MXPA97005763A - Gel oleous formulations containing hydrogen styrene-butadiene-styrene bottle copolymers, with a high content of vin - Google Patents

Abstract

The present invention relates to an oil gel composition with high service temperature, removable, which comprises: (a) 100 parts by weight of hydrogenated vinylaromatic hydrocarbon-butadiene hydrocarbon-vinylaromatic hydrocarbon block copolymer which has a total average weight of molecular weight from 30,000 to 300,000, a vinylaromatic block hydrocarbon with an average molecular weight weight from 4000 to 35,000, and wherein the butadiene block has a vinyl content of at least 45% by weight, and (b) ) from 900 to 4900 parts by weight of an oil, or a mixture of an oil and a polyolefin wax and / or diluting liquid. In a further aspect, the present invention relates to the block copolymer described above.

Description

OLEOUS FORMULATIONS IN GEL CONTAINING FERTILIZER COCOA R > ü HYDROGENATED STYRENE-BUTADIENE-STYRENE BLOCK. mu T7M HIGH VINYL CONTENT DESCRIPTION PE THE INVENTION This invention relates to oily gel compositions for use as filler compounds in wire and cable applications. More particularly, this invention relates to such compositions containing block copolymers of hydrogenated vinylaromatic hydrocarbon-butadiene-vinyl aromatic hydrocarbon with a high content of vinyl and with polymers in. themselves. There are at least three main criteria in the formulation of an oil gel for cables. The oily gel must possess a certain degree of resistance to sinking at high service temperatures. Additionally, the gel needs to be removable so that those who make installations and people who make repairs can make electrical splices with ease in the field. In addition, the oily gel must have good melt working viscosity so that it is easily pumped into the cable.

REF: 25336 The filler compounds used to prevent the access of water to telecommunications cables must have processing characteristics which allow the material to penetrate and fill the gaps between the densely packed insulated conductors. The viscosity of application is critical and the ability to adjust the viscosity by temperature is limited by the potential damage to insulation in copper conductors. Once the cable is filled, the filling compound should not flow outward at temperatures up to 80 ° C, should resist water heads or significant water discharges, should have good resistance handling characteristics, should be compatible with others components in the cable system such as splice encapsulants, and should not add significantly to the rigidity of the cable. Lower molecular weight polymers containing styrene and hydrogenated butadiene blocks, such as KRATON polymers "* G1650, G1726 and G1652, are used in the cable filling industry." RRATON * 1 * G1650 and G1652 polymers have good capacity benefits of detachment (measured by resistance to tearing of the oily gel) and have a viscosity low enough to be pumped into the cable and fill all cracks or crevices between the wire groups in the cables.The main problem with the KRATON G1650 and G1652 polymers is that these polymers in oily gel formulations do not work well at high service temperatures, this is due to the relatively low molecular weight of the polystyrene end blocks, the higher molecular weight version, the KRATON "11 G1651 polymers and G1654, promise excellent service temperature performance. The large styrene end blocks are much more resistant to flow (and loss of elasticity) which provides high performance at the service temperature. The large end blocks also help produce oily gels which, under certain conditions, can be difficult to detach (exhibit high tear strength), and prevent flow at service temperatures. Unfortunately, oily gels based on the KRATON "11 G1651 and G1654 polymers have poor adhesion and their viscosity is too high at application temperatures to allow the gel to flow properly between sets of wires in a cable. KRATON ™ G1651 and G1654 polymers are not widely used in cable filling applications This invention provides the advantages of both low molecular weight polymers and high molecular weight polymers and at the same time minimizes their disadvantages. polymers with a high vinyl content of the present invention in an oil gel application allows the oily gel formulators to manufacture gels with high service temperature properties in a releasable and pumpable form. Current wishes in this technique suggest that high service temperatures and a reduction in viscosity of application should be mutually exclusive for oily gels. This invention provides compositions which show both characteristics. The use of polymers with a high vinyl content as opposed to the polymers with a lower vinyl content described above, fortifies the viscosity / concentration ratio of the polymers, that is, a lower viscosity with other properties that remain approximately the same. Therefore, the present invention relates to an oil gel composition with high service temperature, removable, which comprises: (a) 100 parts by weight of a hydrogenated vinylaromatic hydrocarbon-butadiene hydrocarbon-vinylaromatic hydrocarbon block copolymer which has an average molecular weight weight since ,000 to 300,000, a vinylaromatic block hydrocarbon with an average molecular weight weight from 4000 to 35,000, and wherein the butadiene block has a vinyl content of at least 45% by weight, and (b) from 900 to 4900 parts by weight of an oil, or a mixture of an oil and a polyolefin wax and / or a diluting liquid. According to a further aspect, the present invention relates to a hydrogenated vinyl aromatic-butadiene hydrocarbon-vinylaromatic hydrocarbon block copolymer with a high vinyl content having an average total molecular weight weight from 30,000 to 300,000, an average weight of molecular weight of vinylaromatic block hydrocarbon from 4000 to 35,000, and wherein the butadiene block has a vinyl content of at least 45% by weight. Accordingly, this invention provides oil gel compositions which comprise a hydrogenated vinylaromatic hydrocarbon-butadiene-vinylaromatic hydrocarbon block copolymer which has an average molecular weight weight from 30,000 to 300,000 (preferably from 40,000 to 220,000, and from most preferably from 60,000 to 220,000), an average molecular weight weight of the vinylaromatic hydrocarbon block from 4000 to 35,000 (preferably from 6000 to 33,000, more preferably from 9,000 to 33,000, most preferably from 15,000 to 33,000), and a vinyl content of at least 45% by weight ((% by weight), preferably 45 to 90%, and an oil and, optionally, thickeners such as polyolefin wax, silica gel , smoked silica, fatty acid soaps and diluting fluids such as poly (alpha-olefins). For every 100 parts by weight of copolymer, there must be at least We use 900 parts of oil or a mixture of oil and a polyolefin wax and / or a diluting liquid. The vinylaromatic hydrocarbon end blocks of these novel block copolymers are preferably styrene block polymers. Other vinylaromatic hydrocarbons, including alphamethylstyrene, various alkyl-substituted styrenes, styrenes substituted with alkoxy, vinylnaphthalene and vinyltoluene, can replace styrene and are expressly included in this invention. The alkyl and alkoxy groups of the styrenes substituted with alkyl or substituted with alkoxy, respectively, may be composed of 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms. The butadiene used herein should produce a block polymer with a high vinyl content. In other words, the percent of the 1,2-addition of the butadiene should be at least 45% by weight, preferably 45 to 90%, more preferably 60 to 90%, and most preferably 65 to 80%. %. Below 45% by weight, the viscosity of the polymer is similar to that of conventional polymers and there is no advantage. Above 90%, the viscosity decreases and reaches a plateau and does not decrease further with a content greater than 1.2; therefore, there is no additional advantage. The anionic polymerization of conjugated diene hydrocarbons with lithium initiators is well known as described in U.S. Patent Nos. 4,039,593 and Re. 27,145. The polymerization begins with a monolithium, dilithium or polylithium initiator which constructs a main polymer structure growing at each site with lithium. Typical growth polymer structures contain polymerized conjugated diene hydrocarbons and are: XB-Li XAB-Li XABA-Li Li-BYB-Li Li-ABYBA-Li where B represents polymerized units of one or more conjugated diene hydrocarbons such as butadiene or isoprene, A represents polymerized units of one or more vinylaromatic compounds such as styrene, X is the residue of a onolithium initiator such as sec-butyllithium, and Y is the residue of a dilithium initiator such as the diaduct. of sec-butyllithium and m-diisopropenylbenzene. Some structures, which include those belonging to polylithium initiators or random units of styrene and a conjugated diene, generally have limited practical utility although they are known in the art. The anionic polymerization of the conjugated diene hydrocarbons is typically controlled with structure modifiers such as diethyl ether or ethyl glyme (1,2-diethoxyethane) to obtain the desired amount of 1.2 addition. As described in Re 27,145, the 1,2-addition level of a butadiene polymer or a copolymer can greatly alter the elastomeric properties after hydrogenation. The 1,2-addition of butadiene polymers significantly and surprisingly influences the polymer as described above. A 1.2 addition of about 40% is obtained during the polymerization at 50 ° C, with about 6% by volume of diethyl ether or about 200 ppm of ethyl glyme in the final solution. A 1.2 addition of about 47% (within the scope of this invention) is obtained during the polymerization by the presence of about 250 ppm of ortho-dimethoxybenzene (ODMB) in the final solution. A 1,2-addition of 78% (within the scope of this invention) is obtained during the polymerization in the presence of about 300 ppm of 1,2-diethoxypropane (DEP) in the final solution. One of the benefits of polymers with a high vinyl content, as defined in this specification, is to improve the clarity or transparency of oily gels containing such polymers. This is a particularly valuable feature for oily gels formulated for cosmetic applications. The improvement results from a reduced concentration of crystalline polyethylene which is formed when the butadiene polymerizes in the orientation 1,4 (head to tail) repeatedly and is hydrogenated to polyethylene. The concentration of polyethylene crystals decreases when the 1.2 addition is increased, (ie, vinyl content) and reaches zero above about 55% vinyl content. In general, the polymers useful in this invention can be prepared by contacting the monomer or monomers with an alkaline organometal compound in a suitable solvent at a temperature within the range of -150 ° C to 300 ° C, preferably at a temperature within the range from 0 ° C to 100 ° C. Particularly effective polymerization initiators are organolithium compounds having the general formula: RLi-lo wherein R is an aliphatic, cycloaliphatic, cycloaliphatic hydrocarbon radical substituted with alkyl, aromatic or aromatic substituted with alkyl having 1 to 20 carbon atoms. Suitable solvents include those useful in the polymer polymerization solution and include aliphatic, cycloaliphatic, alkyl substituted cycloaliphatic, alkyl substituted aromatic and aromatic hydrocarbons, ethers and mixtures thereof. Thus, suitable solvents include aliphatic hydrocarbons such as butane, pentane, hexane, and heptane, cycloaliphatic hydrocarbons such as cyclohexane and cycloheptane, alkyl substituted cycloaliphatic hydrocarbons such as methylcyclohexai. and methylcycloheptane, aromatic hydrocarbons such as benzene and alkyl substituted aromatic hydrocarbons such as toluene and xylene, and ethers such as tetrahydrofuran, diethyl ether and di-n-butyl ether. The hydrogenation of these polymers can be carried out by a variety of well-established processes including hydrogenation in the presence of a catalyst such as Raney nickel, noble metals such as platinum and palladium, and soluble transition metal catalysts. Suitable hydrogenation processes which may be used are those in which the diene-containing polymer or copolymer is dissolved in an inert hydrocarbon diluent such as cyclohexane and hydrogenated by reaction with hydrogen in the presence of a soluble hydrogenation catalyst. Such processes are described in U.S. Patent Nos. 3,113,986, 4,226,952 and the new issue number 27,145. The polymers are hydrogenated such that they produce hydrogenated polymers having a residual unsaturation content in polydiene blocks of less than 10 percent, preferably less than 5 percent, more preferably less than 1 percent, and even more preferably as close as possible to 0 percent, of its original unsaturation content before hydrogenation. A titanium catalyst, as described in U.S. Patent No. 5,039,755 can also be used in the hydrogenation process. The molecular weights of the linear polymers or the non-assembled linear segments of polymers such as monobloc, diblock, triblock, etc., or star polymer arms before coupling are conveniently measured by gel permeation chromatography (GPC), when the GPC system has been properly calibrated. For anionically polymerized linear polymers, the polymer is essentially monodisperse (the ratio of the average molecular weight / average molecular weight number approaches unity), and it is both convenient and adequately descriptive to report the "peak" molecular weight of the narrow molecular weight distribution that is observed. Usually, the peak value is between the number and the average weight. The peak molecular weight is the molecular weight of the molecular species shown in the chromatograph. For polydispersed polymers, the average molecular weight should be calculated from the chromatograph and should be used. The materials used in the CPG columns are styrene-divinylbenzene gels or silica gels. The solvent is tetrahydrofuran and the detector is a refractive index detector. In consecuense, the invention provides an oily gel composition comprising a styrene-alkylene-styrene block copolymer whose polyalkylene blocks comprise ethylene / butylene units and an oil, and optionally may include a polyolefin wax and / or a liquid thinner, liquid which is typically a poly (alpha-olefin) and extends and softens the polybutadiene blocks of the copolymer. For every 100 parts by weight (pbw) of the copolymer, there must be at least 900 parts by weight of total polyolefin wax plus oil and / or liquid diluent to obtain the low viscosity and economy required for oil gel applications, although it is possible to reach positions as low as 300 parts by weight for some applications. No more than 4900 parts by weight of wax / oil / liquid diluent per 100 parts of polymer can be used or the polymer will not thicken the composition adequately and will not retain the oil sufficiently well to prevent oil leakage during service. More preferably, the amount is from 1400 to 4850 parts by weight, and more preferably from 1600 to 2500. The oil which may be used includes, for example, paraffinic oils, mineral oils (white) naphthenic oils and those available from Shell Oil Company under the trademark SHELLFLEX ™, Kaydol oil (trademark) produced by Witco, and Fina Chemicals under the trademark Vestan A360B. Drakeol oil 34 (trademark) from Penreco and Witco 380P0 oil (trade mark) from Witco can also be used. If used, the diluent liquid generally constitutes at least 5% by weight of the total oil / diluent liquid portion, but is usually not more than 50% by weight because the polymer may not be able to retain larger proportions due to limited compatibility. The polyolefin wax component of the oily gels, if used, can be selected from those available by standard or simple test and error, and is generally of a low molecular weight polyethylene. Examples of suitable grades are manufactured by Allied under the trademark A-C, by Quantum Chemical under Petrothene (trademark) and by Eastman Chemical Products under Epolene (trademark). The content of polyethylene wax is usually from 3 to 10% of the total composition. More than 10% can reduce the oil retention capacity of the composition, and less than 3% is usually not cost efficient. The poly (alpha-olefin) diluent liquids useful in the compositions of this invention comprising the block copolymer can be selected from those available by trial and error. Examples include those available from Ethyl Corporation under the trademark "Ethylflo." The diluents preferably have a minimum boiling point above the softening point of the block copolymer. The commercially available grades include "Ethylflo 164", "Ethylflo 166", "Ethylflo 168", and "Ethylflo 170". These compositions are generally compared by mixing the oil and the polymer together with some kind of mechanical mixing aid and optionally with the aid of a volatile solvent. When a diluent liquid is used, it is usually mixed with these components at a temperature not r. of the glass transition temperature of the polystyrene blocks of the copolymer. It may be useful to use various additives such as stabilizers, antioxidants and thickeners.

EXAMPLES PP5181 is a SEBS block copolymer with a high vinyl content. Its molecular characteristics are compared with that of polymer A in table 1 below. It can be seen that it is very similar, except for the vinyl content. The other polymers have different characteristics. PP5828, shown below, is similar to polymer B, except that 78% of its rubber block is in a 1.2 microstructure, compared to 38% for polymer B. The flow properties of PP5828 are markedly better in comparison with those of polymer B, as indicated by its viscosity in solution (two orders of lesser magnitude) and by the much higher melt flow rates. Similarly, PP5823 (78% addition 1.2) shows much better flow properties compared to polymer C, which has 38% 1.2 addition. PP5819 has an intermediate level of structure 1,2 (47%), but it is still remarkably better in its flow properties compared to polymer C. The high flow characteristics mean pumping capacity of the oily gel formulations manufactured from of high vinyl polymers which is far superior to conventional block copolymers. The highest glass transition temperatures (see table 2) of the polymers with a high 1,2, is a natural consequence of such a high 1,2 structure. They are still well below the approximate low temperature of use requirement of -10 ° C for cable filling compounds.

Table 1 Table 2 The oil gel samples for formulation # 1 (below) are prepared by adding 6% by weight of polymer to Kaydol mineral oil (trademark) in a Silverson (trademark) mixer at 100 ° C. The samples are mixed until they are completely dissolved and poured out, into a container with a release liner approximately 0.5 cm (0.2 in) thick. When there are problems during the mixing that prevent a good incorporation of the polymer, the temperature in the mixer increases until a uniform mixture is obtained. The mixtures are then cut and tested for their tear strength, according to the ASTM D624 method. The oil gel samples for formulation # 2 are prepared by adding 6% by weight of polymer to Kaydol mineral oil in a Silverson mixer at 100 ° C. Additionally, 6% by weight of polyethylene AC9 is added to the formulation. The samples are mixed until they are completely dissolved and poured out into a container with release liner up to about 0.56 cm (0.2 in) thick. When problems arise during mixing that prevent a good incorporation of the polymer into the oil, the temperature in the mixer is increased until uniform mixing is obtained. The samples are then cut and tested to determine their tear strength, according to the ASTM D624 method. The melt viscosities are carried out in selected gels. Additionally, DMA temperature scans are carried out to determine the temperature at which the gel begins to detach (by loss of elastic modulus).

Table 3 Notes 1. Tear strength is determined by the ASTM D624 method, using 0.5 cm (0.2 in) thick oily gels. Each previous value is the average of 4-8 tests. 2. Formulation 1 contains 6% polymer and 94% Kaydol oil (trademark). Formulation 2 contains 6% polymer, 6% PE wax (AC-9 manufactured by Allied), and 88% Kaydol oil (trademark). The approximate temperature of loss of elasticity is determined at the temperature at which the elastic mode of the oily gel decreases (measured by DMA).

It can be clearly seen from Table 3 that formulations with higher molecular weight polymers (A and D) show a high tear resistance - too high to be useful in a cable filling application. However, they have a high temperature and loss of elasticity and therefore show the high service temperature that is desired. The polymer formulations with lower molecular weight (B and C) have a tear resistance indicative of good peel ability, but their service temperatures without undesirably low. The formulation of this invention with the PP5181 polymer has an appropriate tear strength for good peel ability and high service temperature (as high as that obtained for A, the high molecular weight polymer) yet still maintains a high acceptable viscosity. It is noted that in relation to this date, the best method known by the applicant to carry out the aforementioned invention, is the conventional one for the manufacture of the objects to which it relates. Having described the invention as above, property is claimed as contained in the following:

Claims (8)

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1. An oil gel composition with high service temperature, which can be peeled off, characterized in that it comprises: (a) 100 parts by weight of a block copolymer of hydrogenated vinylaromatic hydrocarbon-butadiene-vinylaromatic hydrocarbon which has a total weight average weight molecular from 30,000 to 300,000, a vinylaromatic block hydrocarbon with an average molecular weight weight from 4000 to 35,000, and in which the butadiene block has a vinyl content of at least 45% by weight, and (b) from 900 to 4900 parts by weight of an oil, or a mixture of an oil and a polyolefin wax and / or a diluting liquid.

2. The oil gel composition according to claim 1, characterized in that the vinylaromatic hydrocarbon is styrene.

3. The oil gel composition according to claim 1 or 2, characterized in that the vinyl content is from 45 to 90% by weight.

4. The oil gel composition according to claim 3, characterized in that the vinyl content is at least 60% by weight.

5. A hydrogenated vinylaromatic hydrocarbon-butadiene-vinylaromatic hydrocarbon block copolymer with a high vinyl content, characterized in that it has a total average molecular weight weight from 30,000 to 300,000, an average molecular weight weight of vinylaromatic hydrocarbon block from 4,000 to 35,000 , and wherein the butadiene block has a vinyl content of at least 45% by weight.

6. The block copolymer according to claim 5, characterized in that the vinylaromatic hydrocarbon is styrene.

7. The block copolymer according to claim 5 or 6, characterized in that the vinyl content ranges from 45 to 90% by weight.

8. The block copolymer according to claim 7, characterized in that the vinyl content is at least 60% by weight.