MXPA97005763A - Gel oleous formulations containing hydrogen styrene-butadiene-styrene bottle copolymers, with a high content of vin - Google Patents
Gel oleous formulations containing hydrogen styrene-butadiene-styrene bottle copolymers, with a high content of vinInfo
- Publication number
- MXPA97005763A MXPA97005763A MXPA/A/1997/005763A MX9705763A MXPA97005763A MX PA97005763 A MXPA97005763 A MX PA97005763A MX 9705763 A MX9705763 A MX 9705763A MX PA97005763 A MXPA97005763 A MX PA97005763A
- Authority
- MX
- Mexico
- Prior art keywords
- weight
- oil
- butadiene
- styrene
- hydrocarbon
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 36
- 229920001577 copolymer Polymers 0.000 title description 7
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 title description 2
- 239000001257 hydrogen Substances 0.000 title description 2
- 229910052739 hydrogen Inorganic materials 0.000 title description 2
- 125000004435 hydrogen atoms Chemical class [H]* 0.000 title 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 23
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 19
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 17
- 229920001400 block copolymer Polymers 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 12
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229920000098 polyolefin Polymers 0.000 claims abstract description 8
- 238000007865 diluting Methods 0.000 claims abstract description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 18
- 229920000642 polymer Polymers 0.000 description 57
- 239000000499 gel Substances 0.000 description 31
- 239000003921 oil Substances 0.000 description 29
- -1 alphamethylstyrene Chemical class 0.000 description 13
- 239000004698 Polyethylene (PE) Substances 0.000 description 8
- 239000003085 diluting agent Substances 0.000 description 8
- 210000001138 Tears Anatomy 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 7
- 238000009472 formulation Methods 0.000 description 7
- 238000005984 hydrogenation reaction Methods 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 229920000573 polyethylene Polymers 0.000 description 6
- 239000003999 initiator Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atoms Chemical group C* 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000002480 mineral oil Substances 0.000 description 3
- 150000003440 styrenes Chemical group 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- ABDKAPXRBAPSQN-UHFFFAOYSA-N 1,2-Dimethoxybenzene Chemical compound COC1=CC=CC=C1OC ABDKAPXRBAPSQN-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical compound [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 description 1
- VPBZZPOGZPKYKX-UHFFFAOYSA-N 1,2-diethoxypropane Chemical compound CCOCC(C)OCC VPBZZPOGZPKYKX-UHFFFAOYSA-N 0.000 description 1
- IBVPVTPPYGGAEL-UHFFFAOYSA-N 1,3-bis(prop-1-en-2-yl)benzene Chemical compound CC(=C)C1=CC=CC(C(C)=C)=C1 IBVPVTPPYGGAEL-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical group C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N Cycloheptane Chemical compound C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229920002633 Kraton (polymer) Polymers 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- 235000009470 Theobroma cacao Nutrition 0.000 description 1
- 240000000280 Theobroma cacao Species 0.000 description 1
- ORGHESHFQPYLAO-UHFFFAOYSA-N Vinyl radical Chemical class C=[CH] ORGHESHFQPYLAO-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 230000000111 anti-oxidant Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 150000008378 aryl ethers Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000001808 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- RUSXXJKVMARGOF-UHFFFAOYSA-N cyclohexane;heptane Chemical compound C1CCCCC1.CCCCCCC RUSXXJKVMARGOF-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000008393 encapsulating agent Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000008079 hexane Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methylcycloheptane Chemical compound CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N n-heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N o-xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 150000002900 organolithium compounds Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000010690 paraffinic oil Substances 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical group C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N α-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
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)
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.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US2283496P | 1996-07-31 | 1996-07-31 | |
US022834 | 1996-07-31 |
Publications (2)
Publication Number | Publication Date |
---|---|
MXPA97005763A true MXPA97005763A (en) | 1998-02-01 |
MX9705763A MX9705763A (en) | 1998-02-28 |
Family
ID=21811674
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
MX9705763A MX9705763A (en) | 1996-07-31 | 1997-07-30 | Oil gel formulations containing high vinyl content hydrogenated styrene-butadiene-styrene block copolymers. |
Country Status (10)
Country | Link |
---|---|
EP (1) | EP0822227B1 (en) |
JP (1) | JPH1077382A (en) |
KR (1) | KR980009376A (en) |
CN (1) | CN1150271C (en) |
BR (1) | BR9705233A (en) |
CA (1) | CA2211944A1 (en) |
DE (1) | DE69732273T2 (en) |
MX (1) | MX9705763A (en) |
TR (1) | TR199700720A3 (en) |
TW (1) | TW416971B (en) |
Families Citing this family (26)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5777043A (en) * | 1997-03-05 | 1998-07-07 | Shell Oil Company | Sealant formulations containing high vinyl content hydrogenated styrene-butadiene-styrene block copolymers |
US6657000B1 (en) * | 1999-06-25 | 2003-12-02 | Kraton Polymers U.S. Llc | Hot melt pressure sensitive positioning adhesive (III) |
US6465557B1 (en) * | 1999-06-25 | 2002-10-15 | Kraton Polymers U.S. Llc | Hot melt pressure sensitive positioning adhesive |
JP2001151980A (en) * | 1999-11-24 | 2001-06-05 | Aron Kasei Co Ltd | Gel composition |
JP2001151979A (en) * | 1999-11-24 | 2001-06-05 | Aron Kasei Co Ltd | Gel composition |
JP2001335640A (en) * | 2000-03-24 | 2001-12-04 | Asahi Kagaku Gosei Kk | Production method of styrene-based thermoplastic elastomer composition |
EP1322707A1 (en) * | 2000-10-04 | 2003-07-02 | Kraton Polymers Research B.V. | An elastomeric film and fiber grade thermoplastic elastomer composition |
ATE250273T1 (en) * | 2000-10-10 | 2003-10-15 | Dynasol Elastomeros Sa | COMPOSITION OF CABLE FILLING MATERIALS |
US7268184B2 (en) | 2002-01-31 | 2007-09-11 | Kraton Polymers U.S. Llc | Blockcopolymer compositions, having improved mechanical properties and processability and styrenic blockcopolymer to be used in them |
JP4090998B2 (en) | 2002-01-31 | 2008-05-28 | クレイトン・ポリマーズ・リサーチ・ベー・ベー | Block copolymer composition with improved mechanical properties and processability |
EP1333058A1 (en) * | 2002-01-31 | 2003-08-06 | KRATON Polymers Research B.V. | Modified styrenic block copolymer and compounds thereof having improved mechanical properties and processability |
US7012118B2 (en) | 2002-02-07 | 2006-03-14 | Kraton Polymers U.S. Llc | Photopolymerizable compositions and flexographic plates prepared from controlled distribution block copolymers |
US20030181584A1 (en) | 2002-02-07 | 2003-09-25 | Kraton Polymers U.S. Llc | Elastomeric articles prepared from controlled distribution block copolymers |
US6987142B2 (en) | 2002-02-07 | 2006-01-17 | Kraton Polymers U.S. Llc | Adhesives and sealants from controlled distribution block copolymers |
US7517932B2 (en) * | 2003-03-24 | 2009-04-14 | Kraton Polymers U.S. Llc | Poly(styrene-butadiene-styrene)polymers having a high vinyl content in the butadiene block and hot melt adhesive composition comprising said polymers |
KR100959327B1 (en) * | 2005-03-11 | 2010-05-26 | 크레이튼 폴리머즈 리서치 비.브이. | Oil gels of controlled distribution block copolymers and ester oils |
US20060205904A1 (en) | 2005-03-11 | 2006-09-14 | St Clair David J | Oil gels of controlled distribution block copolymers and ester oils |
US9304231B2 (en) * | 2014-02-04 | 2016-04-05 | Kraton Polymers U.S. Llc | Heat fusible oil gels |
JP7066413B2 (en) * | 2015-06-12 | 2022-05-13 | クレイトン・ポリマーズ・ユー・エス・エル・エル・シー | Thermal activation gel for cable filling applications |
WO2018013853A1 (en) * | 2016-07-13 | 2018-01-18 | Kraton Polymers U.S. Llc | Block copolymers for gel compositions |
US10899864B2 (en) | 2016-09-09 | 2021-01-26 | Dynasol Elastómeros, S.A. De C.V. | Polar modifier systems for high vinyl block copolymerization |
CN107384272A (en) * | 2017-06-07 | 2017-11-24 | 吴秀兰 | Jelly composition and its manufacture method and safety glass diaphragm, electronic equipment |
CN109535624A (en) * | 2017-09-22 | 2019-03-29 | 湖州赛德新材料科技有限公司 | A kind of power electronics insulated enclosure barrier material and its manufacturing method |
WO2019183302A1 (en) * | 2018-03-23 | 2019-09-26 | Kraton Polymers Llc | Ultrahigh melt flow styrenic block copolymers |
US11542355B2 (en) * | 2018-10-18 | 2023-01-03 | Dynasol Elastómeros, S.A. De C.V. | Polar modifier systems for high vinyl block copolymerization |
KR102428479B1 (en) | 2021-11-12 | 2022-08-03 | 우진라페 주식회사 | Powder transfering system |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
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US3830767A (en) * | 1973-05-02 | 1974-08-20 | Shell Oil Co | Block copolymer compositions |
CA1156450A (en) * | 1981-01-30 | 1983-11-08 | John M. R. Hagger | Electric cables and compositions for use in them |
GB8922445D0 (en) * | 1989-10-05 | 1989-11-22 | Raychem Ltd | Gels |
-
1997
- 1997-07-23 TW TW086110503A patent/TW416971B/en not_active IP Right Cessation
- 1997-07-28 KR KR1019970035574A patent/KR980009376A/en not_active Application Discontinuation
- 1997-07-29 CA CA002211944A patent/CA2211944A1/en not_active Abandoned
- 1997-07-29 DE DE69732273T patent/DE69732273T2/en not_active Expired - Lifetime
- 1997-07-29 CN CNB971179697A patent/CN1150271C/en not_active Expired - Lifetime
- 1997-07-29 JP JP9203457A patent/JPH1077382A/en active Pending
- 1997-07-29 BR BR9705233A patent/BR9705233A/en not_active IP Right Cessation
- 1997-07-29 EP EP97202332A patent/EP0822227B1/en not_active Expired - Lifetime
- 1997-07-30 MX MX9705763A patent/MX9705763A/en unknown
- 1997-07-31 TR TR97/00720A patent/TR199700720A3/en unknown
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