formula (II); in which R6, R7 and R8 independently denote unsubstituted or substituted aliphatic or aromatic hydrocarbon radicals which may contain OH groups; and X1, X2 and X3 independently denote H or an OH group, provided that at least one of X1, X2 and X3 denote an OH group, and optionally an ultraviolet stabiliser.

EFFECT: low emission of additives and products of decomposition thereof in water.

20 cl, 2 tbl, 2 ex

 

The present invention relates to polyolefin compositions with very low emission of used additives and decomposition products, in particular phenols, and therefore the composition is particularly suitable for the manufacture of pipes, for example, for drinking water.

Recent advances in production and processing of polymers has led to the use of plastic materials in almost any of the existing fields. However, the polymers are subject to decay under the action of light, oxygen and high temperatures. This leads to loss of strength, hardness and flexibility, discoloration, susceptibility to mechanical damage and cracking, fading and haze.

Polymers, for example polyolefins, such as polyethylene and polypropylene, are subjected to decomposition by the radical mechanism especially during the stages of processing, which may include molding or casting, extrusion, etc. Decomposition of a radical mechanism continues during operation under the influence of light or high temperatures and, in the end, leads to the loss of polymer properties.

It is known that antioxidants and light stabilizers can prevent or at least reduce these effects. For protection during processing and achieve the desired performance properties in polymers, e.g. the Yat several types of additives. Entered additives are usually divided into stabilizers and modifiers. As a rule, modifiers are antistatics and funds from tarnishing or fading, acid acceptors, the pore-formers, lubricants, tools, forming the nuclei of crystallization centers, contributing to the slide means and antiadhesive, as well as fillers, flame retardants and the crosslinking agents.

Stabilizers, like antioxidants, commonly used at the present time, include spatial employed phenolaldehyde resin, aromatic amines, organophosphate/phosphonites and thioethers. However, the possible combinations of stabilizers should be carefully chosen depending on the final desired properties that should be possessed by the polymer products.

In WO 2004/033545 disclosed compositions antioxidants for increasing the duration of thermal stability of polymeric materials.

In addition to many other areas of the polyolefins used for the manufacture of pipes in distribution systems for drinking water supply. Because of the constant water contact with the inner surface of the pipe some compounds included in the composition of the pipe material, it may enter water. Allowable number of such compounds in drinking water is strictly regulated by a number of normative documents. In addition, it is expected wrest the increase of requirements, requirements for pipes made of polymer materials, with the introduction of the so-called "European schemes tolerance".

Emission stabilizers and modifiers and/or decomposition products that are added to the materials based on polyolefins, depends on many different properties of polymeric materials, such as the diffusion rate of molecules in a polymer matrix, chemical resistance additives, etc. in Addition, it is necessary to take into account that the emission reductions should not be obtained due to the stabilization of the polymer matrix. Thus, the additive composition which have a tendency to reduce the emission of polluting drinking water substances that cannot be obtained by simple addition of known stabilizers and modifiers based on the exercise of their properties, and requires a careful selection of adequate connections.

GB 2305180 discloses polyolefin compositions which are in permanent contact with extracting media. These compositions include organic phosphites/phosphonites phenol derivatives or spatial amines employed as a stabilizing component.

In light of the anticipated legal stricter requirements for pipes made of polymer materials, it is extremely important to the creation of tubes of high thermal and chemical resistance by camassia very small quantities of additives and/or products of their decomposition in the water.

Thus, an object of the present invention is a composition exhibiting a tendency to reduce emissions stabilizers and decomposition products, in particular phenol derivatives, without reducing the activity and the period of validity of the stabilizers. In particular, this concerns the stability properties of polymeric materials during processing and obtaining desirable for long-term operation of the properties are made of this composition products.

The purpose of this invention is to provide polymeric compositions containing a combination of additives comprising a stabilizer of the type of vitamin E, as defined below. The compositions can eliminate the disadvantages of the known compositions.

Therefore, the invention offers a polyolefin composition containing

(a) a polyolefin (A), (b) the stabilizer of the type of vitamin E (B) formula (I):

where R1, R2, R3, R4 and R5 independently of one another denote hydrogen or unsubstituted or substituted aliphatic or aromatic hydrocarbon radicals which may contain heteroatoms, and (c) phenolic stabilizer (C) of the formula (II):

where R6, R7 and R8 independently of one another denote unsubstituted or substituted aliphatic or aromatic hydrocarbon radicals, which may include HE-g is uppy; and X1, X2 and X3 independently of one another denote H or a group provided that at least one of X1, X2 and X3 denotes an OH group and,

(d) optional UV stabilizer (D).

It was found that the proposed resistant polyolefin compositions show when in contact with water, very low emissions of phenol derivatives in comparison with the conventional known stable compositions. At the same time reduced the total number of stabilizers sufficient to obtain the desired stabilization effect.

Heteroatoms, which may be present in unsubstituted or substituted aliphatic or aromatic hydrocarbon radicals R1, R2, R3, R4 and/or R5 of the stabilizer of the type of vitamin E (B) formula (I)can be oxygen, sulfur, nitrogen, phosphorus or similar atoms. However, preferably, R1, R2, R3, R4 or R5, more preferably R1, R2, R3, R4 and R5 do not contain heteroatoms, i.e. mean only unsubstituted or substituted aliphatic or aromatic hydrocarbon radicals or, as mentioned above, the mean N.

In addition, preferably R2, R3, R4 or R5, more preferably R2, R3, R4 and R5 represent H or saturated aliphatic hydrocarbon radicals containing from 1 to 5 carbon atoms, and most preferably R2, R3, R4 or R5, more preferably R2, R3, R4 and R5 are H or methyl is a group.

In addition, preferably R5 means a methyl group, irrespective of the nature of other residues R2 - R4.

In a particularly preferred embodiment, R4 and R5 denote a methyl group, and R2 and R3 denote H or a methyl group.

Most preferably R2, R3, R4 and R5 each denote a methyl group.

Further, preferably R1 denotes unsubstituted or substituted aliphatic or aromatic hydrocarbon radical containing from 5 to 50 carbon atoms, more preferably R1 denotes unsubstituted or substituted aliphatic hydrocarbon radical containing from 5 to 50, more preferably from 10 to 30, carbon atoms, and most preferably R1 means 4,8,12-trimethylacetyl group.

The stabilizer of the type of vitamin E (B) is preferably contained in the composition in an amount of not more than 0.5 wt.%, more preferably not more than 0.2 wt.%, even more preferably not more than 0.1 wt.% and most preferably not more than 0.05 wt.% of the total weight of the composition.

In addition, the stabilizer of the type of vitamin E (B) is preferably contained in the composition in amounts of at least 0.005 wt.%, more preferably at least 0.01 wt.% and most preferably at least of 0.015 wt.% of the total weight of the composition.

In the phenolic stabilizer (C) of the formula (II) R6, R7 and R8 independently of one another are unsubstituted and the and substituted aliphatic or aromatic hydrocarbon radicals, which may contain Oh-groups. This means that in addition to the Oh-groups are no other heteroatoms in R6, R7 and R8, i.e. phenolic stabilizer (C) does not contain, for example, ester groups, amide groups, and phosphate groups.

Preferably R6, R7 and R8 are independently from each other unsubstituted or substituted aliphatic or aromatic, preferably aliphatic hydrocarbon radicals, which may contain Oh-groups have from 2 to 200 carbon atoms.

Preferably R6 and R7 independently from each other have from 2 to 20 carbon atoms, more preferably from 3 to 10 carbon atoms.

In addition, preferably R6 and/or R7, preferably R6 and R7 are aliphatic hydrocarbon groups of at least 3 carbon atoms, which has a branch at the second carbon atom, and most preferably R6 and/or R7, preferably R6 and R7 are tertiary utilname groups.

Preferably R8 is from 20 to 100 carbon atoms, more preferably has from 30 to 70 carbon atoms.

In addition, preferably R8 includes one or more phenyl residues.

Further, preferably R8 includes one or more hydroxyproline residues.

In the preferred embodiment, R8 is 2,4,6-trimethyl-3,5-di-(3,5-di-tert-butyl-4-hydroxyphenyl)benzene ostad the M.

Preferably the phenolic stabilizer (C) of the formula (II) X1 means HE group, and most preferably X1 means HE group and X2 and X3 denote N.

The amount of phenolic stabilizer (C) is preferably 0.02 wt.% or more, more preferably of 0.05 wt.% or more, and most preferably 0.08 wt.% or more.

The upper limit on the amount of phenolic stabilizer (C) is preferably equal to or less than 1 wt.%, more preferably equal to or less than 0.5 wt.% and most preferably equal to or less than 0.3 wt.%.

Preferably the weight ratio of the stabilizer of the type of vitamin E (B) and the phenolic stabilizer (C) is from 1:20 to 1:1, more preferably from 1:10 to 1:2, most preferably from 1:6 to 1:2.

In addition, preferably the total amount of the stabilizers (B) and (C) in the composition is not more than 1.5 wt.%, more preferably not more than 1 wt.% and most preferably not more than 0.5 wt.%.

Preferably the total amount of the stabilizers (B) and (C) in the composition is at least of 0.05 wt.%, more preferably at least 0.08 wt.% and most preferably at least 0.1 wt.%.

The proposed composition optionally includes an ultraviolet stabilizer (D). In a preferred embodiment of the invention the ultraviolet stabilizer (D) is necessarily rootstalk in composition.

The ultraviolet radiation stabilizer (D) preferably comprises, more preferably consists of, spatial difficult amines. Can use regular spatial employed amines, known as stabilizers ultraviolet radiation (in the literature often denoted by the acronym HALS: hindered amine light), for example in WO 2005/014706 disclosed suitable spatial hindered amine.

In the present invention preferably spatially hindered amine contains one or more groups of the formula:

in which G' and G" are the same or different alkyl residues, Z' and Z" are the same or different alkyl residues or Z' and Z together form a linking half of which may be optionally substituted ester, or a simple ester, amide, amino, carboxy or urethane group, and E is oxyl, hydroxyl, alkoxy, cycloalkane, aryloxy or alkyl residue or hydrogen.

In a preferred embodiment, the spatial difficult amine is a polymer of 2,2,4,4-tetramethyl-7-oxa-3,20-diaza-despero-(5.1.11.2)-heneicosan-21-he and epichlorohydrin.

The ultraviolet radiation stabilizer is preferably used in an amount of 0.01-1 wt.%, more preferably it is a number of 0.05-0.5 wt.% of the total weight of the composition.

In another preferred embodiment, the UV stabilizer (D) comprises, more preferably consists of, soot. In this embodiment, carbon black is preferably used in quantities of from 0.2 to 3.5 wt.%, more preferably from 1.0 to 3.5 wt.% and most preferably from 2.0 to 3.0 wt.% of the total weight of the composition.

Preferably, the compositions do not contain any (additional) phosphorus-containing stabilizers, and even more preferably in addition to the stabilizers (B), (C) and optionally (D) in the composition does not contain other stabilizers, i.e. in the composition are present only stabilizers (B) and (C) and optionally (D) in any of these options.

In addition, preferably the polyolefin (A) is a Homo - or copolymer of ethylene or Homo - or copolymer of propylene. Most preferably, the polyolefin is a Homo - or copolymer of ethylene.

The polyolefin (A) may be obtained by any known method.

Of course, the use of the proposed composition involves adding additional components selected from conventional additives, acid acceptors, fillers, mineral and lubricating means for improving the stability during processing and surface properties of the composition.

Preferably proposed polyolefin composition has a total emission of phenol at 200°C and time is no contact for 5 minutes not more than 5 nanograms per milligram of composition (ng/mg), more preferably not more than 3 ng/mg, and most preferably not more than 2 ng/mg, measured by the method of analysis of polymers on overall emissions of phenols, as described in the examples.

In addition, the number of decomposition products of phenolic compounds and/or their by-products passing from the proposed polyolefin composition in water is not more than 1 microgram per liter of water (ág/l), more preferably not more than 0.8 µg/l, and most preferably not more than 0.5 μg/l, measured according to the method of analysis of emissions into the water, as described in the examples.

The term "decomposition of phenolic compounds and/or their by-products" means present in the composition of phenolic compounds produced during decomposition of phenolic components, which were originally included in the composition, or which are phenolic by-products present in the phenolic components as impurities, for example phenolic compounds with different structure from phenolic components added according to the invention. Typically, and preferably, only those phenolic compounds, which are included in the composition, are stabilizers, and typically and preferably, only those products of decomposition of phenolic compounds present in the compositions, which are formed from added stabilizat the ditch.

The proposed composition is preferably used in the manufacture of pipes. They can be black or natural color (i.e. unpainted) or colored pipes.

Preferably this pipe is used in the system of transporting water. As shown below, using the proposed composition in the manufacture of pipes for water supply leads to the emission reduction additives and decomposition products of the compositions in water in contact with the specified pipe.

Preferably the pipe is a pipe for cold water, i.e. it is designed for transportation of cold water.

Examples

1. Definitions and measurement methods

a) the Rate of melt flow (MFR) of the polymer measured according to ISO 1133 at a temperature of 190°C. the magnitude of the load is indicated as a subscript, i.e MFR5means that the measurement is carried out at a load equal to 5 kg

b) analysis of the polymer for full issue of phenols

Samples of pipe (in mg) is placed in an empty glass tube. The tube is heated to 200°C for five minutes in the automatic thermal desorption (ATD), selected organic substances injected into the gas chromatograph (GC) to separate, identify mass spectrometry (MS) and determine their number using a flame ionization detector (FID).

Quantities of the phenolic compounds is determined by the calibration curve, based on data obtained for the same phenolic compounds, where possible (i.e. for those connections that are available). The number found in other samples of phenolic compounds is determined according to a calibration curve constructed on the basis of data obtained for structurally similar compounds.

c) Measurement of emissions into the water decomposition products of phenolic compounds and/or their by-products

Samples of pipe leached chlorine-free water according to EN 12873-1 at room temperature (23±2°C). Analysis on the content of organic compounds is subjected to water the third period emissions. For this purpose, water samples are extracted with methylene chloride. Before extraction in water add labeled with the isotope internal standards. The extracts are concentrated, add labeled with isotopes injected standard and analyzed by gas chromatography with mass-selective detector according to the European draft standards CEN Identification using gas chromatograph and mass spectrometry leached water of organic substances from materials in contact with drinking water". This draft CEN standards has been prepared by CEN TC 164 WG3 AHG7 based on co-normative research work EVK1-CT 2000-00052 and work funded by DG Enterprise and Industry (Grant Agreement S 12.403892).

As ROCEDURES control sample is used ultrapure water (Milli-Q), stored in acid washed glass containers as much time as leached test samples, which are extracted by methylene chloride and add all the standards, as described in the test method.

The ratio of the surface area (S) of the prototype, intended for contact with the test water volume (V) of the tested water is expressed in decimetres, i.e. DM-1(that means DM2/DM3or DM2/l). The ratio of surface to volume (S/V) must be in the range from 5 DM-1up to 40 DM-1. In the present invention the ratio S/V is equal to 15.4 DM-1.

The concentration of the compounds are calculated according to the formula:

[D]=AD/A1 × [I],

where

[D] is the concentration of compounds D (µg/l);

AD is the area of the peak for the compound D;

A1 is the area of the peak for the internal standard;

[I] is the concentration of the internal standard (µg/l).

The amount of phenolic compounds is determined according to a calibration curve constructed on the basis of the data obtained for the same phenolic compounds, where possible (i.e. for those connections that are available). The number found in other samples of phenolic compounds is determined according to a calibration curve constructed on the basis of data obtained for structurally similar compounds.

2. Preparation and measurement of samples

Composition (Examples 1 and 2) mixed/melted to a homogeneous state in a Buss-Co-Kneader 100 MDK/E-11 L/D. The polymer and additives are fed through the inlet into the first mixer Buss Co-Kneader, which is a single screw extruder located downstream of the discharge extruder and granulating device, cut the pill in the molten state and then cooled in water. The temperature profile of the mixer is 113/173/199/193/200°C from the first inlet to the outlet, and the discharge temperature of the extruder is 166°C. the Speed of rotation of the auger mixer is 201 rpm and the throughput of the mixer - 200 kg/h Pipe size 32×3 mm (which means the outer diameter × wall thickness) is prepared by extrusion in the extruder Battenfeld 45-25B capacity 33 kg/h and the speed of rotation of the screw 39 rpm, the Temperature of the melt in the extruder is equal to 207°C.

In the preparation of compositions/pipe you used the following connections:

first stabilizers:

- 2,5,7,8-tetramethyl-2(4',8',12'-trimethylbenzyl)chroman-6-ol (Irganox E 201™, vitamin E), manufactured by Ciba Speciality Chemical.

Tris(2,4-di-tert-butylphenyl)fosfat (Irgafos 168™), manufactured by Ciba Speciality Chemical.

Phenolic stabilizers:

pentaerythrityl-arakis(3-(3',5'-di-tert-butyl-4-hydroxyphenyl))propionate (Irganox 1010™), manufactured by Ciba Speciality Chemicals,

1,3,5-trimethyl-2,4,6-Tris(3,5-di-tert-butyl-4-hydroxyphenyl)benzene (Ethanox 330™), manufactured by Albemarle.

Concentrate soot:

to Central soot (CBMB) contains HDPE (high density polyethylene) 60,4 wt.%, MUSTACHE (carbon black) 39.5 wt.% and Irganox 1010 0.1 wt.%.

Polymer basics:

the polyolefin (A)used as polymer bases in all samples, is unstabilized bimodal high density polyethylene with a total content of co monomer butene of 1.05 wt.%, thus comonomer is exclusively in the high molecular weight part of polyethylene MFR5equal to 0.25 g/10 min and a density of 948 kg/m3.

Prepared with the following composition.

Table 1
Prepared compositions, all quantitative values are given in wt.%
Example 1 (comparative)Example 2
The polymer base (A)93,88of 93.96
Calcium stearate0,1500,150
Concentrate sootof 5.75of 5.75
Irgafos 168 (B)0,11-
Irganox 1010 (C)0,11-
Ethanox 330 (D)-0,11
Vitamin E (E)-0,03
The total number of stabilizers0,220,14

Table 2 gives the results of the analysis of polymers on the total amount of phenols that have fallen into the water at 200°C and time of contact of 5 minutes and measuring the emission of degradation products of phenolic compounds and/or their by-products into the water.

From the results shown in Table 2, one can notice that the low levels of phenol in the composition according to the invention contributes to lower emissions of phenols in water, measured according to the above test method. In addition, significantly lower emission of degradation products of phenolic compounds and/or their by-products into the water.

Table 2
Example 1 (comparative)Example 2
The analysis of polymers (total phenols in the composition, ng/mg)9,91,1
Emissions into water etc the products of decomposition of phenolic compounds and/or their by-products (total in mg/l, (the ratio surface/volume equal to 15.4 DM-1))1,2 (converted to water decomposition products (B) and (C) and/or their by-products)0,1 (converted to water degradation products (D) and (E) and/or their by-products)

1. Pipe made from polyolefin compositions containing
(a) Homo - or copolymer of ethylene or Homo - or copolymer of propylene (A),
(b) a stabilizer of the type of vitamin E (In) of the formula (I):

where R1, R2, R3, R4 and R5 independently of one another denote H or unsubstituted or substituted aliphatic or aromatic hydrocarbon radicals which may contain heteroatoms, and
(c) a phenolic stabilizer (C) of the formula (II):

where R6, R7 and R8 independently of one another denote unsubstituted or substituted aliphatic or aromatic hydrocarbon radicals which may contain an Oh-group, where R6, R7 and R8 in addition to Oh-groups have no other heteroatoms; and X1, x2 and X3 independently of one another denote H or a group provided that at least one of X1, x2 and X3 means HE group
and
(d) optional UV stabilizer (D).

2. The pipe according to claim 1, in which the stabilizer of the type of vitamin E formula (I) R2, R3, R4 and R5 independently of one another denote H or saturated aliphatic hydrocarbon is passed radicals, containing from 1 to 5 carbon atoms.

3. The pipe according to claim 1, in which the stabilizer of the type of vitamin E formula (I) R1 is unsubstituted or substituted aliphatic hydrocarbon radical containing from 5 to 50 carbon atoms.

4. The pipe according to claim 1, in which the stabilizer of the type of vitamin E (In) is contained in the polyolefin composition in an amount of at most 0.5 wt.%.

5. The pipe according to claim 1, in which the stabilizer of the type of vitamin E (In) is contained in the polyolefin composition in the amount of at least 0.005 wt.%.

6. The pipe according to claim 1, in which the phenolic stabilizer (C) of the formula (II) R6, R7 and R8 independently of one another denote unsubstituted or substituted aliphatic hydrocarbon radicals, which may contain an Oh-group, and where R6, R7 and R8, in addition to Oh-groups, have no other heteroatoms, and which have from 2 to 200 carbon atoms.

7. The pipe according to claim 1, in which the phenolic stabilizer (C) of the formula (II) R6 and R7 are aliphatic hydrocarbon groups of at least 3 carbon atoms, which has a branch at the second carbon atom.

8. The pipe according to claim 1, in which the phenolic stabilizer (C) of the formula (II) R8 is from 20 to 100 carbon atoms.

9. The pipe according to claim 1, in which the phenolic stabilizer (C) of the formula (II) R8 includes one or more hydroxyproline residues.

10. The pipe according to claim 1, in which the polyolefin composition to icesto phenolic stabilizer (C) is 0.02 wt.% and more.

11. The pipe according to claim 1, in which the polyolefin composition, the amount of phenolic stabilizer (C) is 1 wt.% or less.

12. The pipe according to claim 1, in which the polyolefin composition the weight ratio of the stabilizer of the type of vitamin E (In) and phenolic stabilizer (C) is from 1:20 to 1:1.

13. The pipe according to claim 1, in which the total number of stabilizers (b) and (C) in the polyolefin composition is at most 1.5 wt.%.

14. The pipe according to claim 1, in which the polyolefin composition the total number of stabilizers (b) and (C) in the composition is at least of 0.05 wt.%.

15. The pipe according to claim 1, in which the polyolefin compositions of ultraviolet stabilizer (D) is necessarily present.

16. The pipe indicated in paragraph 15, in which the ultraviolet stabilizer includes spatial hindered amine and/or soot.

17. The pipe according to claim 1, in which the polyolefin (A) is a Homo - or copolymer of ethylene.

18. The pipe according to claim 1, in which the composition has a total emission of phenol at 200°C and time of contact of 5 minutes at most 5 nanograms per milligram of composition (ng/mg), measured according to the method of analysis of polymers on overall emissions of phenols.

19. The pipe according to claim 1, where the issue of the composition in water is at most 1 micrograms decomposition products of phenolic compounds and/or their by-products per liter of water (ág/l), as change is prohibited according to the method of analysis of emissions into the water.

20. The method of producing pipe using a polyolefin composition containing
(a) Homo - or copolymer of ethylene or Homo - or copolymer of propylene (A),
(b) a stabilizer of the type of vitamin E (In) of the formula (I):

where R1, R2, R3, R4 and R5 independently of one another denote H or unsubstituted or substituted aliphatic or aromatic hydrocarbon radicals which may contain heteroatoms, and
(C) a phenolic stabilizer (C) of the formula (II):

where R6, R7 and R8 independently of one another denote unsubstituted or substituted aliphatic or aromatic hydrocarbon radicals which may contain an Oh-group, where R6, R7 and R8, in addition to Oh-groups, have no other heteroatoms; and X1, x2 and X3 independently of one another denote H or a group provided that at least one of X1, x2 and X3 means HE group
and
(d) optional UV stabilizer (D).



 

Same patents:

Tube-case // 2418226

FIELD: machine building.

SUBSTANCE: tube-case is of cellular structure consisting of net out of high strength material and solid polymer cover. Also, the net is made out of steel and is connected at intersections, while a polymer cover fills meshes of the net to depth less, than net thickness. The net can be made out of corrosion resistant steel wire, out of wire with corrosion resistant coating, out of spring wire (including the one with corrosion resistant coating) or to be solid metal cut-out-drawn (including zinc-coated). Polymer coating is made out of polymer thermo-plastic material, poly-ethylene of low pressure and thickness of 5-8 mm. It fills meshes to depth less, than net thickness facilitating reliable adhesion of internal surface of the tube-case with a functional material.

EFFECT: increased rigidity of tube-case of cellular structure.

8 cl, 3 dwg

FIELD: machine building.

SUBSTANCE: here is disclosed fabrication of pipe out of composite materials consisting in forming adhesion layer on mandrel, in successive forming sealing, stretching, power and under winding layers by winding composite materials impregnated with polymer binding and in following laying polymer binding on it. The sealing layer is formed by either winding two layers of a band out of non-woven material with pitch of 0.5 of band width impregnated with polymer binding and successive laying one layer of glass cloth on it or by winding two layers of the band out of glass cloth impregnated with glue at pitch of 0.5 of band width. The power layer is formed by the method of cross-layered lengthwise-cross winding out of strands of glass twisted complex thread soaked with polymer binding. The stretching layer is made by spiral-screw winding strands of glass twisted complex thread without impregnation with polymer binding. The under winding layer is formed by spiral screw or cross-layered lengthwise-cross winding strands out of glass twisted complex thread soaked with polymer binding.

EFFECT: increased weight perfection of transport-starting container out of pipe fabricated by winding composite materials; facilitation of pressure tightness and rigidity of pipe.

FIELD: chemistry.

SUBSTANCE: invention relates to use of an antioxidant to increase resistance of a polyolefin composition meant for making pipes to decomposition caused by contact with water, which contains CIO2. The antioxidant is selected from a) a group of phenols of formula I, where R is an unsubstituted or substituted aliphatic or aromatic hydrocarbon radical which can contain heteroatoms, or R is a heteroatom, R' and R" independently denote an unsubstituted or substituted hydrocarbon radical which can contain heteroatoms, or H, X1, X2 and X3 independently denote an unsubstituted or substituted hydrocarbon radical which can contain heteroatoms, or H or OH, where at least X1, X2 or X3 is OH, n assumes values from 1 to 4, and at least one of the phenol substitutes R, R' and/or R" contains at least one sulphur, phosphorus and/or nitrogen heteroatom or from b) amine compounds of formula II, where R1, R2, R3, R4, R5 and R6 independently denote a hydrogen atom or an aliphatic or aromatic hydrocarbon radical, possibly containing heteroatoms, or selected from c) sulphur-containing compounds of formula Ra-S-Rb III, where Ra and Rb independently denote an aliphatic or aromatic hydrocarbon radical, possibly containing heteroatoms.

EFFECT: antioxidant used has low susceptibility to extraction with water carried by a pipe made from such a polyolefin composition.

7 cl, 1 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a polyethylene composition for making pipes, which contains a polymer base comprising two polyethylene fractions with different molecular weight, to a pipe containing said composition and to use of said composition to make articles, preferably pipes. The polymer base accounts for not less than 90 wt % of the overall composition and has density of 932-938 kg/m3.The fraction of ethylene homo- or copolymer (A) has lower average molecular weight than the fraction of ethylene homo- or copolymer. The polyethylene composition has melt flow rate MFR5 between 0.1 and 0.6 g/10 min and shearing stress η2.7 kPa between 85 and 230 kPa. The polyethylene composition has improved combination of properties, particularly high flexibility, high mechanical strength and good long-term stability.

EFFECT: pipes obtained from the disclosed polyethylene composition have good operational characteristics, long-term stability and good resistance to rapid propagation of cracks, which facilitates their use in conveying liquids under pressure.

16 cl, 1 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a polyolefin composition which is suitable for making pipes. The composition used to make pipes contains polyolefin (A), a compound (B) which is bis(2,4-dicumyphenyl)pentaerythritol diphosphate, and a phenol compound (C) of formula (I), where R denotes an unsubstituted or substituted aliphatic or aromatic hydrocarbon radical, which can contain heteroatoms, or R denotes a heteroatom; each X1-X5 denotes H, OH and/or R'; where R' denotes a hydrocarbon radical or a hydrogen atom, and n equals 1-4; and g) possibly a stabiliser against UV light (D).

EFFECT: composition has low tendency to migration of additives and their decay products, particularly phenol compounds and a light stabiliser, not more than 1,8 mcg/l with surface to volume ratio S/V between 11,70 and 12,30 dm-1, without loss of stability.

10 cl, 3 tbl, 5 ex

FIELD: chemistry.

SUBSTANCE: polymer base is not less than 90 wt % of the overall composition and has density of 940-947 kg/m3.The fraction of homo- or copolymer of ethylene (A) has lower average molecular weight than the fraction of homo- or copolymer of ethylene. The polyethylene composition has melt flow rate MFR5 of 0.1-0.5 g/10 min and viscosity reduction index during shear (2.7/210) of 10-49, has better combination of properties, in particular high flexibility and high mechanical strength and good long-term stability.

EFFECT: pipes made from the disclosed polyethylene composition have good performance properties, especially in terms of flexibility and rapid propagation of cracks while preserving minimal required strength, processing characteristics, impact viscosity and resistance to slow propagation of cracks.

14 cl, 1 tbl, 3 ex

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

FIELD: machine building.

SUBSTANCE: cooling agent pipeline includes the following layers: outer layer from moulding compound on the basis of polyamide; inner layer having the thickness at least of 0.3 mm and containing polypropene, 0.02 wt % of heat stabiliser. Polypropene is hetero-phase copolymer on the basis of propene, which contains 0.5 wt % to 20 wt % of ethene.

EFFECT: increasing heat stability and mechanical pipeline strength.

10 cl, 1 tbl

FIELD: machine building.

SUBSTANCE: multi-layer pipe is made out of composite material corresponding to reinforced materials in form of alternate mono-layers with cross and lengthwise laying of reinforced material impregnated, for example with thermo-reactive binding. Binding consists of internal and external structure layers divided with a barrier layer. The barrier layer is made out of a layer of heat insulating foam applied on external surface of the internal structure layer and of an additional layer arranged between the layer of heat insulating foam and internal surface of the external structure layer. The latter corresponds to successively lain metal screens out of continuous bands divided with polymer material.

EFFECT: increased heat resistance of wall of multi-layer pipe.

5 cl, 1 dwg

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: chemistry.

SUBSTANCE: invention relates to binder for co-extrusion based on a mixture of co-grafted polyolefins, as well as a multilayer structure containing the binder. The binder contains a mixture of at least homo- or copolymer of ethylene (A1), having density 0.940-0.980 g/cm3, and at least one copolymer of propylene (B) containing at least 51 wt % propylene. (Co)polymers of the said mixture are co-grafted with a functional monomer selected from carboxylic acids and their derivatives. The degree of graft polymerisation of the extrusion binder is more than 0.05 wt % and less than 0.5 wt % of the total weight of the said binder. The mixture is possibly diluted in at least a homo- or copolymer of ungrafted ethylene (A2). Said binder has density of 0.940-0.980 g/cm3.

EFFECT: disclosed binder has sufficient fluidity, high resistance to peeling of layers at temperature higher than 80°C, and is meant for use in a multilayer structure for protecting metal surfaces and for making packaging, rigid hollow housings, particularly bubbles or bottles, or flexible reservoirs, as well as multilayer films.

13 cl, 2 tbl, 4 ex

FIELD: metallurgy.

SUBSTANCE: composition consists of copolymer of propylene, of first copolymer of ethylene with at least one linear or branched alpha-olefine having 3-8 carbon atoms and of second copolymer of ethylene with at least one linear or branched alpha-olefine having 3-8 carbon atms. Copolymer of propylene has value of poly-dispersity index within ranges from 4.5 to 10 and contents of isotactic penthalogy above 97.5 mol %. Also, said copolymer contains at least 95 wt % (relative to copolymer) links derivative from propylene. The first copolymer - copolymer of ethylene contains from 25 to less, than 40 wt % relative to this copolymer) links derivative from ethylene and is soluble in xylol at 25°C within the ranges from over 85 to 95 wt %, while the second copolymer of ethylene contains from 50 to less 75 wt %relative to this copolymer) links derivative from ethylene and is soluble in xylol at 25°C within the ranges from over 50 to 85 wt %, and possesses characteristic viscosity of fraction soluble in xylol below 1.8 sh/g.

EFFECT: composition possesses good resistance to stress causing whitening, and lustre combined with good balance of mechanical properties.

8 cl, 3 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a polyolefin moulding composition with higher resistance to thermal-oxidative decomposition and is especially suitable for making pipes which are in prolonged thermal contact with liquids which contain oxidative disinfection substances. The moulding composition contains thermoplastic polyolefin and an organic polyoxy compound in amount of 0.01-1.0% of the total weight of the moulding composition, with general chemical formula R-[(CH2)n-O]m-H, where n is an integer from 1 to 10; m is an integer from 3 to 500 and R is a hydrogen atom, or an OH- group or an alkyl group containing 1-10 carbon atoms and which can additionally have substitutes such as OH, -COOH, -COOR, -OCH3 or -OC2H5. The moulding composition can also contain an unsaturated aliphatic hydrocarbon in amount of up to 5 wt %.

EFFECT: moulding composition has good processability when making pipes and endows pipes made from the composition with higher thermal stability and high rupture resistance combined with improved organoleptic properties.

9 cl, 1 tbl, 5 ex

FIELD: chemistry.

SUBSTANCE: composition contains crystalline propyelen polymer, elastomeric copolymer of ethylene and propylene and polyethylene. When combined with components with certain values of polydispersity index and characteristic viscosity in given ratios, the composition exhibits high hardness, impact resistance and resistance to bleaching under loading. The composition has flexural modulus higher than 1300 MPa, resistance to bleaching during impact corresponding to diametre of the bleaching area not greater than 1.7 cm, caused by a die falling from a height of 76 cm and diametre of the bleaching area not greater than 1.2 cm, caused by a die falling from a height of 20 cm, and Izod impact resistance at 23°C greater than 14 kJ/m2 and at least equal to 6.5 kJ/m2 at -20°C.

EFFECT: composition has good balance of mechanical properties, is suitable for making articles through pressure casting, such as casings of batteries and consumer goods, and during hot shaping processes.

2 cl, 4 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: mixture contains two different polyolefin and ethylene/α-olefin copolymers. The ethylene/α-olefin copolymer is a block-copolymer containing at least one hard block and at least one soft block. The ethylene/α-olefin copolymer can function as a component which improves compatibility between two polyolefins which may be incompatible. The disclosed polymeric mixtures can be used in making various articles such as tyres, hoses, belts, linings, shoe soles, cast and moulded articles. Said mixtures are especially useful for applications requiring melt strength, such as big articles made by blow moulding, foam and bundled bars.

EFFECT: improved compatibility of mixtures.

27 cl, 10 dwg, 13 tbl, 40 ex

FIELD: chemistry.

SUBSTANCE: description is given of an olefin polymer composition used in pressure moulding and in hot moulding equipment, containing the following (in terms of weight): A) 60-85% crystalline propylene homopolymer characterised by polydispersity index (P.I) value ranging from 4.5 to 6 and content of isotactic pentades (mmmm) of over 96%, measured from 13C NMR in a fraction which is insoluble in xylene at 25°C; B) 15-40% partially amorphous ethylene copolymer containing from 35% to 70% propylene; the said olefin polymer composition has breaking stretching, in accordance with ISO 527, ranging from 150% to 600%. Also described is a method of preparing an olefin polymer composition through polymerisation in paragraph 1, involving at least two successive steps on which components (A) and (B) are obtained at different successive steps, carrying out each step, except the first, in the presence of the obtained polymer and the catalyst used at the previous step, and in the presence a Ziegler-Natta polymerisation catalyst containing a solid catalyst component which contains: a) Mg, Ti and a halogen and at least two electron donor compounds, said catalyst component is characterised by that, at least one of the electron donor compounds, present in amount ranging from 15 to 50 mol % of the total amount of donors, is selected from a class of succinates which are not extractable above 20 mol % and at least another electron donor compound which is extracted above 30 mol %; b) alkyl aluminium and optionally, c) one or more electron donor compounds.

EFFECT: highly elastic olefin polymer composition with high breaking elongation value is obtained.

5 cl, 3 tbl, 3 ex

Additive mixture // 2374277

FIELD: chemistry.

SUBSTANCE: invention relates to mixtures of additives to polymers, specifically to additive mixtures which are used as clarifiers for propylene homo- or copolymers. According to this invention, additive mixtures contain components (A), (B), (C) and (D). Component (A) is at least one compound of formula (I-1) , ,

and , component (B) is a compound of formula (II-1)

and component (D) is a compound of formula (III-1)

EFFECT: use of the additive mixture in accordance with this invention improves the processed propylene homo- or copolymers.

13 cl, 2 ex

FIELD: chemistry.

SUBSTANCE: invention relates to polyolefin compositions with good balance of hardness and impact-resistance and high elongation rating. A hetero-phase polyolefin composition is described, containing (wt %): (A) from 50 to 80 wt % crystalline propylene polymer with polydispersity index from 5.2 to 10 and isotactic pentad (mmmm) content over 97.5 mol %, determined by 13C-NMR spectroscopy in a fraction which is insoluble in xylene at 25°C; wherein the said polymer is chosen from a propylene homopolymer or propylene copolymer and at least a comonomer, chosen from ethylene and α-olefin with formula H2C=CHR, where R is a linear or branched C2-6-alkyl radical, containing at least 95 % repeating units derived from propylene; (B) from 5 to 20 % of the first elastomeric ethylene copolymer with at least a comonomer chosen from propylene and another α-olefin with formula H2C=CHR, where R is a linear or branched C2-6-alkyl radical; wherein the said first elastomeric copolymer contains from 25 to less than 40% ethylene and is soluble in xylene at room temperature in amount ranging from over 85 wt % to 95 wt %, where characteristic viscosity [η] of the fraction soluble in xylene ranges from 2.5 to 4.5 dl/g; and (C) from 10 to 40% of a second elastomeric ethylene copolymer with at elast a comonomer, chosen from propylene and another α-olefin with formula H2C=CHR, where R is a linear or branched C2-6-alkyl radical; wherein the said second elastomeric copolymer contains 50 to 75% ethylene and is soluble in xylene at room temperature in amount ranging from 50 wt % to 85 wt %, where characteristic viscosity [η] of the fraction which is soluble in xylene ranges from 1.8 to 4.0 dl/g; in which total amount of copolymer (B) and copolymer (C) ranges from 20 to 45 % of the total amount of components (A)-(C), total amount of ethylene with respect to total amount of components (A)-(C) is 23 wt %, and the ratio of ethylene content in the fraction which is insoluble in xylene at room temperature, (C2xif), multiplied by the weight percent content of the fraction which is insoluble in xylene at room temperature, (%XIF), and ethylene content in the fraction which is soluble in xylene at room temperature, (C2xsf), multiplied by weight percent content of the fraction which is soluble in xylene at room temperature (%SXF), i.e. C2xif x % XIF)/(C2xsf x % SXF), satisfies the following relationship (I): (C2xif x % XIF)/(C2xsf x % SXF)>0.01 x + 0.261, where x is total amount of ethylene. Described also is a method of polymerisation of the polyolefin composition described above, involving at least three consecutive steps, where components (A), (B) and (C) are obtained on separate consecutive steps, where operations on each step, except the first step, take place in the presence the polymer formed in the previous step and catalyst used in the previous step.

EFFECT: obtaining polyolefin compositions with high hardness, without reducing impact resistance, especially impact resistance at low temperatures and elastic properties.

2 cl, 3 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: invention relates to polyolefin composition which are resistant to dynamic loading and to the method of producing said composition. The composition contains A) 60 to 95 wt % propylene (co)polymer of with polydispersity index (P.I) from 4.6 to 10 and isotactic pentad content (mmmm) over 98 mol %, determined using 13C-NMR spectroscopy for a fraction which is insoluble in xylene at 25°C and B) 5 to 40 wt % ethylene copolymer, containing 40 to 70 wt % propylene or C4-C10 α-olefins or their combination and, optionally, small diene proportions. The composition has temperature rising elution fractionation (TREF) profile, obtained through fractionation in xylene with tapping fractions at temperature 40°C, 80°C and 90°C, in which ethylene content Y in the fraction tapped at 90°C satisfies relationship (I): Y≤-0.8+0.035X+0.0091X2, where X is ethylene content in the fraction tapped at 40°C, and both values of X and Y are expressed in weight percent, and value of intrinsic viscosity [η] of the fraction which is soluble in xylene at 25°C ranges from 1.8 to 4.2 dl/g.

EFFECT: obtaining olefin polymer with good balance of properties, more specifically with high hardness and good resistance to dynamic loading.

3 cl, 3 ex, 3 tbl

FIELD: chemistry.

SUBSTANCE: rubber composition consists of, wt %: polypropylene - 3-21, butadiene-nitrile rubber - 22-55, olefin rubber - 2.5 -9.5, modificator, cross-linking agent for rubbers - 1.5-3.5, activator - 0.18-0.3, plasticiser - 3.0-7.5, mineral oil - 8-40. The composition contains polyisocyanate containing not less than two isocyanate groups (0.05-2.3 wt %) as a modificator and polypropylene with 1-6% of grafted maleic anhydride or maleic acid - 6-20 wt %. Plasticiser solubility parametre of is not less than 18 (kJ/m3)1/2.

EFFECT: oil resistance enhancing, decrease of relative residual elongation and melt flow index.

1 tbl, 9 ex

FIELD: process engineering.

SUBSTANCE: invention relates to production of microporous polyolefin membranes to be sued in storage battery separators. Membrane is made from polyethylene resin, the main component, and features (a) cutout temperature of 135°C or lower whereat air permeability measured at heating at temperature rise rate of 5°C/minute reaches 1×105 s/100 cm3, (b) air permeability variation degree of 1×104 a/100 cm3/°C or higher that makes gradient of curve describing dependence of said air permeability upon temperature at air permeability of 1×104 s/100 cm3, and (c) fusion temperature of 150°C or higher whereat air permeability measured at further increase of temperature after reaching cutout temperature, again, equals 1×105 s/100 cm3.

EFFECT: well-balances air permeability variation after cutout start, low cutout temperature and better fusion properties.

11 cl, 7 dwg, 2 tbl, 13 ex

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