Binder for co-extrusion of co-grafted polyethylene and polypropylene, diluted in ungrafted polyethylene

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

 

The present invention relates to a coextrusion binder in a mixture together grafted polyolefins.

More precisely, it refers to a mixture that is used as a coextrusion binder, at least, high density polyethylene (PEHD) (A1) and at least Homo - or copolymer of propylene (C), the mixture (A1) and (B) grafted by means of a functional monomer and possibly diluted unvaccinated polyethylene high density (PEHD) (A2). The percentage of grafted monomer in the binder is more than 0.05% and less than 0.5%, preferably more than 0.10% and less than 0.4% of the total weight of the binder, regardless of whether there is or is missing (A2) in the binder.

Very often three-layer coatings are used to protect the outer surface of the metal pipe intended for the construction of oil or gas pipelines. Depending on the metal surface they consist of:

the primary layer, presents epoxy resin;

"binder that reacts with the epoxy composition;

- polyethylene, preferably, medium or high density.

Binder described in document WO 99/61246 contains

(A) 50-100 parts of the Homo - or copolymer of polyethylene with a density greater than or equal to 0.9;

(C) 0-50 parts of a polymer selected from (B1) Homo - or copolymer polypro is a,

the sum (A)+(B) equals 100 parts, and the mixture (A)+(B) grafted at least 0.5 wt.% functional monomer. In turn, the mixture is diluted, at least in Homo - or copolymer of polyethylene (C).

The task is to create a new binder having a high resistance to removal of the layers at a temperature exceeding 80°C, and intended for use, preferably in the composition of the protective coating of pipes (insulation), including structure, containing at least one layer PEHD or PEMD. Moreover, a binder to facilitate its use must have sufficient fluidity to the degree of graft polymerization of less than 0.5%, preferably less than 0.4 wt.% the total weight of the binder.

The applicant shows that the types of the binder according to the invention, the density (0,940-0,980 g/cm3) binder plays an important role in adhesion at low and high temperatures. A binder according to the invention allows to achieve the following levels of adhesion: needlemaster at room temperature and the use of force to remove a layer of more than 100 N/cm at a temperature of 80°C in the following conditions.

The invention is particularly applicable in structures, including metal surface. The present invention is used in polyethylene coated metal surfaces, the company is in the pipes, the outer surface of which is covered with PEHD or PEMD.

The present invention also relates to a multilayer structure that includes a layer containing the above-mentioned binder, which is directly connected layer of nitrogen-containing or oxygen-containing polar resin, such as a layer (E) polyamide resin, saponified copolymer of ethylene and vinyl acetate, polyester resin, mineral oxide deposited on a polymer, such as polyethylene, polyethylene terephthalate, ethylene vinyl alcohol or better on the metal layer.

The objective of the invention is a coextrusion binder containing a mixture of at least one Homo - or copolymer of ethylene (A1)having a density of 0,940-0,980 g/cm3and at least one Homo - or copolymer of propylene (); this mixture grafted functional monomer and possibly diluted at least Homo - or copolymer grafting of ethylene (A2)having a density of 0,940-0,980 g/cm3while

- the degree of graft polymerization of this coextrusion binder is less than 0.5 wt.% the total weight of the specified binder;

the density of the specified binder is 0,940-0,980 g/cm3.

According to a variant of the invention, the binder is characterized by the fact that the degree of graft polymerization is more than 0.05% and less than 0.5 wt.% from the total the ena of this binder.

According to a variant of the invention, the binder is characterized by the fact that the degree of graft polymerization is less than 0.4 wt.% the total weight of this binder.

According to a variant embodiment of the invention a binder characterized in that the degree of graft polymerization is more than 0.10% and less than 0.4 wt.% the total weight of this binder.

According to a variant of the invention, the binder is characterized by the fact that the density of (A1) is 0,940-0,980 g/cm3.

According to a variant of the invention, the binder is characterized by the fact that the density of (A2) is 0,940-0,980 g/cm3.

According to a variant of the invention, the binder is characterized by the fact that the density of (A1) and/or (A2) is 0,945-0,960 g/cm3.

According to a variant of the invention, the binder is characterized by the fact that the density () is 0,860-0,920 g/cm3.

According to a variant of the invention, the binder is characterized by the fact that (A1) and (A2) are the same polymers.

According to a variant of the invention, the binder differs in that it contains

- from 99.5 to 80% (A1), preferably from 99 to 90%;

from 0.5 to 20% (In), preferably from 0.5 to 10%;

- 0% (A2);

- the percentage (by weight) of the total weight of this binder.

According to a variant implementation of the image is to be placed binder differs it contains

- 5-60% (A1), preferably 5-40%;

- 0.5 to 20%, preferably, 0.5 to 10%;

- 94,5% and 40% (A2), preferably, 94,5-60%;

- the percentage (by weight) of the total weight of this binder.

The present invention also relates to a multilayer structure containing at least one layer of the above-mentioned coextrusion binder.

According to a variant embodiment of the invention the structure is the fact that consistently contains the following layers: metal/epoxy resin/binder coextrusion/PEHD or PEMD.

The present invention is also the use of the binder described above.

In addition, the present invention relates to the use of coextrusion binder that contains at least a mixture of high density polyethylene (A1) and at least one Homo - or copolymer of propylene (), this blend of grafted functional monomer and possibly diluted the unvaccinated high-density polyethylene (A2), while

- the degree of graft polymerization specified coextrusion binder is more than 0.05 and less than 0.5%, preferably from 0.15 to 0.4 wt.% the total weight of the specified binder;

the density of this binder is 0,940-0,980 g/cm3preferably 0,940-0,960 g/cm3;

in the multilayer article is ucture, contains the following successive layers: metal/epoxy/specified coextrusion binder/ PEHD or PEMD.

According to a variant embodiment of the invention the use is characterized by the fact that as (V) use of ethylene-propylene rubber (EPR).

The polyethylene (A1) selected from Homo - or copolymers of polyethylene. Density (A1) is 0,940-0,980 g/cm3preferably 0,945-0,960 g/cm3. (A1) is a high density polyethylene (PEHD). Its MFI (a measure of viscosity at a temperature of 190°C, 2,16 kg) is 1-100 g/10 min, preferably 1 to 40 g/10 minutes

The comonomers include

- alpha-olefins, preferably containing from 3 to 30 carbon atoms.

Examples of alpha-olefins containing from 3 to 30 carbon atoms as additional comonomers include propylene, 1-butene, 1-penten, 3-methyl-1-butene, 1-hexene, 4-methyl-1-penten, 3-methyl-1-penten, 1-octene, 1-mission 1-dodecene, 1-tetradecene, 1-hexadecene, 1 octadecene, 1 achozen, 1-cocozen, 1-tetracosane, 1-hexacosane, 1-octacosane, 1 triacetin. Data alpha-olefins may be used singly or in mixture of two or more components;

- esters of unsaturated carboxylic acids, such as alkyl(meth)acrylate, and alkali, can contain up to 24 carbon atoms.

Examples of alkylacrylate and alkylmethacrylamide are, in particular, metalmetal ilat, the acrylate, n-butyl acrylate, isobutylamine, 2-ethyl hexyl acrylate.

vinyl esters of saturated carboxylic acids such as vinyl acetate or finalproject;

unsaturated epoxides.

Examples of unsaturated epoxides are, in particular,

- esters and ethers of aliphatic glycidyl, such as allylglycidyl ether, vinylpyridine ether, the ether maleic acid, glycidylether, glycidylmethacrylate and glycidylmethacrylate;

- esters and ethers of alicyclic glycidyl, such as 2-cyclohexen-1-glycidyloxy ether, cyclohexene-4,5-diglycidylether, cyclohexen-4-glycidyloxy, 5-norbornene-2-methyl-2-glycidyloxy and endotis-bicyclo(2,2,1)-5-hepten-2,3-digitalliteracy;

unsaturated carboxylic acids, their salts, their anhydrides.

Examples of anhydrides of unsaturated carboxylic acids are, in particular, maleic anhydride, itacademy anhydride, citraconic anhydride, tetrahydrophthalic anhydride.

- diene, such as, for example, 1,4-hexadiene.

(A1) may include several comonomers.

Preferably, the polymer (A1), which can be a mixture of several polymers contains at least 51%, preferably 75% by mole. of ethylene.

(A2) selected from (A1), such as defined above. Preferably, (A2) are identical (the 1). However, (A2) in contrast to (A1) is not vaccinated. Index MFI (A2), a measure of viscosity at a temperature of 190°C. under of 2.16 kg) is less than 10 g/10 min, preferably less than 6 g/10 min, and more preferably 6-1 g/10 min, 6-2 g/10 min, 6-3 g/10 min and even 6-4 g/10 minutes

(C) is a Homo - or copolymer of polypropylene. As comonomers can be called

- alpha-olefins, preferably containing from 2 to 30 carbon atoms. Examples of such alpha-olefins similar to that shown for the case of (A1) except that in this list of propylene should be replaced with ethylene;

- diene.

(B) may also be a block copolymer of polypropylene.

Examples of the polymer (C) can be

- polypropylene;

- a mixture of polypropylene and ethylene propylene diene monomer Montana (EPDM) or ethylene-propylene rubber (EPR).

Will not occur beyond the invention of the if () will be represented by ethylene-propylene rubber (EPR) or ethylene-propylene-Montana (EPDM).

Preferably, the polymer (C), which may be a mixture of several polymers, comprises at least 51 wt.%, preferably 75 wt.% propylene.

Density (B) can be 0,86-0,98 g/cm3preferably 0,860-0,920 g/cm3. Its viscosity index (MFI) is preferably 1-30 g/10 minutes

In case, if the binder is missing (A2), (A2) is equal to 0%.

The proportion of (A1) connecting the leaves from 99.5 to 80 wt.%, preferably 99-90% wt. the total weight of the binder.

Share (C) in the binder is from 0.5 to 20 wt.%, preferably 0.5 to 10 wt.% the total weight of the binder.

If (A2) is present in the binder, then (A2) is not equal to 0%.

The proportion of (A1) in the binder is from 5 to 60 wt.%, preferably 5-40 wt.% the total weight of the binder.

Share (C) in the binder is from 0.5 to 20 wt.%, preferably 0.5 to 10 wt.% the total weight of the binder.

The share of (A2) in the binder is from 94,5 up to 40 wt.%, preferably 94,5-60 wt.% the total weight of the binder.

The total content is 100%.

A mixture of (A1) and (B) grafted functional monomer. Examples of grafted monomers may be carboxylic acids and their derivatives, acid chlorides, isocyanates, oxazolines, epoxides, amines or hydroxides.

Examples of unsaturated carboxylic acids include acid containing 2-20 carbon atoms, such as acrylic, methacrylic, maleic, fumaric and taconova. Functional derivatives of these acids include, for example, anhydrides, ether derivatives, amide derivatives, kidnie derivatives and metal salts (in particular alkali metal salts) of unsaturated carboxylic acids.

Unsaturated dicarboxylic acids containing 4 to 10 carbon atoms and their functional derivatives, in particular their anhydrides, represent the FDS is th monomers, particularly preferably grafted. The most preferred maleic anhydride (MAN).

These grafted monomers include, for example, the following:

- acid: maleic, fumaric, taconova, citraconate, allylamino, cyclohex-4-ene-1,2-dicarboxylic, 4-methylcyclohex-4-ene-1,2-dicarboxylic, bicyclo(2,2,1)hept-5-ene-2,3-dicarboxylic, x-methylbicyclo(2,2,1)hept-5-ene-2,3-dicarboxylic;

- anhydrides: maleic, fumaric, takenby, citraconic, alliactively, cyclohex-4-ene-1,2-dicarboxylic, 4-metalenclosed-4-ene-1,2-dicarboxylic, bicyclo(2,2,1)hept-5-ene-2,3-dicarboxylic and x-methylbicyclo(2,2,1)hept-5-ene-2,2-dicarboxylic.

Examples of other grafted monomers include

- C1-C8alkalemia esters or derivatives glycidyloxy esters of unsaturated carboxylic acids such as methyl acrylate, methyl methacrylate, acrylate, methacrylate, butyl acrylate, butylmethacrylate, glycidylmethacrylate, glycidylmethacrylate, monoethylether, diethylmaleate, monomethylfumarate, dimethylfumarate, monomethylfumarate and diethylmalonate; amide derivatives of unsaturated carboxylic acids, such as acrylamide, methacrylamide, maleic monoamide, maleic diamide, maleic N-monoethylamine, maleic N,N-diethylamide, maleic N-monobutyltin, maleic N,N-dibutylamino, fumaric monoamide, fumaric diamide, fumaric N-MES is ethylamide, fumaric N,N-diethylamide, fumaric N-monomethylated and fumaric N,N-dibutylamino; kidnie derivatives of unsaturated carboxylic acids, such as maleimide, N-butylmalonic and N-phenylmaleimide, as well as salts of unsaturated carboxylic acids with metals, such as sodium acrylate, sodium methacrylate, potassium acrylate and potassium methacrylate.

There are various methods that can be used to develop grafted monomer to the mixture (A1) and ().

For example, the cultivation may be carried out by heating grafted polymers at elevated temperatures, of about 150-300°C), with or without the use of a solvent with or without initiator radicals. Solvents that can be used in this reaction are benzene, toluene, xylene, chlorobenzene and cumene. Apply appropriate initiators radicals include tert-butyl hydroperoxide, cumene hydroperoxide, diisopropylethylamine, peroxide, di-tert-butyl peroxide tert-butilkama, dicumylperoxide, 1,3-bis-(tert-butylperoxyisopropyl)benzene, acetyl peroxide, benzoyl peroxide, peroxide isobutyryl, peroxide, bis-3,5,5-trimethylhexanoyl, methyl ethyl ketone peroxide.

In the mixture, modified by grafting and obtained through the above, the amount of grafted monomer is chosen appropriately to obtain at the end of Pref is party or if necessary after dilution, the degree of graft polymerization of less than 0.5 wt.% the total weight of the binder, preferably more than 0.05% and less than 0.5%, more preferably less than 0.4% and even more preferably more than 0.10% and less than 0.4%.

The amount of grafted monomer is determined by performed by means of infrared spectroscopy quantitative analysis succinamic groups.

In addition, the binder according to the invention may contain various additives, including antioxidants, ultraviolet absorbers rays, antistatic agents, pigments, dyes, agents of formation of crystallization centers, fillers, slip agents, lubricants, flame-retardant materials and agents that prevent sticking.

Examples of antioxidants may be 2,6-di-tert-butyl-para-cresol, ortho-tert-butyl-para-cresol, tetrakis-[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, steam-naphtylamine and para-phenylenediamine.

Examples of absorbers of ultraviolet rays are 2,4-dihydroxybenzophenone, 2-(2'-hydroxy-3'5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3-tert-butyl-5-were)-5-chlorobenzotriazole and bis-(2,2',6,6'-tetramethyl-4-piperidine)sebacina.

Examples of antistatic agents are lauryldimethylamine, palmitoylethanolamide, stelldichein, allergically, running imdiately, polyoxyethylenated, steelmagnolias and 2-hydroxy-4-n-acetoxybenzoic.

Examples of dyes containing pigments and colorants are carbon black, titanium white, cadmium yellow, copper-phtalocyanine blue.

Examples of agents the formation of crystallization centers are para-tert-butylbenzoate aluminum, dibenzylideneacetone and hydroxy-di-para-tert-butylbenzoate aluminum.

Examples of fillers are glass fiber, fibers of carbon, talc, clay, silica, calcium carbonate, barium sulfate, magnesium hydroxide, calcium hydroxide and calcium oxide.

Examples of slip agents are stearic acid amide, oleamide and arotinoid.

Examples of lubricants include calcium stearate, zinc stearate, aluminum stearate, magnesium stearate, and polyethylene wax.

Examples of fire-retardant materials are antimony oxide, decabromobiphenyl simple ether and bis(3,5-dibromo-4-bromopropionitrile)sulfon.

Examples of agents for preventing adhesion are silicon dioxide and polystyrene.

Selection of the amount of other additives is carried out appropriately and should not have a negative impact on the binder according to the invention. For example, with regard to the total weight of (A1)+(C) number of relevant additives is: Antioch identi - 0.01 to 5 wt.%, absorbers of ultraviolet rays is 0.01-5 wt.%, the antistatic agents of 0.01-1 wt.%, the dye is 0.01-5 wt.%, agents of formation of crystallization centers of 0.01-5 wt.%, the filler is 0.1 to 60 wt.%, agents slip of 0.01-1 wt.%, the lubricant is 0.01-1 wt.%, fire-resistant materials is 0.01-50 wt.%, agents that prevent the adhesion of 0.01-30%.

The multilayer structure according to the present invention consists of a layer containing the above-mentioned binder, and a layer of oxygen-containing or nitrogen-containing polar resin or mineral oxide deposited on a polymer, such as polyethylene (PE), polyethylene terephthalate (PET), ethylene vinyl alcohol (EVOH) or the metal layer.

Preferred examples of the polar resin in the layer other than the layer of binder is polyamide resin, saponified copolymer of ethylene and vinyl acetate, polyesters, and epoxy resins.

In particular, they include synthetic polyamides with long-chain-containing structural units of aminogroup in the main chain, such as PA-6, PA-6,6, PA-6,10, PA-11 and PA-12; saponified copolymer of ethylene and vinyl acetate with a degree of saponification of about 90-100% mole., obtained by saponification of a copolymer of ethylene and vinyl acetate with ethylene content of about 15-60% mole.; polyesters such as polyethylene terephthalate, polybutylene terephthalate, polietilentereftalat (epoxy resin which is) and mixtures of these resins. Epoxy resins are used in the form of a powder or liquid.

The layer of mineral oxide may be represented, for example, silicon dioxide, while it is applied to the layer of polyethylene (PE), polyethylene terephthalate (PET) or ethylene vinyl alcohol (EVOH). The structure according to the invention includes, therefore, accordingly, a binder layer, a layer of SiO2(or SiOx), and a layer of polyethylene (PE), polyethylene terephthalate (PET), ethylene vinyl alcohol (EVOH)or the metal layer.

The metal layer may, for example, be represented by a sheet, a film or sheet metal, in particular aluminum, iron, copper, tin, Nickel or alloy containing as a main component at least one of these metals. The thickness of the film or sheet may be selected accordingly and be, for example, from 0.01 to 0.2 mm. In practice is usually done by degreasing the surface of the metal layer before application to him of the binder according to the invention.

Not is beyond the scope of the invention, when the above-mentioned structure will be connected to other layers. Preferred is a structure containing the following layers: metal/epoxy/binding/high-density polyethylene or medium-density polyethylene.

The invention also relates to the aforementioned article is ucture, attachable side of the binder to the layer (F), based on the polyolefin. The polyolefin (F) is a polyethylene of high (PEHD) or medium (PEMD) density of, preferably, high density polyethylene.

These structures are also used for the manufacture of packaging, such as a hard hollow housings, in particular bubbles, or bottles, or flexible tanks, as well as multilayer films. You can bring materials containing polyamide film (RA) and polyethylene film (PE), polyethylene film may be laminated on top of the polyamide film or coextrusion with polyamide. Connecting the extrusion is applied between the polyethylene and polyamide for better bonding of polyamide and polyethylene films. Data multilayer materials can be a three-layer polyethylene/binder/ethylene vinyl alcohol) structure, in which the ethylene vinyl alcohol copolymer is ethylene vinyl alcohol or a partially or completely saponified copolymer of ethylene and vinyl acetate (EVA), or five-layer structure of polyethylene/binder/ethylene vinyl alcohol/binder/PE).

Binders according to the invention are used in the following structures:

- polyethylene/binder/ethylene vinyl alcohol/binder/polyethylene;

- polyethylene/binder/ethylene vinyl alcohol;

- poly is tilen/binder/polyamide;

- polypropylene/ binder/polyamide;

- polypropylene/binder/ethylene vinyl alcohol/binder/polypropylene.

These structures and packing can be produced by the method of co-extrusion, lamination, extrusion, followed by blowing or powder coating of several types (electrostatic, powder-coated or hot, or preheat the base.

Hereinafter the invention will be demonstrated by examples.

Binder (examples 1-3 and comparative figures 1-3) were obtained as shown in the attached table 1.

Table 1
A1InA2Total percentage of grafted maleic anhydride
DensityMFI (190° under 2,16 kg)Total percentage
(by weight)
MFI (230° under 2,16 kg)Total percentage
(by weight)
DensityMFI (190° under 2,16 kg) Total percentage
(by weight)
Example 10,9542022,5%87,5%0,9534,570%0,20%
Example 20,9542012%73%0,9534,585%0,34%
Example 30,9544,398%72%---0,36%
Comparative data 10,95420was 12.75%8of 2.25%0,923,685%0,28%
Comparative data 20,916was 12.75%8of 2.25%0,9534,585%0,25%
Comparative data 30,9173,3was 12.75%8of 2.25%0,923,685%0,24%
MFI - melt flow index.

In example 1, comparative data 1, 2 and 3 homopolymers is ().

In example 2, example 3 (B) is a high impact copolymer polypropylene (PP).

For the formation of structures such as metal/epoxy/binding/high-density polyethylene steel pipe was coated with the following conditions:

Typical blasting:

- state surface Sa 21/2:

the surface roughness Rz of 70-80 microns

The heat pipe by induction: 180-220°C.

Application of basic epoxy resin (EUROKOTE 714-41) by electrostatic spraying.

The time of extrusion of the binder for epoxy the maul is 24 sec.

The time of bonding of the binder with the upper layer 30 sec.

The cooling of the top layer is 30 seconds.

The cooling water flow for 3 minutes epoxy resin to achieve complete crosslinking epoxy layer.

Extrusion of high density polyethylene on the binder.

EUROKOTE 714-41 is an epoxy resin with tg=105°C (as supplied by Société BITUMES SPECIAUX)that have the following characteristics:

- density at 23°C (NFT 30-043) - 1,5±0,05 g/ml;

- humidity (IBS 319) <0,50%

- particle size (IBS 316) average diameter of 38±4 microns with a denial of 96 μm <10%.

- tg (NFA 49-706) - 105±5°C

the hardening time of 25±10 sec at a temperature of 180°C and 9±3 seconds at a temperature of 220°C.

The thickness of the layers:

- layer epoxy - 110 µm;

the binder layer is 250 μm;

- outer layer (high density polyethylene) - 2.5 mm

Measurement of force used to remove the layer were performed in accordance with DIN 30670, and the summarized results are shown in the attached table 2.

Table 2
The power to delete layer
at a temperature of 23°C (N/cm)
The power to delete layer
at a temperature of 80°C (N/cm)
Example 1 Uninstallable164
Example 2Uninstallable161
Example 3Uninstallable182
Comparative data 122373
Comparative data 28714
Comparative data 324241

1. Binder co-extruded, containing a mixture of at least Homo - or copolymer of ethylene (A1)having a density of 0,940-0,980 g/cm3and at least one propylene copolymer (B)containing at least 51 wt.% propylene, and (co)polymers of the mixture together grafted functional monomer selected from carboxylic acids and their derivatives, and inoculated mixture, possibly diluted, at least in Homo - or copolymer grafting of ethylene (A2)having a density of 0,940-0,980 g/cm3while
- the degree of graft polymerization of this coextrusion binder is more than 0.05 wt.% and less than 0.5 wt.% the total weight of the specified binder;
the density of the specified binder is th is 0,940-0,980 g/cm 3.

2. A binder according to claim 1, characterized in that the degree of graft polymerization is more than 0.05 wt.% and less than 0.4 wt.% the total weight of the specified binder.

3. A binder according to claim 1 or 2, characterized in that the degree of graft polymerization is more than 0.10 wt.% and less than 0.4 wt.% the total weight of this binder.

4. A binder according to claim 1 or 2, characterized in that the density of (A1) and/or (A2) is 0,945-0,960 g/cm3.

5. A binder according to claim 1 or 2, characterized in that the density () is 0,860-0,920 g/cm3.

6. A binder according to claim 1 or 2, characterized in that (A1) and (A2) are the same polymers.

7. A binder according to claim 1 or 2, characterized in that it contains
- from 99.5 to 80% (A1), preferably from 99 to 90%;
from 0.5 to 20%, preferably from 0.5 to 10%;
- 0% (A2);
- percentages are expressed in weight% the total weight of this binder.

8. A binder according to claim 1 or 2, characterized in that it contains
- 5-60% (A1), preferably 5-40%;
- 0.5 to 20%, preferably 0.5 to 10%;
- 94,5% and 40% (A2), preferably 94,5-60%;
- percentages are expressed in weight% the total weight of this binder.

9. Multilayer structure designed for protection of metal surfaces and for the manufacture of packaging, rigid hollow housings, in particular vials or bottles, or flexible tanks, as well as multilayer films, with whom containing a series, at least one layer of the above-mentioned binder coextrusion, according to one of claims 1 to 8.

10. The structure according to claim 9, characterized in that it comprises the following successive layers: metal/epoxy resin/binder coextrusion/high density polyethylene (PEHD) or medium-density polyethylene (PEMD).

11. The use of coextrusion binder according to one of claims 1 to 8 in the multi-layer structure for protection of metal surfaces and for the manufacture of packaging, rigid hollow housings, in particular vials or bottles, or flexible tanks, as well as multilayer films.

12. The use of coextrusion binder containing at least a mixture of high density polyethylene (A1) and, at least, of the propylene copolymer (B)containing at least 51 wt.% propylene, and (co)polymers of the mixture together grafted functional monomer selected from carboxylic acids and their derivatives, and inoculated mixture, possibly diluted, at least in Homo - or copolymer grafting of ethylene (A2)having a density of 0,940-0,980 g/cm3while
- the degree of graft polymerization of this coextrusion binder is more than 0.05 wt.% and less than 0.5 wt.%, preferably from 0.15 to 0.4 wt.% the total weight of the specified binder;
the density of the specified binder is 0,940-0,980 g/cm3preferably 0,940 is 0.60 g/cm 3,
in multilayer structures containing the following successive layers: metal/epoxy resin/binder coextrusion/high density polyethylene (PEHD) or medium-density polyethylene (PEMD).

13. The application of item 12, wherein (C) is used ethylene-propylene rubber (EPR).



 

Same patents:

FIELD: polymer materials.

SUBSTANCE: mixture of graft copolymers useful as adhesion promoter contains following components: (i) ethylene/acrylic acid copolymer and/or ethylene/acrylic acid/acrylic acid terpolymer in amounts of 10 to 50% of the total weight of mixture; (ii) ethylene/α-olefin copolymer, 50-90 wt %; and (iii) ethylenically unsaturated dicarboxylic acids and/or anhydrides thereof, the latter being grafted to (i) and (ii) components. Mixture is prepared in single step. Laminated composite material comprises at least one layer consisting of above copolymer mixture and one or several layers selected from metal, plastic, glass, ceramics, and polymer materials. Invention makes it possible to prepare copolymer mixture containing minimum amount of grafted monomer.

EFFECT: increased adhesion strength in a wide temperature range and facilitated processing with simultaneous limited deformation relaxation and high resistance to formation of fatigue fractures.

9 cl, 2 tbl, 3 ex

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SUBSTANCE: present invention relates to the technology of modifiers production on the basis of nuclear-shell type particles used for production of molding such as films, pipes, mirror housings etc. from poly(meth)acrylates. The nuclear-shell type particle consists of a nucleus, the first shell and, if required, the second shell that on every single case consist of alkylmetacrylate and styrene recurring units with minimum glass-transition temperature of 30°C. The said particles are produced by multistage emulsion polymerisation.

EFFECT: invention ensures implementation of the process with minimum labour costs and small investments for commercial deployment.

15 cl, 2 tbl

FIELD: organic chemistry, polymers.

SUBSTANCE: invention relates to polymers additives for lubricant oils improving viscosity index and representing dispersers. Disperser-additive improving viscosity index is prepared by a method involving grafting in solution on hydrocarbon polymer prepared from at least one (C2-C28)-polymerizing hydrocarbon wherein abovementioned polymer has an average molecular mass value in the range from about 5000 Da to about 500000Da, compounds of ethylene-unsaturated type comprising from 3 to 10 carbon atoms and at least one group of carboxylic acid or anhydride group, or nitrogen-containing monomer of ethylene-unsaturated type comprising from 6 to 30 carbon atoms and from 1 to 4 nitrogen atoms and with using free-radical initiator wherein the process is carried out in the presence of ester as oil corresponding to the formula: wherein R1, R2, R3, R4, R5 and R6 are chosen independently from the group consisting of hydrogen atom, -COOR7, -COOR8, -COOR9, -COOR10, -COOR11 and -COOR12 under condition that 5 radicals (not above) among R1, R2, R3, R4, R5 and R6 represent hydrogen atom, and R7, R8, R9, R10, R11 and R12 are chosen independently from the group consisting of alkyl and alkyl esters. Disperser-additive improved viscosity index of lubricant oils and elicits dispersing capacity providing suspending sediment that can form in the process of exploitation or using lubricant and prevents carbon formation in engines. Method shows the improved qualities in grafting in solution of unsaturated fragments on hydrocarbon polymer by carrying out the grafting reaction in solution medium containing at least one aromatic ester.

EFFECT: improved preparing method, valuable technical properties of additive.

20 cl, 4 tbl, 4 ex

FIELD: polymer production.

SUBSTANCE: in the first step of two-step polymer-polyol preparation, polyether, notably Laprol 5003 or Laprol 5003/Laprol 3003 mixture, is combined with polymer selected from group, including polystyrene, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, acrylonitrile-butadiene-styrene plastic, and mixtures thereof, at temperature 100°C. In the second step, at 90°C and pressure 0.2 MPa, monomer selected from group including acrylonitrile, styrene, acrylate, vinylidene chloride, and mixtures thereof is added before addition of catalyst. Resulting mixture is stirred at 100-110°C and pressure 0.25 MPa.

EFFECT: enabled preparation of stable dispersion, reduced process cycle time, and lowered power consumption.

2 cl, 2 tbl, 5 ex

FIELD: polymers, in particular composition for molded articles useful in building materials.

SUBSTANCE: claimed composition contains (A) 100 mass pts of vinyl chloride-based resin; (B) from 1 to 30 mass pts of graft copolymer obtained by graft polymerization; (C) from 0.1 to 5 mass pts of methylmethacrylate-based polymer obtained by two-step method in presence of polymer, wherein 0.1 g of said polymer in 100 ml of chloroform has intrinsic viscosity (ηsp) at 30°C of 0.7 or more and contains 0-50 mass % of methylmethacrylate repeated units, and 0.1 g of in two step obtained polymer in 100 ml of chloroform has intrinsic viscosity (ηsp) at 30°C of 0.5 or more; and (D) from 1 to 20 mass pts of calcium carbonate.

EFFECT: articles with high processibility, whether resistance, impact resistance and luster.

5 cl, 19 ex, 3 tbl

FIELD: polymer materials.

SUBSTANCE: composition comprises polyolefin A, containing anhydride function and having viscosity at least 20 g/10 min measured at 190°C and loading 2,16 kg, and epoxy function-containing product B destined for cross-linking polyolefin A. Relative proportions of A and B are such that for each epoxy function there are from 0.1 to 1.5 anhydride functions. Composition can be used in slush molding process, in thermal molding of sheets, or in on-rod casting process.

EFFECT: increased flowability resistance and wear resistance.

6 cl, 1 tbl, 6 ex

The invention relates to polymeric compositions and method of slow depolymerization

Polymer composition // 2171821
The invention relates to compositions containing graft copolymers of polypropylene, polycarbonate, aliphatic polyester and, optionally, a rubber component and/or polypropylene

The invention relates to compositions comprising graft copolymers, which include polystyrene grafted to the main chain or the basis of polypropylene, and in particular, this invention relates to compositions based on graft copolymers having a heterogeneous morphology, characterized in that the polypropylene is a continuous phase, and the polystyrene dispersed phase

Polymer composition // 2088614
The invention relates to polymeric compositions based on thermoplastic elastomer grafted copolymer of vinyl chloride (I) a copolymer of ethylene-vinyl acetate (EVA) for medical products that do not contain low molecular weight plasticizer, characterized by increased flexibility, transparency, resistance to various types of sterilization

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

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