Composition based on halogenated thermoplastic polymers and its method of preparation and use

FIELD: polymer materials.

SUBSTANCE: invention provides polymer composition containing one or several halogenated thermoplastic polymers and being characterized by RMFI between 1.1 and 6, where RMFI is ratio of melt flow indexes MFI8/2 and MFI0.3/1 measured in accordance with standard ASTM D1238. Invention also discloses preparation method and use for these compositions.

EFFECT: enabled preparation of compositions exhibiting a rheological property (stretching viscosity), which is characterized by elevated resistance to deformation during foaming.

14 cl, 2 dwg, 3 tbl, 8 ex

 

The invention relates to compositions based on halogenated thermoplastic polymers, method of production thereof, their use for the production of films, sheet materials, slabs, foam shells, pipes, foams, bottles or termoformovannyh and/or cast products and the application of foam shells for covering electrical cables.

In many cases, the possible use of halogenated thermoplastic polymers, in particular fluorinated thermoplastic polymers, it is necessary that these polymers were characterized by the ability to harden under tension in the molten state. Such applications can be called using foam shells for covering electrical cables.

However, most of halogenated thermoplastic polymers, in particular fluorinated thermoplastic polymers, does not possess this property to harden under tension in the molten state.

The object of the present invention are compositions based on halogenated thermoplastic polymers that do not have the above disadvantages.

The object of the present invention is also a method of obtaining such compositions.

The object of the present invention is also the use of such compositions for the production of films, sheets, plates, in peninnah shells, pipes, foams, bottles or termoformovannyh and/or cast products.

Finally, an object of the present invention is the use of foam shells for covering electrical cables.

To this end, the invention relates to compositions based on halogenated thermoplastic polymer, characterized in that the value of RMFI is from 1.1 to 6.

Under halogenated compositions of thermoplastic polymers according to the present invention involve compositions based on one or more halogenated thermoplastic polymers. Preferably the compositions according to the invention contain one halogenated thermoplastic polymer.

Under RMFI according to the present invention involve the relationship between two values of melt flow index MFI, measured at the same temperature, as described below, namely the relationship between MFI8/2obtained by using a cylindrical die (height 8 mm +/- 0,025 diameter 2,095 mm +/- 0.003) and MFI0,3/1obtained through a conical die. Conical filler characterized by a cone angle of 60° +/- 0.5V, external diameter equal 9,48 mm, an inner diameter of 1.0 mm +/- 0,025 total height equal to 2.55 mm +/- 0,025, and a height of cylindrical cross-section, equal to 0.3 mm +/- 0,025.

Both the MFI values obtained by measurement in accordance with article what hartom ASTM D1238 amount of polymer, passing through a calibrated die plate, the characteristics of which are described above, under a load of 10 kg, and at the same temperature. Temperature measurements are usually higher by at least 20°With than the melting temperature of the halogenated thermoplastic polymer, if the composition contains one halogenated thermoplastic polymer, it is higher by at least 20°With than the melting temperature of the halogenated thermoplastic polymer having the highest melting temperature, if the composition contains several halogenated thermoplastic polymers. The MFI values are expressed in g/10 minutes

The RMFI value indicates the degree of branching of the polymer in the compositions according to the invention. The RMFI value from 1.1 to 6.0 usually corresponds to a low, but not zero degree of branching.

Compositions according to the invention are usually characterized by the RMFI value above 1.1, preferably greater than or equal to 1.2, most preferably less than or equal to 1.3.

Compositions according to the invention are usually characterized by the RMFI value below 6, preferably below or equal to 5.5, most preferably less than or equal to 5.

Compositions according to the invention are generally characterized by the content of insoluble fractions of polymers (FI) less than or equal to 20 weight %, preferably less than or equal to 15 weight and most preferably less than or equal to 5 weight %.

Under the content of insoluble fractions of polymers (FI) according to the present invention involve the content of the polymer, insoluble in dimethylformamide (DMF). Insoluble substance produce by centrifugation after dissolution of the sample by boiling under reflux in DMF.

According to the applicable method 1 g of polymer is refluxed (in terms of shaking) for 30 min in 20 ml of DMF. The contents are cooled at room temperature, then centrifuged speed 27000 rpm for 3 hours. Located on the surface fraction is filtered in the filter crucible. Undissolved fraction is washed with the use of DMF at room temperature. Then it is centrifuged again under the same conditions and the surface fraction is filtered using the same filter crucible. After another wash using DMF undissolved substances from the bucket centrifuge and the crucible was dispersed in methanol to remove residual DMF. Undissolved substances in the last centrifuged under these conditions (27000 rpm for 1 hour), and then dried to constant weight at 60°on a heating plate, and then under vacuum (about 10 NDA). When applying this technology, the minimum quantitative content of the undissolved fraction of the costs is t 1%.

Compositions according to the invention mainly have the property of hardening under tension in the molten state, characterized by an exponential increase in viscosity tensile depending on the time.

Under viscosity tensile imply such a viscosity, which is determined by using a rheometer with a gradient of strain equal to 1-1on the sample obtained by extrusion, and which were subjected to relaxation for stress relief before making measurements. The temperature at which carry out measurements tend to be higher by at least 20°With than the melting temperature of the halogenated thermoplastic polymer, if the composition contains one halogenated thermoplastic polymer, it is higher by at least 20°With than the melting temperature of the halogenated thermoplastic polymer having the highest melting temperature, if the composition contains several halogenated thermoplastic polymers.

In addition, compositions according to the invention are characterized generally by the fact that the inflection point of the curve corresponding to the exponential increase in viscosity tensile depending on the time usually corresponds to less than 3 seconds, preferably less than 2 seconds.

Compositions based on halogenated t is moplastic polymers also typically characterized by a quasi-linear relationship (no Newtonian plateau) between the dynamic viscosity and the frequency of deformation when building a logarithmic graph.

Dynamic viscosity is usually measured in the range from 0.1 to 100 rad/sec using Reaganomics forced deformation of the sample with a diameter of 25 mm and a thickness of 2 mm, cut from the molded plate positioned between two parallel plates and subjected to periodic deformation. Temperature measurements are usually higher by at least 20°With than the melting temperature of the halogenated thermoplastic polymer, if the composition contains one halogenated thermoplastic polymer, it is higher by at least 20°With than the melting temperature of the halogenated thermoplastic polymer having the highest melting temperature, if the composition contains several halogenated thermoplastic polymers.

Under thermoplastic polymers mean according to the present invention the polymers, which at room temperature have their glass transition temperature, if they are amorphous, or between its glass transition temperature and its melting temperature, if they are crystalline. These polymers can soften when heated and re-harden when cooled without significant chemical change. Such determination may, for example, be found in the encyclopedia "Polymer Science Dictionary", Second Edition, Mark Alger, School of Polymer Technology, University of North Londo, London, UK, Chapman & Hall Edition, 1997.

Under halogenated polymers according to the present invention involve as homopolymers and copolymers and terpolymer halogenated monomers. Of them can be called, in particular, homopolymers of halogenated monomers, such as vinylidenefluoride, viniferin, triptorelin, chlorotrifluoroethylene, vinyl chloride, vinylidenechloride; copolymers and terpolymer, which is formed such halogenated monomers; copolymers and terpolymer at least one of the above halogenated monomers with at least one fluorinated monomer that does not contain hydrogen atoms, such as tetrafluoroethylene and HEXAFLUOROPROPYLENE; copolymers and terpolymer formed by at least one of the above halogenated monomers with at least one other monomer with ethylene communication, such as olefins, for example ethylene and propylene; styrene and styrene derivatives, simple vinyl ethers; complex vinyl esters such as vinyl acetate; acrylic esters, NITRILES and amides, methacrylic esters, NITRILES and amides.

Halogenated thermoplastic polymers according to the invention are preferably fluorinated thermoplastic polymers.

Under the fluorinated polymers according to the present invention mean is how the homopolymers, and copolymers and terpolymer fluorinated monomers. Of them can be called, in particular, homopolymers of vinylidenefluoride, winifrida, triptorelin or chlorotrifluoroethylene, copolymers and terpolymer, which is formed such fluorinated monomers or in addition to them, at least one other fluorinated monomer not containing a hydrogen atom such as tetrafluoroethylene and HEXAFLUOROPROPYLENE, such as copolymers and terpolymers of vinylidenefluoride with at least one other fluorinated monomer (including those that do not contain hydrogen atoms), as described above, and copolymers and terpolymer of chlorotrifluoroethylene with at least one other fluorinated monomer (including those which do not contain hydrogen atoms), as described above. Can also be referred to as copolymers and terpolymer at least one of fluorinated monomers mentioned above, with at least one other monomer with ethylene bond, for example olefins such as ethylene and propylene; styrene and styrene derivatives; chlorinated monomers such as vinyl chloride and vinylidenechloride; simple vinyl ethers; complex vinyl esters such as vinyl acetate; acrylic esters, NITRILES and amides, methacrylic esters, NITRILES and amides.

Halogenated thermoplastic polymers and according to the finding is most preferably selected from thermoplastic polymers vinylidenefluoride and thermoplastic polymers chlorotrifluoroethylene.

Under the polymers of vinylidenefluoride according to the present invention involve as homopolymers of vinylidenefluoride and its copolymers and terpolymers with other monomers with ethylene communication, regardless of whether they are fluorinated (viniferin, triptorelin, tetrafluoroethylene, chlorotrifluoroethylene, HEXAFLUOROPROPYLENE) or not (olefins, such as ethylene and propylene; styrene and styrene derivatives; chlorinated monomers such as vinyl chloride and vinylidenechloride; simple vinyl ethers; complex vinyl esters such as vinyl acetate; acrylic esters, NITRILES and amides, methacrylic esters, NITRILES and amides). Preferably the copolymers and terpolymers contain at least 50 weight % of monomer units derived vinylidenefluoride.

Under the polymers of chlorotrifluoroethylene according to the present invention involve as homopolymers of chlorotrifluoroethylene and its copolymers and terpolymers with other monomers having ethylene communication, regardless of whether they are fluorinated (vinylidenefluoride, viniferin, triptorelin, tetrafluoroethylene, HEXAFLUOROPROPYLENE) or not (olefins, such as ethylene and propylene; styrene and styrene derivatives; chlorinated monomers such as vinyl chloride and vinylidenechloride; simple vinyl ethers; complex vinyl the new esters, such as vinyl acetate; acrylic esters, NITRILES and amides, methacrylic esters, NITRILES and amides). Preferably the copolymers contain at least about 50 weight percent of monomer units derived of chlorotrifluoroethylene.

Halogenated thermoplastic polymers according to the invention most preferably are thermoplastic polymers of vinylidenefluoride.

Halogenated thermoplastic polymers according to the invention mainly selected from homopolymers of vinylidenefluoride and copolymers and terpolymers of vinylidenefluoride with at least one other fluorinated monomer.

Compositions according to the invention can additionally contain one or more additives usual for halogenated thermoplastic polymers, in particular fluorinated polymers, such as traps acid, lubricating agents, organic or mineral dyes, salt, fillers, stabilizers and flame retardant agents.

Compositions according to the invention can be obtained in any way. Good results obtaining compositions by the method according to the invention.

The invention relates also to a method for producing compositions based on halogenated thermoplastic polymer, which is that in the molten mass in extrude the e interact one or more halogenated thermoplastic polymer with an initiator radicals and agent education bridge connection (cross-stitch) and output a received composition from the extruder.

Determination of halogenated thermoplastic polymers given above, and they are preferably fluorinated thermoplastic polymers.

Preferably the method according to the invention lies in the fact that interact in the molten mass in the extruder halogenated thermoplastic polymer with an initiator radicals and agent education bridge connection.

Hereinafter, the terms "halogenated thermoplastic polymers and fluorinated thermoplastic polymers for the purposes of the present invention are used as in the plural and in the singular.

In the method according to the invention, the initiator radicals are usually used in a quantity sufficient to effect the interaction between cross-linking agent and a halogenated thermoplastic polymers. The amount of initiator radicals is from 0.5 to 10 g/kg halogenated thermoplastic polymers.

The amount of initiator radicals is at least 0.5, and preferably 0.75 and most preferably at least 1 g/kg halogenated thermoplastic polymers.

Number generator radicals maximum equal to 10, most preferably equal to 9 and most preferably maximally equal to 8 g/kg halogenated thermoplastic who polymers.

As a generator of radicals preferably used an organic peroxide, and more specifically alkylperoxide. Of them can be called peroxide tertbutylamine, 1,3-di(2-tert-butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5-di(tert-BUTYLPEROXY)hexane, di(tert-butyl)peroxide and 2,5-dimethyl-2,5-di(tert-BUTYLPEROXY)-3-hexyne. Most preferred is 2,5-dimethyl-2,5-di-tert-butylperoxide.

In the method according to the invention, the agent education bridge connection is usually used in a quantity sufficient to provide branching halogenated thermoplastic polymer. The number of agent education bridge connection is from 0.5 to 50 g/kg halogenated thermoplastic polymers.

The number of agent education bridge connection at least equal to 0.5, preferably at least equal to 2 and most preferably at least 2.5 g/kg halogenated thermoplastic polymers.

The amount of crosslinking agent is maximally equal to 50, most preferably equal to 40 and most preferably maximally equal to 30 g/kg halogenated thermoplastic polymers.

In the method according to the invention, the agent education bridge connection is usually chosen from the functional compounds containing at least two groups selected from vinyl ties, lilovyh relations and carboxyl, amine, a silanol hydroxyl and epoxy groups. Agent education bridge connection is preferably selected from the group consisting of triallylisocyanurate, divinylbenzene, VINYLTRIMETHOXYSILANE and allyltriethoxysilane. Triallylisocyanurate is the most preferred.

Initiator radicals and agent education bridge connection, you can enter in any way, ensuring continuity of their input and good distribution in the molten substance. Initiator radicals and agent education bridge connection, you can enter by dispersing, for example, using an injector-type spray or spray or by injection into the molten mass. You can also enter the initiator radicals and agent education bridge connection comprising masterbatches (masterbatch) together with a halogenated thermoplastic polymers in powder state or in a part of masterbatches with filler.

In accordance with a preferred embodiment of the invention, the initiator radicals and agent education bridge connection is introduced into the extruder in the mixture with carbon dioxide. With this purpose you can use any device, which serves to obtain a mixture of initiator radicals or agent education bridge connection with carbon dioxide and putting the mixture in the extruder.

In soo is according to the preferred embodiment of the invention, the agent education bridge connection introduced earlier, than the initiator radicals.

Under the interaction of a molten mass according to the present invention involve any interaction, performed almost in the absence of a solvent or diluent and at a temperature at least equal to the melting temperature halogenated thermoplastic polymers.

Under the extruder imply any known device consisting of at least one of the load and the output from the same output, which is the area of compression, where the molten mass push for passage through the zone output. In addition, the zone output can be granulator or device, which serves to give an extrudable material its final form. Mostly use known extruders, which are based on two augers, regardless of whether they rotate in the same or in opposite directions, or extruders type BUSS.

Mainly the extruder used according to the present invention, sequentially consists of a loading zone, zone melting substances, the homogenization zone, the reaction zone, optional fields additives and compression zones / o, which is the degassing zone. Each of these zones has a specific function and a specific temperature.

The download area provides the ability to download galogenirovannami thermoplastic polymer. The temperature in this zone is usually less than or equal to 50°C.

Zone melting substances ensures the melting of the substance.

Area homogenization ensures homogenization of the molten substance.

The reaction zone ensures the implementation of the response.

The temperature in the melting zone and in the zone homogenization of the substance is usually higher than or equal to the melting temperature halogenated thermoplastic polymers.

The temperature in the reaction zone is usually higher than or equal to the temperature at which the half-life of the initiator radicals is less than the period of the substance in this area.

The zone of injection of additives provides input additives, if any, is introduced into the extruder. The temperature in this zone is usually dependent on the viscosity of the substance and nature of the introduced additives.

Area of compression / o provides compression of matter and its conclusion. The temperature in the zone of compression / o usually depends on the viscosity of the output substance.

Agent education bridge connection is preferably introduced into the extruder before homogenization.

Initiator radicals is preferably introduced into the reaction zone of the extruder.

In the process of implementing the method, you can enter one or more additives usual for halogenated thermoplastic polymers, in particular fluorinated thermoplastic polymers, such as traps acid, smash the interacting agents, organic or mineral dyes, salt, fillers, stabilizers and flame retardant agents. One or more of such additives can be introduced into the extruder or in the composition after their withdrawal from the extruder.

The present invention also concerns the use of the compositions according to the invention for the production of films, sheet materials, slabs, foam shells, pipes, foams, bottles or termoformovannyh and/or cast products.

The invention also applies to films obtained from the compositions according to the invention.

The invention concerns also sheet materials obtained from the compositions according to the invention.

The invention also concerns the plates obtained from the compositions according to the invention.

The invention also concerns a foam shells obtained from the compositions according to the invention.

The invention also applies to pipes produced from compositions according to the invention.

The invention also concerns the foams obtained from the compositions according to the invention.

The invention also concerns the bottles obtained from the compositions according to the invention.

The invention also concerns termoformovannyh and/or molded products obtained from the compositions according to the invention.

The invention also concerns the application of the expandable membranes obtained from the compositions according to the invention for coating elektricheskij cables.

Compositions based on halogenated thermoplastic polymers, in particular fluorinated thermoplastic polymers according to the invention, therefore, are those that are predominantly of a rheological property (viscosity tensile), which is characterized by high deformation resistance at the time of foaming, thanks to the way the foam is very stable, and in this way we obtain a foamed shell, characterized by a homogeneous distribution of closed regular cells, very low variation in cell size and the formation of a continuous film having no surface defects caused by the presence of open cells.

Compositions according to the invention are distinguished, in addition, the low content of insoluble fractions of the polymers, making the resulting products have little or no very small number of heterogeneous sites.

The following examples illustrate the present invention without limiting its scope.

Halogenated thermoplastic polymer

As a halogenated thermoplastic polymer used is a copolymer of vinylidene of chlorotrifluoroethylene manufactured by SOLVAY under the name SOLEF® 31508.

Initiator radicals

As an initiator radicals used 2,5-dimethyl-2,5-d is-tert-butylperoxide (DHBP), produced by PEROXIDE CHEMIE, brand LUPERSOL® 101.

Agent education bridge connection

As agent for the formation of bridging ties were used triallylisocyanurate (TAIC), stabilized with 100 ppm of 2,6-di-tert-butyl-4-METHYLPHENOL manufactured by ACROS.

Extruder to obtain compositions

To obtain compositions used extruder CLEXTRAL model SU 21 with two screws rotating in the same direction. The screw diameter of 25 mm, an Inner case, a size of 900 mm (L/D=36) with a double cylinder, consists of 9 independent zones, as well as from the nozzles and dies.

Used the following temperature profile:

The feed area: 50°

Zone 2: 150°

Zone 3: 190°C (melting zone)

Zone 4: 190° (zone homogenization)

Zones 5 and 6: 190°With (reaction zone)

Area 7: 190° (zone degassing)

Area 8 and 9: 200°With (compression zones / o)

Attachment: 210°

Filler: 210°

Agent education bridge connection was introduced in zone 3, and the initiator radicals in zone 5.

The input device (initiator radicals and agent education bridge connection

The device used for input of initiator radicals in a mixture with carbon dioxide and to enter agent education bridge connection in a mixture with carbon dioxide, are described in detail below.

DBHP kept in the tank, Padova is in a mixer with pump. Liquid carbon dioxide stored in the container, cooled to -10°in createremote before you enter it using the pump to the mixer. The mixture DBHP and carbon dioxide obtained in the mixer, and then introduced into the injector, in which pressure was increased by using a pressure sensor.

The tank containing liquid carbon dioxide, were under the pressure of carbon dioxide.

Used two pump type GILSON 806. The upper part of the pump used to supply carbon dioxide, with the head 10SC and thermostat 10SC GILSON, which provides cooling head down to -10°C. as the coolant used isopropanol, cooled in createremote type JULABO F30.

The same criteriathat used for cooling the liquid carbon dioxide.

Used analytical type mixer GILSON 811C, equipped with a screw.

Used injector, used to work in conditions of high pressure (above 74 bar).

Pressure sensor type GILSON 806 is positioned between the pump carbon dioxide and mixer in order to measure the pressure in the injector (from 90 to 120 bar).

Same setting used for filing agent education bridge connection.

The head of the pump TAIC and the tube was heated to 35°in order to prevent crystallization reagent. Used device is in JULABO FP50, ethylene glycol (eg. Carbon dioxide was mixed with TAIC using a static mixer type ASI STATIC MIXER adapted to small expense.

The injector feed device was installed perpendicular to the inner casing of the extruder and was tangentially with respect to the thread of the screw of the extruder.

Characteristics of the compositions

For characterization of the obtained compositions was carried out:

measurement of MFI to determine RMFI,

measuring the rheology tensile (RME) to determine the viscosity tensile,

measurement of dynamic rheology (RDS) to determine the viscoelastic properties (dynamic viscosity, tan δ) depending on frequency,

measurement of the content of insoluble fractions of polymers (FI).

Definition RMFI

The RMFI value is obtained by calculating the ratio between the two MFI, measured at the same temperature, as described below, namely the relationship between MFI8/2obtained by using a cylindrical die (height 8 mm +/- 0,025 diameter 2,095 mm +/- 0,003), and MFI0,3/1obtained through a conical die. Conical filler characterized by a cone angle of 60° +/- 0.5V, external diameter equal 9,48 mm, an inner diameter of 1.0 mm +/- 0,025 total height equal to 2.55 mm +/- 0,025, and a height of cylindrical cross-section, equal to 0.3 mm +/- 0,025.

The value of both MFI on ucaut by measurement in accordance with ASTM D1238 amount of polymer, passing through each calibrated die plate described above, this value is expressed in g/10 minutes

To measure MFI used a device (Melt Indexer) CEAST type 6542/000. It mainly consists of, on the one hand, of a steel cylinder, the bottom of which is calibrated filler, and on the other side of the piston, on which you can set a different mass. The measurements were carried out in relation to the polymer PVDF SOLEF® 31508 at 230°s, when the load of the node of the piston-mass, equal to 10 kg

Measurement of rheology tensile (RME)

Rheometrics measuring tensile carried out using a rheometer manufactured by Rheometrics called RME. This analysis allowed us to quantify the curing tensile polymer in the molten state, exploring its properties when it is stretched in the molten state. To this end, first to extrudible the polymer sample. The deformation of the sample was recorded at fixed temperature (230° (C) and strain rate (1-1).

The measurement result (chart RME) was reflected in the change in 230 °viscosity under tension in the molten state (expressed in kPa· (C) depending on time (expressed in s) for the gradient of the strain (expressed in-1), is equal to 1.

Measurement of dynamic rheology (RDS)

The measurement is dinamicheskoi rheology was performed using reagonomics forced deformation, manufactured by Rheometrics called Advanced Rheological Expansion System (ARES). This technique allowed to determine the viscoelastic properties of shear deformation of the polymer in the molten state.

Viscoelastic properties (elastic modulus G', the module loss, G", tan δ (the ratio G"/G') and dynamic viscosity η) was determined on samples with a diameter of 25 mm and a thickness of about 2 mm pressed plates in geometry, a plane-plane. Periodic shear deformation was carried out by moving the lower plate, while the upper plate was fitted with sensors torque and force "normal". Test specimens were prepared at a constant temperature (230 ° (C) and the frequency of deformation from 0.1 to 100 rad/sec.

The measurement result is expressed as a change in 230 °dynamic viscosity, expressed in PA·with or modules G' and G", expressed in PA, depending on the frequency expressed in rad/sec.

Measurement of the content of insoluble fractions of polymers (FI)

The method consists in determining the content of insoluble fractions of the polymer in dimethylformamide (DME). The insoluble substance was removed by centrifugation after dissolution of the sample by boiling under reflux in DME. The technique has been described above. Marginal quantitative value for this method is 1 weight %.

The extruder used for the floor is to be placed foam shells

Foam shell were obtained using the extruder of the type Nokia-Maillefer Sel 30, single screw extruder with a diameter D=30 mm and length L=25D; used the die plate, which made it possible to obtain a hollow shell.

The auger profile consisted of the transmission members and provided a compression ratio equal to 3 (15D-3D-7D).

Used the following temperature profile:

The zone: 10 °

Zone 1: 185 °

Zone 2: 195 °C (melting zone)

Zone 3: 205 ° (zone homogenization)

Zone 4: 215 °With (reaction zone)

Attachment: 220 °

Filler: 220 °

Screw rotation speed was 77 rpm Speed of the extrusion product was 12 m/min

The pore-forming

As pore-forming substance used an endothermic blowing agent, releasing carbon dioxide at a temperature of from 135 to 284 °C.

Feature foam shells

The obtained foamed shell are characterized by:

its density,

mechanical properties,

dielectric properties

microscopy microcosmically slices.

Measuring density foam shells

Measuring density foam shells were carried out using the method based on the Archimedes ' principle. The sample foamed shell weighed in air, was placed on a boat (nacelle) and immersed in water, the temperature of which b is La constant. Weight of boat + the sample was pushed by the water, which made it possible to determine the density by Archimedes ' principle (by subtracting the mass of the boat).

Underwater weighing was carried out immediately after the dive. Before you weigh in the water, removed the air bubbles appearing on the internal and external surfaces.

The mechanical properties of the foam shells

The elongation at break and tearing voltage foam membranes was determined at room temperature (23 °C) and 50% relative humidity according to ASTM D1238. Stretch speed was 50 mm/min, and the distance between the clamps - 50 mm extensometer was set at 25 mm Used the device INSTRON 4301. It is equipped with flat clamps G29 and extensometer LONG TRAVEL EL1. The power element of the brand 1kN fl/995.

Dielectric properties of foam shells

The external surface of the foam shells were covered with adhesive copper sheet. He served as an external electrode. As an internal electrode used metal harness, inserted into the foam shell.

As a measuring bridge used the bridge WAYNE KERR Precision Compound Analysis 6425. With his help, at a given frequency was measured capacitance and loss tangent (tan δ). The dielectric constant (ε) was calculated on the basis of these two quantities and sizes of the foam shell. And the intent was carried out at room temperature (27 ° C).

Microscopy microcosmically slices of foam shells

Samples of foam shells were placed on a metal support, the temperature was lowered to -20 °C. Then dripping water, which had turned to ice around the shell. This allowed us to make samples sufficiently stiff so they can be cut (in the longitudinal and transverse directions) into thin strips with a thickness of 35 microns.

Using a microscope WILD MACROSCOP M420 camera TOSHIBA 3 CCD and printer HEWLET PACKARD Deskjet 890C got a picture of these ribbons with a 50-fold magnification. It is possible to obtain a photograph with the above increase.

Examples 1-2 (comparative)examples 3-4 (according to the invention)

Halogenated polymer SOLEF®31508 introduced into the feeding zone of the extruder described above (extruder to obtain compositions) with a flow rate of 8 kg/h, and skipped through the various zones of the extruder.

DHBP in a mixture with carbon dioxide and TAIC in a mixture with carbon dioxide caused by dispersion on halogenated polymer using the above-described device for input. Dose TAIC and DHBP, expressed in g/kg halogenated polymer SOLEF®31508 introduced into the extruder, respectively, in zone 3 and zone 5, are listed in table 1 for each of examples 1 to 4.

Table 1: the eskers TAIC and DHBP
TAICDHBP
Example 1 (compare.)00
Example 2 (compare.)03
Example 343
Example 452,5

Values RMFI, the content of insoluble fractions of polymers (FI), and the values of tan δ at 0.1 rad with-1measured in respect of the compositions shown in table 2.

Table 2
RMFIFItan δ when

0,1 happy with-1
Example 1 (comparative)10with 3.27
Example 2 (comparative)102,61
Example 343,30,73
Example 4the 4.74Not

defined

The viscosity tensile (expressed in kPa· (C) at 230 °depending on the time (expressed in s) for the gradient of the strain (expressed in-1), is equal to 1, as shown in figure 1 for the compositions according to example 1 (symbol 0), according to example 2 (the symbol ⋄), according to the but example 3 (the symbol and according to example 4 (+).

The change in dynamic viscosity (expressed in kPa· (C) at 230 °depending on the time (expressed in s) for the gradient of the strain (expressed in-1), is equal to 1, as shown in figure 2 for the compositions according to example 1 (symbol 0), according to example 2 (the symbol ⋄)according to example 3 (the symbol).

Examples 5 and 6 (comparative)

Compositions according to examples 1 and 2 are then used for extrusion foaming. To this end, the foaming agent described above, were introduced into the compositions according to examples 1 and 2 at the rate of 1.5 weight % to their passage through the extruder described above (extruder to obtain a foam shells).

It was not possible to obtain foamed sheath by extrusion foaming compositions according to examples 1 and 2.

Examples 7 and 8 (according to the invention)

Compositions according to examples 3 and 4 are then used for extrusion foaming. To this end, the foaming agent described above, were introduced into the compositions according to examples 3 and 4 at the rate of 1.5 weight % to their passage through the extruder described above (extruder to obtain a foam shells).

Thus was obtained a flexible, hollow, high-quality foam shell with an inner diameter of 3 mm, and a thickness of 0.5 is m The foaming process was stable.

Values of density, elongation at break, stress at break, the dielectric constant (ε) and loss tangent (tan δ) at 100 kHz, measured on foam shells obtained from the compositions according to example 3 (example 7) and according to example 4 (example 8), are shown in table 3.

The study by microscopy microcosmically slices of foam shells clearly showed that the obtained foamed shell high quality, characterized by the presence of a closed, regular cells of small size, uniformly distributed, only a few large cell size and the complete absence of surface defects.

Table 3
Density g/cmRasteenie at break %Destructive voltage of

MPa
Dielectric conductivity at 100 kHztan δ at 100 kHz
Example 71,062549,640,05
Example 81,0036011,13,10,046

From the analysis of table 2 that the compositions according to the invention the characteristics of eresource greater magnitude of RMFI, than compositions known from the prior art, and very low fractions of insoluble polymers.

Compositions according to the invention are distinguished, in addition, the smaller value of tan δthan compositions known from the prior art. When considering Fig. 1 it becomes apparent that the compositions according to the invention are distinguished, in addition, an exponential increase in viscosity tensile depending on the time characteristic of the structural hardening in tension, in contrast to the compositions known from the prior art.

In addition, the inflection point corresponding to the exponential increase in viscosity tensile depending on time less than 3 seconds in contrast to the compositions known from the prior art.

When considering Fig. 2 (logarithmic plot) it becomes apparent that the compositions according to the invention differ almost linear relationship between dynamic viscosity and frequency. The compositions known from the prior art, on the contrary, different growth dynamic viscosity at lower frequencies, expressed in the form of a plateau of Newton.

When considering the results obtained in the foam shells, it becomes apparent that the compositions according to the invention allow to obtain foamed sheath is very high quality, appropriate density, becausee tensile strength and very good dielectric properties. The compositions known from the prior art, on the contrary, does not allow to obtain a foamed shell.

1. Polymer composition containing one or more halogenated thermoplastic polymer, characterized in that it has a value of RMFIfrom 1.1 to 6, and RMFIrepresents the ratio between the MFI8/2and MFI0,3/1measured in accordance with ASTM D1238.

2. Polymer composition according to claim 1, characterized in that the content of insoluble fractions of polymers (FI) is less than or equal to 20 wt.%, in fact the content of insoluble fractions of polymers (FI) represents the content of the polymer is not soluble in dimethylformamide (DMF), isolated by centrifugation after dissolution of the polymer by boiling under reflux in DMF.

3. Polymer composition according to claim 1 or 2, characterized in that it has the property to harden under tension in the melt, characterized by an exponential increase in viscosity tensile depending on the time.

4. Polymer composition according to any one of the preceding paragraphs, characterized in that the halogenated thermoplastic polymers are fluorinated thermoplastic polymers.

5. Polymer composition according to any one of claims 1 to 4, characterized in that the halogenated thermoplastic polymers are selected from t is moplastic polymers of vinylidenefluoride and thermoplastic polymers chlorotrifluorethylene.

6. Polymer composition according to claim 5, characterized in that the halogenated thermoplastic polymers selected from homopolymers of vinylidenefluoride and copolymers and terpolymers of vinylidenefluoride with at least one other fluorinated monomer.

7. Polymer composition according to any one of the preceding paragraphs, characterized in that it contains one or more standard additives selected from traps acid, lubricating agents, organic dyes or mineral pigments, nucleating, materials, fillers, stabilizers and flame retardant agents.

8. A method of producing compositions based on halogenated thermoplastic polymer according to any one of claims 1 to 7, characterized in that one or more halogenated thermoplastic polymer lead in the interaction in the melt in the extruder with the initiator radicals and agent education bridge connection, and the obtained composition is removed from the extruder.

9. The method according to claim 8, characterized in that the number of initiator radicals is from 0.5 to 10 g/kg halogenated thermoplastic polymers.

10. The method according to claim 8 or 9, characterized in that the number of agent education bridge connection is from 0.5 to 50 g/kg halogenated thermoplastic polymers.

11. The method according to any of PP-10, characterized in that the agent was formed who I bridge the connection selected from the group consisting of triallylisocyanurate, divinylbenzene, VINYLTRIMETHOXYSILANE and allyltriethoxysilane.

12. The method according to any of PP-11, characterized in that the agent education bridge communication injected before the initiator radicals.

13. The use of compositions according to any one of claims 1 to 7 or obtained by the method according to any of p-12 for the production of films, sheets, plates, foam shells, pipes, foams, bottles or termoformovannyh and/or cast products.

14. The use of foamed membranes obtained from compositions according to any one of claims 1 to 7, for coating electric cables.



 

Same patents:

FIELD: polymer materials.

SUBSTANCE: invention relates to polymer mixture for use in membrane manufacture. Mixture contains (i) at least one acrylic polymer or at least one acrylic polymer and at least one vinyl polymer, which polymers comprise at least one ionic or ionizable group, in particular sulfurized group, and (ii) at least one thermoplastic fluoropolymer, provided that components (i) and (ii) differ from each other. Invention also related to polymeric ionic membrane, membrane electrode complex, fuel cell, battery, and to a polymer mixture and composition preparation process.

EFFECT: enabled production of fluoropolymer uniformly mixing with other polymers, enabled manufacture of membrane directly from aqueous fluoropolymer dispersions, and increased chemical resistance and mechanical strength of membranes.

25 cl, 5 tbl, 13 ex

FIELD: polymer materials.

SUBSTANCE: composition contains, wt %: vinylidene fluoride 20-40, methyl methacrylate homopolymer or copolymer, acryl elastomer 5-18, and UV-absorbing substance 1-4. Invention also discloses jointly extruded films (options) and substrates covered by these films. Invention enables preparing composition with not rising UV-absorbing substances and manufacturing films showing high mechanical strength and providing high-quality adhesion to substrate while being resistant to radiation.

EFFECT: improved consumer's properties of films.

14 cl, 7 ex

FIELD: polymer materials.

SUBSTANCE: invention provides elastic and resilient composition containing (A) at least one homopolymer of vinylidene fluoride or copolymer of vinylidene fluoride with at least one other monomer capable of being copolymerized with vinylidene fluoride wherein proportion of this other monomer ranges between 0 and 30 wt parts per 100 wt parts vinylidene fluoride, (B) at least one fluorinated elastomer, which is copolymer of vinylidene fluoride and at least one other fluorinated monomer, and optionally (C) plasticizer. Composition is characterized by that, on the one side, it contains 0.5 to 10 wt parts B and 0 to 10 wt parts C per 100 wt parts A, provided that B+C = 0.5 tp 10.5 wt parts, and, on the other side, such vinylidene fluoride homopolymer or copolymer is chosen in such a way that it has coefficient of fluidity below 5 g/10 min, as measured according to standard ISO 1133 at 230°C under load 5 kg, and critical modulus G ranging between to 5and 22 kPa, as measured in intersection of shear moduli G' and G" in molten state at 190°C.

EFFECT: essentially increased stability of composition in air and in crude oil.

7 cl, 6 tbl, 12 ex

The invention relates to a method for coating a rubber-based GFR-32 to protect the rubber surface from the action of aggressive media

The invention relates to the rubber industry

The invention relates to compositions based on fluorinated polymers, and method of production thereof

The invention relates to utverzhdennym forecaster - copolymers vinylidenefluoride and hexaferrite, which are used for production of industrial products such as gaskets, seals for shafts, sleeves and seals with metal inserts

The invention relates to polymeric compositions tribological purposes, intended for use in friction units of machines and equipment

The invention relates to a new rubber compound based on silicone elastomer and can be used as anti-friction coatings on metal and rubbers

The invention relates to compounds for the manufacture of prepregs

Polymer composition // 2098438
The invention relates to composite materials based on phenol-formaldehyde Novolac resins and fillers, suitable for the manufacture of thin-walled parts of compressors for household refrigerators

The invention relates to polymer compositions and can be used as a protective coating for fire pressure hoses, as artificial leather, film coating for wood and other decorative plates

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to compositions comprising methylpropyl ketone peroxide that provide safety work at environment temperature values. Invention proposes methylpropyl ketone peroxide compositions comprising above 60 wt.-% of methylpropyl ketone peroxide of type-4 (as measured for mass of active oxygen of methylpropyl ketone peroxide of type-4 for the full mass of active oxygen of all methylpropyl ketone peroxides) wherein abovementioned methylpropyl ketone peroxide of type-4 represents above 25 wt.-% of the total composition mass, and an anhydrous retarder in the amount providing safety of work and transporting at temperature 0-50°C based on test for self-accelerating degradation, Dutch test in autoclave and Kenen's test, and to a method for hardening resin based on unsaturated polyester by using in the amount from 0.1 to 8 wt.-% as measured for resin of the proposed peroxide composition.

EFFECT: improved and valuable properties of composition.

9 cl, 6 tbl, 24 ex

FIELD: polymers, chemical technology.

SUBSTANCE: invention relates to oil-filled 1,2-polybutadiene that can be used as different molded articles, to a method for its preparing, its composition and molded article, shoes footing material. Oil-filled 1,2-polybutadiene is prepared by addition of the definite amount of oily filling agent to 1,2-polybutadiene solution wherein polymerization process is terminated followed by stirring in the polymerization solution containing organic solvent and removing the solvent at the second stage of the method. The composition of oil-filled 1,2-polybutadiene for making molded article comprises abovementioned oil-filled 1,2-polybutadiene and one component taken among the group involving a foaming agent, functional compound for rubber or plastics and at least one component taken among the group consisting of thermoplastic resin, thermoplastic elastomer, natural rubber and synthetic rubber. The molded article is prepared by molding the oil-filled 1,2-polybutadiene. Material for shoes footing is prepared by foaming the composition of oil-filled 1,2-polybutadiene or by cross-linking and molding. Oil-filled 1,2-polybutadiene or composition based on thereof show excellent functions by abrasion resistance, fluidity, technological effectiveness, capacity for coloring, high image precision, flexibility and attachment capacity. Also, oil-filled 1,2-polybutadiene and compositions based on thereof can be used for different types of foodstuffs, material for shoes footing with high exploitation indices.

EFFECT: improved preparing method, improved and valuable properties of composition and article.

13 cl, 17 tbl, 43 ex

FIELD: electrical engineering; automobile and ship building, mechanical engineering, construction , oil extraction, and oil refining industries.

SUBSTANCE: proposed electric drive has stranded copper conductor with strand sectional area of 1.0 - 50 mm3 and rubber sheath , 0.4 - 7.0 mm thick, made of rubber mixture whose matrix is polymeric mixture of high-molecular polymethyl vinyl-siloxane and low-molecular polymethyl vinyl-siloxane rubber of mole mass of 20 -70 thousands in combination with silica powder, quartz, anti-texturing agent in the form of αω-dihydroxide methylsiloxane and organic peroxide. Rubber mixture is applied by extrusion at speed of 0.2 - 2 m/s and cured under radiation-chemical curing conditions with aid of cobalt gun incorporating γ-radiation source at dose rate of 2.5 - 20 megarad. and/or by thermal curing. Electrical conductor produced in the process is capable of fire self-suppression and is suited to operate at -60 to +300 °C.

EFFECT: enhanced fire, crack, oil, and gasoline resistance, improved electrical and physical characteristics.

3 cl, 1 tbl

The rubber mixture // 2241010
The invention relates to rubber industry and can be used in aggressive environments, in particular in the communication system for the manufacture of bushings for the suspension of the self-supporting fiber optic cables

The invention relates to the field of polymeric compositions, such as compositions based on chemically cross-linked polyethylene, and may find application upon receipt of the products obtained by thermoforming, in particular, a variety of specialized products: pipes, fittings, flanges, used for hot water systems in thermal networks

The invention relates to the field of chemical technology, in particular to the creation of rubber compounds based on siloxane rubbers, and can be used for manufacturing insulating tubes and insulating sheaths of the cable, polymer insulators of high-voltage lines, rubber products and materials, working in contact with gasoline, organic solvents and mineral oils

The invention relates to compositions containing cyclic ketone peroxide and phlegmatizer, having a point 95% boiling within 220-265oS, most preferably 235-250oWith
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