The composition of the gel and the device that includes the composition of the gel

 

(57) Abstract:

The gel containing block copolymer is a styrene-alkylene-styrene and at least 300 wt.h. fluid-filler per 100 wt.h. the block copolymer, and said fluid provides expansion and softening of the blocks polyalkylene specified block copolymer, characterized in that the block copolymer is a styrene-alkylene-styrene copolymer contains 20 to 100% of the units of propylene by weight of the total mass of blocks polyalkylene, and as a liquid-filler it contains poly(alpha-olefin) or its mixture with a non-aromatic oil-filler, up to 90% by weight of the mixture. Describes the device that includes the composition of the gel. The above gels due to their higher temperature softening improve resistance to subsidence at elevated temperatures in comparison with the known gels. 2 C. and 12 C.p. f-crystals, 1 Il., table 1.

The invention relates to a new and better from a technological point of view, the compositions of the gels containing the block copolymer is a styrene- (ethylene/propylene)-styrene (SEPS) and at least 300 mass parts, preferably at least 400 mass parts, more preferably at least 500 mass parts) fluid-filler per 100 mass parts of the block copoly alternatively, the specified proportion of the filler can be expressed in terms of weight percent of the copolymer, that is: 300=25%, 400=20%, 500= 17%.

Known gel composition comprising the block copolymer is a styrene-(ethylene/propylene) styrene, oil filler (0-15 wt. %) and the polyolefin, including poly (-olefin) - 3-25 wt. percent, and the number of links polyethylenepropylene in the block copolymer ranges: 10:90-25:75 (see US patent 5093422, CL 08 L 53/00, 1992).

Also known composition of the gel, including the block copolymer is a styrene-alkylene-styrene and > 500 wt.h. liquid filler, selected from the group of paraffinic or naphthenic oil (minarine) or synthetic oils, for example polypropylene, or mixtures thereof (see WO 90/05166, CL 08 L 53/00, H 02 R 15/18, 1990).

The number of units of ethylene/propylene included in the polyalkylene block copolymer CAPS, you can change from 100% to only 20% when you receive it from the mixed raw materials isoprene/butadiene, which is lightly copolymerized and hereroense with getting triblocal CAPS with mixed medium blocks the ethylene/propylene: ethylene/butylene of polyalkylene. Various advantages of gels from SAPS arise due to the presence of units of ethylene/propylene, and the preferred high aspect ratio up to at least 30% or 40%, preferably at least 50% of units of ethylene/propylene in the middle blocks polyalkylene. Osobukola 60% of units of ethylene/propylene and about 40% of units of ethylene/butylene. Also suitable a higher proportion of units of ethylene/propylene, for example at least 80% or 90%, and the blocks of one unit of alkylene of, in principle, 100% of units of ethylene/propylene. These shares are expressed in mass percent.

It is believed that units of alkylene non-ethylene/butylene, you can enable units of ethylene/propylene for education other suitable block copolymers CAPS, but ethylene/butylene is preferable.

Known gels derived from block copolymers of styrene-(ethylene/butylene)-styrene (SEBS), and test methods for determination of gels and their characteristics are described in International applications WO-A-8800603 and WO-A-9005166.

However, the gels CAPS usually have superior performance at high temperatures and an increased ability to retain fluid-filler under pressure in different types of end use. Gels CAPS also usually have better adhesiveness than the known gels SALT, which reduces the need to add imparts stickiness of the substance to achieve the desired level of adhesion to the surfaces with which they come into contact with the end use.

As gels CAPS and known gels SABS may not have the desired degree is aniah outdoors for example, when sealing electrical cables in cable boxes. The present invention reduces this phenomenon, without compromising other properties of the gels.

The invention provides a gel composition containing the block copolymer is a styrene-alkylene-styrene and at least 300 mass parts of a liquid-filler per 100 mass parts of the block copolymer, and said fluid provides expansion and softening of the blocks polyalkylene specified block copolymer, the block copolymer is a styrene-alkylene-styrene copolymer contains 20 to 100% of units of ethylene/propylene by weight of the total mass of blocks polyalkylene, and as a liquid-filler it contains poly(alpha-olefin) or its mixture with a non-aromatic oil-filler, up to 90% by weight of the mixture.

Fillers of poly(alpha-olefin) is preferably used in mixtures with previously used oils-fillers, which include, for example, supplied by the firm IPA Chemicals under the trademark "Vestan AV" (preferred), "Drakeo134" company Penreco and Witco RO" company Witco. Preferably at least 10%, more preferably at least 20%, most preferred at least 30% substitution of known oils, fillers poly(alpha-olefins). Was amnestic processing. Now, preferred mixtures of known oil: poly(alpha-olefin) in the range from 30:70 to 70:30, and for some applications it may be preferred mixture in the range from 70:30 to 80:20 or even 90:10. These percentages and proportions are expressed by weight based on the weight of the mixture of filler.

In the compositions according to the present invention, the mass ratio units/propylene units polyalkylene is at least 30%, preferably at least 40% and more preferably at least 50%.

The proportion of units of ethylene/propylene is at least 80% or at least 90%. Blocks polyalkylene include units of ethylene/butylene together with units of ethylene/propylene.

Gels CAPS is preferably resistant to high temperatures and subsidence elastic compositions of gels, which are meant advanced liquid polymer compounds having a critical elongation (measured according to the method of American society for testing and materials (ASTM D412-modified as will be described below) of more than 100%, preferably at least 200%, and the ratio of elastic deformation (i.e., in principle without hysteresis) to the elongation is at least 100%, ultimate tensile RAS zero subsidence at temperatures up to 100oC, preferably up to 120oC, more preferably up to 135oC and in particular up to 150oC.

According to the invention for some specific uses of the gel contains from 4 % to 20%, preferably from 5 to 15, more preferably from 6 to 12 by weight of the block copolymer CAPS and at least 400, preferably 500 mass parts of a liquid-filler per 100 mass parts of the block copolymer, which block copolymer CAPS contains more than 50%, preferably more than 75%, more preferably more than 90% and especially more than 95% by weight or, in principle, the whole mass of all present gelatinous polymer. May contain various additives, for example, giving a sticky substance that is described in WO-A-9005166, or oxide Polyphenylene described in WO-F-8800603, or diblock copolymers, styrene-alkylene to reduce the loss of fluid-filler, as described in our concurrently pending application, the UK 91192612.7. However, improved operating parameters of these gels CAPS can reduce or eliminate the need for such additives.

A device for protecting electrical conductors by using a tool that protects the conductors, which uses meniu well suitable among other things for a reusable seal boxes for electrical connections. The present invention provides a device containing a box for electrical conductors, cable filler based gel according to the present invention to protect the conductors from contamination and/or corrosion in the specified box and the tool retention of filler. In these or other applications, the gels are subjected to continuous pressure, because what is important is their ability to retain fluid-filler.

The composition can be in principle free from" compatible with polystyrene components that significantly increase or decrease the softening temperature (Ts) of the composition, either in principle such components are present, either in the sense that the number of such components present is not enough to significantly affect the softening temperature. The use of such components for a significant increase in the softening temperature (Ts) claimed in the aforementioned application WO-F-8800603, and can be applied in this case. The decrease of Ts in the General case, it is undesirable for the purposes of the present invention, and therefore preferably nonaromatic filler, i.e., it contains less than 2%, more preferably less than 1% and especially the principle 0% aromatic material.

It was found that gels CAPS due to their higher temperature softening improve resistance to subsidence at elevated temperatures compared to the same gels SALT in achieving the desired "soft" and "elasticity". Subsidence usually occurs when several tens of degrees above the onset of the softening temperature Ts. Therefore, these gels are clearly different from known materials cable fillers, which when used, must settle and flow.

Even at higher levels Jew who otnositelno free from selection of the filler, many quality improved while maintaining an adequate balance of other properties. When the adhesion of the compositions of the gels to another surface or to each other they are usually purely removed release the adhesive substance from the surface of contact, almost without breaking the cohesion within the structure of the gel.

For the purposes of the present invention is particularly interested in those block copolymers CAPS, in which the block copolymer contains from 20 to 50 mass percent, preferably from 25 to 40 mass%, particularly from 28 to 35 weight percent polystyrene blocks.

The block copolymers preferably contain from 80 to 50 mass%, more preferably from 75 to 60 weight percent, especially from 72 to 65 weight percent poly blocks(alkylene). Blocks polyalkylene preferably contain, in principle, fully hydrogenated blocks of poly(ethylene/propylene), especially predominantly (e.g. > 90% or > 95 %) containing units of the formula

-(CH2CH(CH3)CH2CH2)-

possibly with small amounts of these isomers, as

-(CH2- (CH3)(CH2CH3)) -

-(CH2-CH-[CH(CH3)2])-

The formation of cross-links in the connection, although it is not PTS CLASS="ptx2">

In the specified range of properties of the gels according to the present invention the preferred gels with a critical elongation of at least 200%. Preferred elastic deformation to a relative elongation of at least 200%.

Liquid-filling of poly(alpha-olefin), suitable compounds of the present invention and containing the block copolymer can be chosen by simple trial and error. Preferred materials are also supplied by the company Ethyl Corporation under the trademark "Ethylflo". Preferably, the fillers have a minimum boiling point higher than the softening point of the block copolymer (copolymer) and any additional polymer or copolymer. Liquid-filled poly(alpha-olefin) has a point of not fill above the 30oC, more preferably not higher than - 40oC and most preferably not higher than - 50oC.

Fillers of poly(alpha-olefin) can be obtained by reaction of ethylene, obtained from natural gas or/and from kikirevenge oil for the formation of C4-C30 linear alpha-olefins, a mixture which is then polymerized to obtain a poly(alpha-olefins) in the range of compositions and viscosity values.

Among the commercially available grades include Ethylflo 164", sod is% tetramer, 17.4% of pentamer and 3.8% hexamer point fill - 63oC; "Ethylflo 168", containing about 6% of trimer, 55,7% tetramer, 27.5 % of pentamer, 7% hexamer and 4.1% of heptamer point fill - 60oC; and Ethylflo 170" containing about 1.1% of trimer, 42.5% of the tetramer, and 32.3% of pentamer, 11,8% hexamer and 12.2% of heptamer point fill - 54oC. value of viscosity in Centistokes at -40oC these varieties of Ethylflo" 164 and 170 are respectively about 2490, 7877, 18305 and 32650, while the above-mentioned oil AW is solid at - 40oC.

Famous oil-fillers are preferably used in mixtures with poly(alpha-olefins) include the principle of non-aromatic paraffinic/naphthenic mineral oil with the ratio of paraffin: naphthene (N : N) carbon in the range of 1.75 : 1 to 5 : 1, preferably from 1.77 : 1 to 3 : 1, more preferably from 1.9:1 to 2.7 : 1 and most preferably from 2.2: 1 to 2.5: 1.

These oil-fillers, especially when the preferred relations P : N, usually give gels with characteristics well suited for these reusable boxes. Preferably the oil has a relative density at 20oC according to ASTM D2140 in the range from 0,861 to 0,865, preferably from 0,862 to 0,864.

Soedinenii (copolymers) at a temperature not less than the transition temperature of the glass blocks of polystyrene block-copolymer CAPS, as mostly described (for SALT) in the application WO-A-8800603.

However, you can use the mixture of (abrasion) or other methods of mixing at lower temperatures, possibly with the use of volatile solvents, if the resulting composition is suitable for the intended end use.

The compositions according to various aspects of the present invention can be manufactured with a wide range of physical properties, such as dynamic module accumulation, critical elongation and tensile strength, to meet the requirements of the final product. Preferred compositions of the critical elongation of at least 200% (ASTM D412) is particularly suitable as sealing materials. These compositions preferably contain more than 500 and preferably not more than 5000 mass parts of a liquid-filler per 100 mass parts of the block copolymer.

It may be useful to apply different additives for different purposes in any of the compositions of the present invention. Such additives may be stabilizers, antioxidants, substances that prevent burning, giving a sticky substance, corrosion inhibitors, etc., In all the compositions of the present invention are useful antioxidants.

can be used as sealing materials for boxes with electrical connections, for example, as shown in published application for the European patent 0108518 and 0191609, although the compositions of the present invention may have different applications depending on the desired properties and operating temperature.

Gels and kelloidnye compositions within the invention preferably are defined by criteria from (1) to (8), obtained from tests 1 - V, as described in WO-A-8800603. From these criteria, preferably not more than one (1) or (2)) will be outside these ranges.

Preferred block copolymers CAPS to the present invention are selected from commercially available under the trademark "SEPTON" Japanese firm Kuraray, and SEPTON 4055, 4155 2006 and is the preferred variety. The presence of the desired range of properties of the optimized gel compositions according to the present invention can be determined by simple trial and error relative to the specified criteria.

Now will be described examples of gels CAPS with the use of fillers of poly(alpha-olefin) according to the present invention in comparison with the corresponding gels containing previously known fillers.

The polymers listed in the table, mixed with filler (E) of the poly the authorities for 50 minutes at 195-210oC in vacuum. The mixture of oil - polymer contained the specified mass% of the polymer. Module dynamic accumulation (G), softening temperature (Ts), elongation at break (EB) and tensile strength (T. S.) was determined as follows.

In the test, the melting point TMA of the piston with the load placed on the top of the sample gel. Then the sample was heated and the deviation of the sensor was measured as a function of temperature. The resulting trajectory was flat linear region (A), followed by the transition region (melting) (C), followed by a second flat region (C), where the piston is stopped. This is shown schematically in the drawing. This softening point is at the temperature at which cross extrapolated straight through a and B.

In our method we used a thermomechanical analyzer, Du Pont (TMA) thermal analyzer, Du Pont 1090. Used quartz sensor with a flat bottom with a diameter of 2.5 mm and with a load of 2 g Sample of the gel was in the form of a disk with a diameter of 6.25 mm and a thickness of 2 mm, the Sample is brought to equilibrium at -40oC for 5 minutes, then was heated to 300oC with a speed of 5oC per minute.

Test p is lovelis 2 "dumbbell" type BS 903 with a base of 40 mm Speed drawing was 100 mm/min

G (module) was measured by using a rheometer Bolin VOR-melting and software. The rheometer was used in the mode of vibrations of the measuring system with a parallel plate with a diameter of 25 mm and a core Converter torsion in 90 GSM. The gel samples was a disk with a diameter of 25 mm and thickness 3+/-0,2 mm the Measurements were performed at the indicated temperature with a frequency of 0.1 Hz. The tool worked with the maximum deformation in torsion, the corresponding strain of about 6% in these samples. A/E = mass ratio of the oil-filler AV at Ethylflo poly(alpha-olefin).

Septon 4055 is the above block copolymer containing mixed semiblocks EP/EB, whereas Septon 2005 and Septon 2006 contain only semiblocks EP. The mass percentage of blocks of styrene around the block copolymer is about 20% for 2005 and about 35% for 2006.

The ratio G in the table clearly shows that the known oil-filler AV gives gels, becoming at least 8 or 10 times harder after cooling from 20 to -40oOn the other hand, fillers Ethylflo poly(alpha-olefin) limit the ratio of solidification to less than half of what gives AW, I 27 similarly limits the curing, but dramatically reduces Ts 132 to just 86oC, whereas fillers Ethyflo usually increase Ts.

It was observed that the gels of the triblock copolymers of styrene with semiblocks EV or mixed semiblocks EB/EP, show some degree of hysteresis in your module G after heating and cooling, while triblock with only semiblocks EP, show relatively small hysteresis or lack of it. The absence of hysteresis means that the copolymers with problemami EP restore its mechanical properties faster when deviations from the low temperature.

1. The gel containing block copolymer is a styrene-alkylene-styrene and at least 300 wt.h. fluid-filler per 100 wt.h. the block copolymer, and said fluid provides expansion and softening of the blocks polyalkylene specified block copolymer, wherein the block copolymer is a styrene-alkylene-styrene copolymer contains 20 to 100% of the units of propylene by weight of the total mass of blocks polyalkylene, and as a liquid-filler it contains poly(alpha-olefin) or its mixture with a non-aromatic oil-filler, up to 90% by weight of the mixture.

2. Composition under item 1, characterized in that the content of poly(alpha-olefin) is m, that the mass ratio of the ethylene units/propylene units polyalkylene is at least 30%, preferably at least 40% and more preferably at least 50%.

4. The composition according to p. 3, characterized in that the proportion of units of ethylene/propylene is at least 80% or at least 90.

5. The composition according to PP. 1-4, characterized in that the blocks polyalkylene include units of ethylene/butylene, together with units of ethylene/propylene.

6. The composition according to PP. 1-5, characterized in that it contains at least 400, preferably at least 500 wt. including fluid-filler per 100 wt.h. this block copolymer.

7. The composition according to PP. 1-6, characterized in that it has a critical elongation of more than 100%, preferably at least 200%, and in principle the ratio of elastic deformation to an elongation of at least 100%.

8. The composition according to any one of paragraphs. 1-7, characterized in that it has an ultimate tensile strength less than 1 MPa.

9. The composition according to PP. 1-8, characterized in that it has a module dynamic accumulation G' less than 50,000 PA at 1 Hz.

10. The composition according to PP. 1-9, characterized in that it contains from 4 to 20, preferably from 5 to 15, more preferably from 6 to 12 wt.% specify the C.%, preferably from 25 to 40 wt.% especially from 28 to 35 wt.% blocks of polystyrene and from 80 to 50 wt.%, preferably from 75 to 60 wt.%, especially from 72 to 65 wt.% blocks of poly(alkylene).

12. The composition according to PP. 1-11, characterized in that the blocks of poly(ethylene-propylene) predominantly contain units of the formula -(CH2CH(CH3)CH2CH2)-.

13. The composition according to PP. 1-12, characterized in that the liquid-filler poly(alpha-olefin) has a point of not fill above the 30oC, preferably not higher than - 40oS, more preferably not higher than - 50oC.

14. The device contains a box for electrical conductors, cable filler based gel to protect conductors from contamination and/or corrosion in the specified box, means for holding the filler, characterized in that as a cable filler, based on gel it contains the gel on PP. 1-13.

 

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FIELD: composite materials.

SUBSTANCE: invention discloses a method for manufacturing composite material for shielding-mediated protection against electromagnetic emission and can be used in electronics, in radio engineering, and also in a series of special-destination articles. In addition, material may be used for anechoic boxes and in various assemblies of technical devices and radio apparatuses. Method comprises mixing modified graphite-containing conducting filler and polymeric binder at weight ratio (50-80):(20-50). Once ingredients combined, mixture is additionally subjected to thermal expansion in thermal shock mode at 250-310оС and then molded. Polymeric binder is selected from polyolefins, polystyrene, fluoroplastic, polyvinylchloride paste and modified graphite is product obtained by modifying graphite with concentrated sulfuric and nitric acids. Material is characterized by that, in wavelength band from 2 to 5 cm at thickness of material up to 0.1 mm, transmission coefficient is decreased from -40 to -85 dB.

EFFECT: improved performance characteristics.

6 cl, 1 tbl, 2 ex

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