WO2003066738A1 - Gels from controlled distribution block copolymers - Google Patents

Gels from controlled distribution block copolymers Download PDF

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Publication number
WO2003066738A1
WO2003066738A1 PCT/NL2003/000099 NL0300099W WO03066738A1 WO 2003066738 A1 WO2003066738 A1 WO 2003066738A1 NL 0300099 W NL0300099 W NL 0300099W WO 03066738 A1 WO03066738 A1 WO 03066738A1
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Prior art keywords
block
styrene
percent
mono alkenyl
alkenyl arene
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PCT/NL2003/000099
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French (fr)
Inventor
Dale L. Handlin, Jr.
Carl L. Willis
David J. St. Clair
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Kraton Polymers Research B.V.
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Priority to DE60314843T priority Critical patent/DE60314843T2/en
Priority to EP03705499A priority patent/EP1474481B1/en
Priority to AU2003207423A priority patent/AU2003207423A1/en
Publication of WO2003066738A1 publication Critical patent/WO2003066738A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J153/02—Vinyl aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F287/00—Macromolecular compounds obtained by polymerising monomers on to block polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
    • C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L95/00—Compositions of bituminous materials, e.g. asphalt, tar, pitch
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D153/00—Coating compositions based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D153/02—Vinyl aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D153/00—Coating compositions based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D153/02—Vinyl aromatic monomers and conjugated dienes
    • C09D153/025—Vinyl aromatic monomers and conjugated dienes modified
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J153/02—Vinyl aromatic monomers and conjugated dienes
    • C09J153/025—Vinyl aromatic monomers and conjugated dienes modified
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/24—Graft or block copolymers according to groups C08L51/00, C08L53/00 or C08L55/02; Derivatives thereof

Definitions

  • This invention relates to gels prepared from novel anionic block copolymers of mono alkenyl arenes and conjugated dienes.
  • SBC's have a long history of use as adhesives, sealants and gels.
  • a recent example of a gel may be found in US patent No. 5,879,694.
  • This invention comprises a new class of SBC s in which the polymer manufacturer can vary the compatibility characteristics of the rubber segment, resulting in improved oil gels.
  • Such gels may also be used, for example, as a water proofing encapsulant/sealant for electronics and in wire and cable applications
  • a novel oil gel composition comprising 100 parts by weight of at least one hydrogenated block copolymer having a controlled distribution block of a mono alkenyl arene and conjugated diene, and from 350 to 2000 parts by weight of an extender oil, wherein said hydrogenated block copolymer has at least one polymer block A and at least one polymer block B, and wherein (a.) prior to hydrogenation each A block independently is a mono alkenyl arene homopolymer block and each B block independently is a controlled distribution copolymer block of at least one conjugated diene and at least one mono alkenyl arene; (b.) subsequent to hydrogenation from 0-10 % of the arene double bonds have been reduced, and at least 90% of the conjugated diene double bonds have been reduced; (c.) each A block having a number average molecular weight between 3,000 and 60,000 and each B block having a number average molecular weight between 30,000 and 300,000;
  • the general configuration of the block copolymer is preferably one of A-B, A-B-A, (A-B) n , (A-B) n -A, (A-B-A) n X or (A-B) n X; where n is an integer from 2 to 30, preferably 2 to 15, more preferably 2 to 6, and X is coupling agent residue.
  • the key component of the present invention is the novel block copolymer containing mono alkenyl arene end blocks and a unique mid block of a mono alkenyl arene and a conjugated diene.
  • a unique control for the monomer addition and (2) the use of diethyl ether or other modifiers as a component of the solvent results in a certain characteristic distribution of the two monomers (herein termed a "controlled distribution" polymerization, i.e., a polymerization resulting in a "controlled distribution” structure) , and also results in the presence of certain mono alkenyl arene rich regions and certain conjugated diene rich regions in the polymer block.
  • controlled distribution is defined as referring to a molecular structure having the following attributes: (1) terminal regions adjacent to the mono alkenyl arene homopolymer ("A") blocks that are rich in (i.e., having a greater than average amount of) conjugated diene units; (2) one or more regions not adjacent to the A blocks that are rich in (i.e., having a greater than average number of) mono alkenyl arene units; and (3) an overall structure having relatively low blockiness.
  • “rich in” is defined as greater than the average amount, preferably greater than 5% of the average amount.
  • This relatively low blockiness can be shown by either the presence of only a single glass transition temperature (Tg) for the controlled distribution block intermediate between the Tg' s of either monomer alone, when analyzed using differential scanning calorimetry (“DSC”) thermal methods or via mechanical methods, or as shown via proton nuclear magnetic resonance (“H-NMR”) methods.
  • Tg glass transition temperature
  • DSC differential scanning calorimetry
  • H-NMR proton nuclear magnetic resonance
  • the potential for blockiness can also be inferred from measurement of the UV- visible absorbance in a wavelength range suitable for the detection of polystyryllithium end groups during the polymerization of the B block. A sharp and substantial increase in this value is indicative of a substantial increase in polystyryllithium chain ends. In this process, this will only occur if the conjugated diene concentration drops below the critical level to maintain controlled distribution polymerization.
  • styrene blockiness as measured by those skilled in the art using proton NMR, is defined to be the proportion of S units in the polymer having two S nearest neighbors on the polymer chain. The styrene blockiness is determined after using H-l NMR to measure two experimental quantities as follows:
  • the total number of styrene units is determined by integrating the total styrene aromatic signal in the H-l NMR spectrum from 7.5 to 6.2ppm and dividing this quantity by 5 to account for the 5 aromatic hydrogens on each styrene aromatic ring.
  • the blocky styrene units are determined by integrating that portion of the aromatic signal in the H-l NMR spectrum from the signal minimum between 6.88 and 6.80 to 6.2ppm and dividing this quantity by 2 to account for the 2 ortho hydrogens on each blocky styrene aromatic ring.
  • the assignment of this signal to the two ortho hydrogens on the rings of those styrene units which have two styrene nearest neighbors was reported in F. A . Bovey, High Resolution NMR of Macromolecules (Academic Press, New York and London , 1972) , chapter 6.
  • the styrene blockiness is simply the percentage of blocky styrene to total styrene units:
  • Blocky % 100 times (Blocky Styrene Units / Total Styrene Units)
  • Polymer-Bd-S- (S) n-S-Bd-Polymer where n is greater than zero is defined to be blocky styrene.
  • n 8 in the example above, then the blockiness index would be 80%. It is preferred that the blockiness index be less than 40. For some polymers, having styrene contents of ten weight percent to forty weight percent, it is preferred that the blockiness index be less than 10.
  • This controlled distribution structure is very important in managing the strength and Tg of the resulting copolymer, because the controlled distribution structure ensures that there is virtually no phase separation of the two monomers, i.e., in contrast with block copolymers in which the monomers actually remain as separate "microphases", with distinct Tg's, but are actually chemically bonded together.
  • This controlled distribution structure assures that only one Tg is present and that, therefore, the thermal performance of the resulting copolymer is predictable and, in fact, predeterminable .
  • the subject controlled distribution copolymer block has three distinct regions - conjugated diene rich regions on the end of the block and a mono alkenyl arene rich region near the middle or center of the block.
  • a mono alkenyl arene/conjugated diene controlled distribution copolymer block wherein the proportion of mono alkenyl arene units increases gradually to a maximum near the middle or center of the block and then decreases gradually until the polymer block is fully polymerized.
  • This structure is distinct and different from the tapered and/or random structures discussed in the prior art.
  • Starting materials for preparing the novel controlled distribution copolymers of the present invention include the initial monomers.
  • the alkenyl arene can be selected from styrene, alpha-methylstyrene, para-methylstyrene, vinyl toluene, vinylnaphthalene, and para-butyl styrene or mixtures thereof. Of these, styrene is most preferred and is commercially available, and relatively inexpensive, from a variety of manufacturers.
  • the conjugated dienes for use herein are 1, 3-butadiene and substituted butadienes such as isoprene, piperylene, 2 , 3-dimethyl-l, 3-butadiene, and 1- phenyl-1, 3-butadiene, or mixtures thereof. Of these, 1,3- butadiene is most preferred. As used herein, and in the claims, "butadiene” refers specifically to "1, 3-butadiene” .
  • the controlled distribution polymer block has diene rich region (s) adjacent to the A block and an arene rich region not adjacent to the A block, and typically near the center of the B block.
  • the region adjacent to the A block comprises the first 15 to 25% of the block and comprises the diene rich region (s), with the remainder considered to be arene rich.
  • the term "diene rich" means that the region has a measurably higher ratio of diene to arene than the arene rich region. Another way to express this is the proportion of mono alkenyl arene units increases gradually along the polymer chain to a maximum near the middle or center of the block (if we are describing an ABA structure) and then decreases gradually until the polymer block is fully polymerized.
  • the weight percent of mono alkenyl arene is between about 10 percent and about 75.
  • thermoplastic block copolymer is defined as a block copolymer having at least a first block of a mono alkenyl arene, such as styrene and a second block of a controlled distribution copolymer of diene and mono alkenyl arene.
  • the method to prepare this thermoplastic block copolymer is via any of the methods generally known for block polymerizations.
  • the present invention includes as an embodiment a thermoplastic copolymer composition, which may be either a di-block, tri-block copolymer or multi-block composition.
  • one block is the alkenyl arene-based homopolymer block and polymerized therewith is a second block of a controlled distribution copolymer of diene and alkenyl arene.
  • the tri-block composition it comprises, as end-blocks the glassy alkenyl arene-based homopolymer and as a mid-block the controlled distribution copolymer of diene and alkenyl arene.
  • the controlled distribution diene/alkenyl arene copolymer can be herein designated as "B” and the alkenyl arene-based homopolymer designated as "A".
  • the A-B-A, tri-block compositions can be made by either sequential polymerization or coupling.
  • the sequential solution polymerization technique the mono alkenyl arene is first introduced to produce the relatively hard aromatic block, followed by introduction of the controlled distribution diene/alkenyl arene mixture to form the mid block, and then followed by introduction of the mono alkenyl arene to form the terminal block.
  • the blocks can be structured to form a radial (branched) polymer, (A-B) n X, or both types of structures can be combined in a mixture.
  • Some A-B diblock polymer can be present but preferably at least about 30 weight percent of the block copolymer is A- B-A or radial (or otherwise branched so as to have 2 or more terminal resinous blocks per molecule) so as to impart strength.
  • desired block weights are 3,000 to 60,000 for the mono alkenyl arene A block, and 30,000 to 300,000 for the controlled distribution conjugated diene/mono alkenyl arene B block. Preferred ranges are 5000 to 45,000 for the A block and 50,000 to 250,000 for the B block.
  • the triblock which may be a sequential ABA or coupled (AB) 2 X block copolymer
  • the A blocks should be 3,000 to 60,000, preferably 5000 to 45,000
  • the B block for the sequential block should be about 30,000 to 300,000, and the B blocks (two) for the coupled polymer half that amount.
  • the total average molecular weight for the triblock copolymer should be from 40,000 to 400,000, and for the radial copolymer from 60,000 to 600,000. These molecular weights are most accurately determined by light scattering measurements, and are expressed as number average molecular weights.
  • Another important aspect of the present invention is to control the microstructure or vinyl content of the conjugated diene in the controlled distribution copolymer block.
  • the term "vinyl content" refers to a conjugated diene which is polymerized via 1,2-addition (in the case of butadiene - it would be 3,4-addition in the case of isoprene) .
  • 1,2-addition in the case of butadiene - it would be 3,4-addition in the case of isoprene
  • a pure "vinyl" group is formed only in the case of 1,2-addition polymerization of 1, 3-butadiene, the effects of 3,4-addition polymerization of isoprene (and similar addition for other conjugated dienes) on the final properties of the block copolymer will be similar.
  • vinyl refers to the presence of a pendant vinyl group on the polymer chain.
  • butadiene as the conjugated diene
  • This is effectively controlled by varying the relative amount of the distribution agent.
  • the distribution agent serves two purposes - it creates the controlled distribution of the mono alkenyl arene and conjugated diene, and also controls the microstructure of the conjugated diene.
  • thermoplastic elastomeric di-block and tri-block polymers of the present invention including one or more controlled distribution diene/alkenyl arene copolymer blocks and one or more mono alkenyl arene blocks, is that they have at least two Tg's, the lower being the combined Tg of the controlled distribution copolymer block which is an intermediate of its constituent monomers' Tg's.
  • Tg is preferably at least -60°C, more preferably from -40 to +30°C, and most preferably from -40 to + 10 °C.
  • the second Tg that of the mono alkenyl arene "glassy” block, is preferably more than 80°C, more preferably from 80 to 110°C.
  • the block copolymer is selectively hydrogenated. Hydrogenation can be carried out via any of the several hydrogenation or selective hydrogenation processes known in the prior art. For example, such hydrogenation has been accomplished using methods such as those taught in, for example, U.S. Patents 3,494,942; 3,634,594; 3,670,054; 3,700,633; and Re. 27,145. Hydrogenation can be carried out under such conditions that at least 90 percent of the conjugated diene double bonds have been reduced, and between zero and 10 percent of the arene double bonds have been reduced. Preferred ranges are at least 95 percent of the conjugated diene double bonds reduced, and more preferably 98 percent of the conjugated diene double bonds are reduced. Alternatively, it is possible to hydrogenate the polymer such that aromatic unsaturation is also reduced beyond the 10 percent level mentioned above. In that case, the double bonds of both the conjugated diene and arene may be reduced by 90 percent or more.
  • the block copolymer of the present invention may be functionalized in a number of ways.
  • One way is by treatment with an unsaturated monomer having one or more functional groups or their derivatives, such as carboxylic acid groups and their salts, anhydrides, esters, imide groups, amide groups, and acid chlorides.
  • the preferred monomers to be grafted onto the block copolymers are maleic anhydride, maleic acid, fumaric acid, and their derivatives.
  • a further description of functionalizing such block copolymers can be found in Gergen et al, U.S. Pat. No. 4,578,429 and in U. S. Pat. No. 5,506,299.
  • the selectively hydrogenated block copolymer of the present invention may be functionalized by grafting silicon or boron containing compounds to the polymer as taught in U.S. Pat. No. 4,882,384.
  • the block copolymer of the present invention may be contacted with an alkoxy-silane compound to form silane-modified block copolymer.
  • the block copolymer of the present invention may be functionalized by reacting at least one ethylene oxide molecule to the polymer as taught in U.S. Pat. No. 4,898,914, or by reacting the polymer with carbon dioxide as taught in U. S. pat. No. 4,970,265.
  • block copolymers of the present invention may be metallated as taught in U.S. Pat. Nos. 5,206,300 and 5,276,101, wherein the polymer is contacted with an alkali metal alkyl, such as a lithium alkyl.
  • the block copolymers of the present invention may be functionalized by grafting sulfonic groups to the polymer as taught in U. S. 5,516,831.
  • One of the components used in the oil gels of the present invention is a polymer extending oil or plasticizer.
  • oils that are compatible with the elastomeric segment of the block copolymer. While oils of higher aromatics content are satisfactory, those petroleum-based white oils having low volatility and less than 50% aromatic content are preferred. Such oils include both paraffinic and naphthenic oils.
  • the oils should additionally have low volatility, preferable having an initial boiling point above 260°C (500°F) .
  • plasticizers which may be used in the present invention are oligomers of randomly or sequentially polymerized styrene and conjugated diene, oligomers of conjugated diene, such as butadiene or isoprene, liquid polybutene-1, and ethylene-propylene-diene rubber, all having a weight average molecular weight in the range from 300 to 35,000, preferable less than 25,000 mol weight .
  • the amount of oil or plasticizer employed varies from 350 to 2000 parts by weight per hundred parts by weight rubber, or block copolymer, preferably 400 to 1000 parts by weight .
  • Suitable fillers include calcium carbonate, clay, talc, silica, zinc oxide, titanium dioxide and the like.
  • the amount of filler usually is in the range of 0 to 30% weight based on the formulation, depending on the type of filler used and the application for which the oil gel is intended.
  • compositions of the present invention may be modified further with the addition of other polymers, reinforcements, antioxidants, stabilizers, fire retardants, anti blocking agents, lubricants and other rubber and plastic compounding ingredients without departing from the scope of this invention.
  • Such components are disclosed in various patents including US Pat. No. 3,239,478; and US Pat. No 5,777,043, the disclosures of which are incorporated by reference.
  • compositions of the present invention may be designed for a wide variety of uses and applications. They may be applied as a water proofing encapsulant/sealant for electronics and in wire and cable applications, but also in the preparation of candles and the like.
  • CD Polymer refers to the controlled distribution polymer of the present invention:
  • Various controlled distribution block copolymers of the present invention were prepared according to the process disclosed in copending patent application Serial Number 60/355,210 referenced above, including it's continuing application filed concurrently. All polymers were selectively hydrogenated AB or ABA block copolymers where the A blocks were polystyrene blocks and the B block prior to hydrogenation was a styrene butadiene controlled distribution block having terminal regions that are rich in butadiene units and a center region that was rich in styrene units. The various polymers are shown in Table 1 below. These polymers were then used in the various applications described in the other Examples.
  • Step I MW is the molecular weight of the first A block
  • Step II MW is the molecular weight of the AB blocks
  • Step III MW is the molecular weight of the ABA blocks.
  • the polymers were hydrogenated such that greater than about 95% of the diene double bonds have been reduced.
  • Polymer #25 is a linear ABA tri-block copolymer having number average block mol weights of 9,500 - 80,000 - 9,500;
  • Polymer #27 is a linear ABA tri-block copolymer having block mol weights of 7,500 - 62,600 - 7,300;
  • Polymer #28 is an AB di-block copolymer having block mol weights of 7,800 - 31,500;
  • Polymer #26 is a linear ABA tri-block copolymer having block mol weights of 7,300 - 35,800 - 7,300.
  • Example 2 shows the use of the novel CD Polymer #25 in oil gels.
  • Samples #2-1, 202 and 2-3 show the properties of gels based on a conventional hydrogenated SBC, SEBS #1.
  • SEBS #1 is a selectively hydrogenated SBS block copolymer having polystyrene end blocks of about 10,000 and a hydrogenated polybutadiene mid block of about 50,000. Results show that the polymer content increases, softening point and tensile properties improve and melt viscosity increases.
  • Samples #2-4, 2-5, and 2-6 show that the same trend is found using CD Polymer #25. Surprisingly, however, CD Polymer #25 gives the gel higher tensile strength and higher elongation than the conventional hydrogenated polymer.
  • DRAKEOL 34 is available from Penreco and is a paraffinic processing oil have a Tg of -64° C.

Abstract

The present invention relates to gels prepared from novel anionic block copolymers of mono alkenyl arenes and conjugated dienes. The block copolymers are selectively hydrogenated and have mono alkenyl arene end blocks and controlled distribution blocks of mono alkenyl arenes and conjugated dienes. The block copolymer may be combined with oils and other components to form the gels of the present invention.

Description

GELS FROM CONTROLLED DISTRIBUTION BLOCK COPOLYMERS
Field of the Invention
[0001] This invention relates to gels prepared from novel anionic block copolymers of mono alkenyl arenes and conjugated dienes.
Background of the Art
[0002] The preparation of block copolymers of mono alkenyl arenes and conjugated dienes is well known. One of the first patents on linear ABA block copolymers made with styrene and butadiene is U.S. Pat. 3,149,182. These polymers in turn could be hydrogenated to form more stable block copolymers, such as those described in U.S. Pat. 3,595,942 and U.S. Re. 27,145. Such polymers are broadly termed Styrenic Block Copolymers or SBC's.
[0003] SBC's have a long history of use as adhesives, sealants and gels. A recent example of a gel may be found in US patent No. 5,879,694. With the increase use of oil gels, which have become a popular gift as candles, the need for increased properties (expressed in terms of higher tensile strength and higher elongation) exist. This invention comprises a new class of SBC s in which the polymer manufacturer can vary the compatibility characteristics of the rubber segment, resulting in improved oil gels. Such gels may also be used, for example, as a water proofing encapsulant/sealant for electronics and in wire and cable applications
[0004] Now a novel anionic block copolymer based on mono alkenyl arene end blocks and controlled distribution mid blocks of mono alkenyl arenes and conjugated dienes has been discovered and is described in copending, commonly assigned U.S. patent application Serial Number 60/355,210, entitled "NOVEL BLOCK COPOLYMERS AND METHOD FOR MAKING SAME". Methods for making such polymers are described in detail in the above-mentioned patent application. Patentees have found that these new polymers will allow the preparation of improved oil gels.
Summary of the Invention
[0005] In one aspect of the present invention we have discovered a novel oil gel composition comprising 100 parts by weight of at least one hydrogenated block copolymer having a controlled distribution block of a mono alkenyl arene and conjugated diene, and from 350 to 2000 parts by weight of an extender oil, wherein said hydrogenated block copolymer has at least one polymer block A and at least one polymer block B, and wherein (a.) prior to hydrogenation each A block independently is a mono alkenyl arene homopolymer block and each B block independently is a controlled distribution copolymer block of at least one conjugated diene and at least one mono alkenyl arene; (b.) subsequent to hydrogenation from 0-10 % of the arene double bonds have been reduced, and at least 90% of the conjugated diene double bonds have been reduced; (c.) each A block having a number average molecular weight between 3,000 and 60,000 and each B block having a number average molecular weight between 30,000 and 300,000; (d.) each B block comprises terminal regions adjacent to the A blocks that are rich in conjugated diene units and one or more regions not adjacent to the A blocks that are rich in mono alkenyl arene units; (e.) the total amount of mono alkenyl arene in the hydrogenated block copolymer is from 20 to 80 percent weight; and (f.) the weight percent of mono alkenyl arene in each B block is between 10 and 75 percent.
[0006] The general configuration of the block copolymer is preferably one of A-B, A-B-A, (A-B)n, (A-B)n-A, (A-B-A)nX or (A-B)nX; where n is an integer from 2 to 30, preferably 2 to 15, more preferably 2 to 6, and X is coupling agent residue. Detailed Description of the Preferred Embodiments
[0007] The key component of the present invention is the novel block copolymer containing mono alkenyl arene end blocks and a unique mid block of a mono alkenyl arene and a conjugated diene. Surprisingly, the combination of (1) a unique control for the monomer addition and (2) the use of diethyl ether or other modifiers as a component of the solvent (which will be referred to as "distribution agents") results in a certain characteristic distribution of the two monomers (herein termed a "controlled distribution" polymerization, i.e., a polymerization resulting in a "controlled distribution" structure) , and also results in the presence of certain mono alkenyl arene rich regions and certain conjugated diene rich regions in the polymer block. For purposes hereof, "controlled distribution" is defined as referring to a molecular structure having the following attributes: (1) terminal regions adjacent to the mono alkenyl arene homopolymer ("A") blocks that are rich in (i.e., having a greater than average amount of) conjugated diene units; (2) one or more regions not adjacent to the A blocks that are rich in (i.e., having a greater than average number of) mono alkenyl arene units; and (3) an overall structure having relatively low blockiness. For the purposes hereof, "rich in" is defined as greater than the average amount, preferably greater than 5% of the average amount. This relatively low blockiness can be shown by either the presence of only a single glass transition temperature (Tg) for the controlled distribution block intermediate between the Tg' s of either monomer alone, when analyzed using differential scanning calorimetry ("DSC") thermal methods or via mechanical methods, or as shown via proton nuclear magnetic resonance ("H-NMR") methods. The potential for blockiness can also be inferred from measurement of the UV- visible absorbance in a wavelength range suitable for the detection of polystyryllithium end groups during the polymerization of the B block. A sharp and substantial increase in this value is indicative of a substantial increase in polystyryllithium chain ends. In this process, this will only occur if the conjugated diene concentration drops below the critical level to maintain controlled distribution polymerization. Any styrene monomer that is present at this point will add in a blocky fashion. The term "styrene blockiness", as measured by those skilled in the art using proton NMR, is defined to be the proportion of S units in the polymer having two S nearest neighbors on the polymer chain. The styrene blockiness is determined after using H-l NMR to measure two experimental quantities as follows:
First, the total number of styrene units (i.e. arbitrary instrument units which cancel out when ratioed) is determined by integrating the total styrene aromatic signal in the H-l NMR spectrum from 7.5 to 6.2ppm and dividing this quantity by 5 to account for the 5 aromatic hydrogens on each styrene aromatic ring.
Second, the blocky styrene units are determined by integrating that portion of the aromatic signal in the H-l NMR spectrum from the signal minimum between 6.88 and 6.80 to 6.2ppm and dividing this quantity by 2 to account for the 2 ortho hydrogens on each blocky styrene aromatic ring. The assignment of this signal to the two ortho hydrogens on the rings of those styrene units which have two styrene nearest neighbors was reported in F. A . Bovey, High Resolution NMR of Macromolecules (Academic Press, New York and London , 1972) , chapter 6.
The styrene blockiness is simply the percentage of blocky styrene to total styrene units:
Blocky % = 100 times (Blocky Styrene Units / Total Styrene Units)
Expressed thus, Polymer-Bd-S- (S) n-S-Bd-Polymer, where n is greater than zero is defined to be blocky styrene. For example, if n equals 8 in the example above, then the blockiness index would be 80%. It is preferred that the blockiness index be less than 40. For some polymers, having styrene contents of ten weight percent to forty weight percent, it is preferred that the blockiness index be less than 10.
[0008] This controlled distribution structure is very important in managing the strength and Tg of the resulting copolymer, because the controlled distribution structure ensures that there is virtually no phase separation of the two monomers, i.e., in contrast with block copolymers in which the monomers actually remain as separate "microphases", with distinct Tg's, but are actually chemically bonded together. This controlled distribution structure assures that only one Tg is present and that, therefore, the thermal performance of the resulting copolymer is predictable and, in fact, predeterminable . Furthermore, when a copolymer having such a controlled distribution structure is then used as one block in a di- block, tri-block or multi-block copolymer, the relatively higher Tg made possible by means of the presence of an appropriately-constituted controlled distribution copolymer region will tend to improve flow and processability . Modification of certain other properties is also achievable.
[0009] In a preferred embodiment of the present invention, the subject controlled distribution copolymer block has three distinct regions - conjugated diene rich regions on the end of the block and a mono alkenyl arene rich region near the middle or center of the block. What is desired is a mono alkenyl arene/conjugated diene controlled distribution copolymer block, wherein the proportion of mono alkenyl arene units increases gradually to a maximum near the middle or center of the block and then decreases gradually until the polymer block is fully polymerized. This structure is distinct and different from the tapered and/or random structures discussed in the prior art. [0010] Starting materials for preparing the novel controlled distribution copolymers of the present invention include the initial monomers. The alkenyl arene can be selected from styrene, alpha-methylstyrene, para-methylstyrene, vinyl toluene, vinylnaphthalene, and para-butyl styrene or mixtures thereof. Of these, styrene is most preferred and is commercially available, and relatively inexpensive, from a variety of manufacturers. The conjugated dienes for use herein are 1, 3-butadiene and substituted butadienes such as isoprene, piperylene, 2 , 3-dimethyl-l, 3-butadiene, and 1- phenyl-1, 3-butadiene, or mixtures thereof. Of these, 1,3- butadiene is most preferred. As used herein, and in the claims, "butadiene" refers specifically to "1, 3-butadiene" .
[0011] As discussed above, the controlled distribution polymer block has diene rich region (s) adjacent to the A block and an arene rich region not adjacent to the A block, and typically near the center of the B block. Typically the region adjacent to the A block comprises the first 15 to 25% of the block and comprises the diene rich region (s), with the remainder considered to be arene rich. The term "diene rich" means that the region has a measurably higher ratio of diene to arene than the arene rich region. Another way to express this is the proportion of mono alkenyl arene units increases gradually along the polymer chain to a maximum near the middle or center of the block (if we are describing an ABA structure) and then decreases gradually until the polymer block is fully polymerized. For the controlled distribution block B the weight percent of mono alkenyl arene is between about 10 percent and about 75.
[0012] As used herein, "thermoplastic block copolymer" is defined as a block copolymer having at least a first block of a mono alkenyl arene, such as styrene and a second block of a controlled distribution copolymer of diene and mono alkenyl arene. The method to prepare this thermoplastic block copolymer is via any of the methods generally known for block polymerizations. The present invention includes as an embodiment a thermoplastic copolymer composition, which may be either a di-block, tri-block copolymer or multi-block composition. In the case of the di-block copolymer composition, one block is the alkenyl arene-based homopolymer block and polymerized therewith is a second block of a controlled distribution copolymer of diene and alkenyl arene. In the case of the tri-block composition, it comprises, as end-blocks the glassy alkenyl arene-based homopolymer and as a mid-block the controlled distribution copolymer of diene and alkenyl arene. Where a tri-block copolymer composition is prepared, the controlled distribution diene/alkenyl arene copolymer can be herein designated as "B" and the alkenyl arene-based homopolymer designated as "A". The A-B-A, tri-block compositions can be made by either sequential polymerization or coupling. In the sequential solution polymerization technique, the mono alkenyl arene is first introduced to produce the relatively hard aromatic block, followed by introduction of the controlled distribution diene/alkenyl arene mixture to form the mid block, and then followed by introduction of the mono alkenyl arene to form the terminal block. In addition to the linear, A-B-A configuration, the blocks can be structured to form a radial (branched) polymer, (A-B)nX, or both types of structures can be combined in a mixture. Some A-B diblock polymer can be present but preferably at least about 30 weight percent of the block copolymer is A- B-A or radial (or otherwise branched so as to have 2 or more terminal resinous blocks per molecule) so as to impart strength.
[0013] It is also important to control the molecular weight of the various blocks. For an AB diblock, desired block weights are 3,000 to 60,000 for the mono alkenyl arene A block, and 30,000 to 300,000 for the controlled distribution conjugated diene/mono alkenyl arene B block. Preferred ranges are 5000 to 45,000 for the A block and 50,000 to 250,000 for the B block. For the triblock, which may be a sequential ABA or coupled (AB)2 X block copolymer, the A blocks should be 3,000 to 60,000, preferably 5000 to 45,000, while the B block for the sequential block should be about 30,000 to 300,000, and the B blocks (two) for the coupled polymer half that amount. The total average molecular weight for the triblock copolymer should be from 40,000 to 400,000, and for the radial copolymer from 60,000 to 600,000. These molecular weights are most accurately determined by light scattering measurements, and are expressed as number average molecular weights.
[0014] Another important aspect of the present invention is to control the microstructure or vinyl content of the conjugated diene in the controlled distribution copolymer block. The term "vinyl content" refers to a conjugated diene which is polymerized via 1,2-addition (in the case of butadiene - it would be 3,4-addition in the case of isoprene) . Although a pure "vinyl" group is formed only in the case of 1,2-addition polymerization of 1, 3-butadiene, the effects of 3,4-addition polymerization of isoprene (and similar addition for other conjugated dienes) on the final properties of the block copolymer will be similar. The term "vinyl" refers to the presence of a pendant vinyl group on the polymer chain. When referring to the use of butadiene as the conjugated diene, it is preferred that from 20 to 80 mol percent of the condensed butadiene units in the copolymer block have 1,2 vinyl configuration as determined by proton NMR analysis, preferably from 30 to 70 mol percent of the condensed butadiene units should have 1,2-vinyl configuration. This is effectively controlled by varying the relative amount of the distribution agent. As will be appreciated, the distribution agent serves two purposes - it creates the controlled distribution of the mono alkenyl arene and conjugated diene, and also controls the microstructure of the conjugated diene. Suitable ratios of distribution agent to lithium are disclosed and taught in US Pat. Re 27,145, which disclosure is incorporated by reference. [0015] An important feature of the thermoplastic elastomeric di-block and tri-block polymers of the present invention, including one or more controlled distribution diene/alkenyl arene copolymer blocks and one or more mono alkenyl arene blocks, is that they have at least two Tg's, the lower being the combined Tg of the controlled distribution copolymer block which is an intermediate of its constituent monomers' Tg's. Such Tg is preferably at least -60°C, more preferably from -40 to +30°C, and most preferably from -40 to + 10 °C. The second Tg, that of the mono alkenyl arene "glassy" block, is preferably more than 80°C, more preferably from 80 to 110°C. The presence of the two Tg's, illustrative of the microphase separation of the blocks, contributes to the notable elasticity and strength of the material in a wide variety of applications, and its ease of processing and desirable melt-flow characteristics.
[0016] The block copolymer is selectively hydrogenated. Hydrogenation can be carried out via any of the several hydrogenation or selective hydrogenation processes known in the prior art. For example, such hydrogenation has been accomplished using methods such as those taught in, for example, U.S. Patents 3,494,942; 3,634,594; 3,670,054; 3,700,633; and Re. 27,145. Hydrogenation can be carried out under such conditions that at least 90 percent of the conjugated diene double bonds have been reduced, and between zero and 10 percent of the arene double bonds have been reduced. Preferred ranges are at least 95 percent of the conjugated diene double bonds reduced, and more preferably 98 percent of the conjugated diene double bonds are reduced. Alternatively, it is possible to hydrogenate the polymer such that aromatic unsaturation is also reduced beyond the 10 percent level mentioned above. In that case, the double bonds of both the conjugated diene and arene may be reduced by 90 percent or more.
[0017] In an alternative, the block copolymer of the present invention may be functionalized in a number of ways. One way is by treatment with an unsaturated monomer having one or more functional groups or their derivatives, such as carboxylic acid groups and their salts, anhydrides, esters, imide groups, amide groups, and acid chlorides. The preferred monomers to be grafted onto the block copolymers are maleic anhydride, maleic acid, fumaric acid, and their derivatives. A further description of functionalizing such block copolymers can be found in Gergen et al, U.S. Pat. No. 4,578,429 and in U. S. Pat. No. 5,506,299. In another manner the selectively hydrogenated block copolymer of the present invention may be functionalized by grafting silicon or boron containing compounds to the polymer as taught in U.S. Pat. No. 4,882,384. In still another manner, the block copolymer of the present invention may be contacted with an alkoxy-silane compound to form silane-modified block copolymer. In yet another manner, the block copolymer of the present invention may be functionalized by reacting at least one ethylene oxide molecule to the polymer as taught in U.S. Pat. No. 4,898,914, or by reacting the polymer with carbon dioxide as taught in U. S. pat. No. 4,970,265. Still further, the block copolymers of the present invention may be metallated as taught in U.S. Pat. Nos. 5,206,300 and 5,276,101, wherein the polymer is contacted with an alkali metal alkyl, such as a lithium alkyl. And still further, the block copolymers of the present invention may be functionalized by grafting sulfonic groups to the polymer as taught in U. S. 5,516,831.
[0018] One of the components used in the oil gels of the present invention is a polymer extending oil or plasticizer. Especially preferred are the types of oils that are compatible with the elastomeric segment of the block copolymer. While oils of higher aromatics content are satisfactory, those petroleum-based white oils having low volatility and less than 50% aromatic content are preferred. Such oils include both paraffinic and naphthenic oils. The oils should additionally have low volatility, preferable having an initial boiling point above 260°C (500°F) .
[0019] Examples of alternative plasticizers which may be used in the present invention are oligomers of randomly or sequentially polymerized styrene and conjugated diene, oligomers of conjugated diene, such as butadiene or isoprene, liquid polybutene-1, and ethylene-propylene-diene rubber, all having a weight average molecular weight in the range from 300 to 35,000, preferable less than 25,000 mol weight .
[0020] The amount of oil or plasticizer employed varies from 350 to 2000 parts by weight per hundred parts by weight rubber, or block copolymer, preferably 400 to 1000 parts by weight .
[0021] Various types of fillers and pigments can be included in the oil gel formulations to pigment the oil gel and reduce cost. Suitable fillers include calcium carbonate, clay, talc, silica, zinc oxide, titanium dioxide and the like. The amount of filler usually is in the range of 0 to 30% weight based on the formulation, depending on the type of filler used and the application for which the oil gel is intended.
[0022] The compositions of the present invention may be modified further with the addition of other polymers, reinforcements, antioxidants, stabilizers, fire retardants, anti blocking agents, lubricants and other rubber and plastic compounding ingredients without departing from the scope of this invention. Such components are disclosed in various patents including US Pat. No. 3,239,478; and US Pat. No 5,777,043, the disclosures of which are incorporated by reference.
[0023] The compositions of the present invention may be designed for a wide variety of uses and applications. They may be applied as a water proofing encapsulant/sealant for electronics and in wire and cable applications, but also in the preparation of candles and the like.
[0024] Regarding the relative amounts of the various ingredients, this will depend in part upon the particular end use and on the particular block copolymer that is selected for the particular end use. Table A below shows some notional compositions that are included in the present invention. "CD Polymer" refers to the controlled distribution polymer of the present invention:
Table A: Applications, Compositions and Ranges
Figure imgf000013_0001
Examples
[0025] The following examples are provided to illustrate the present invention. The examples are not intended to limit the scope of the present invention and they should not be so interpreted. Amounts are in weight parts or weight percentages unless otherwise indicated. The test methods used in the examples are American Society for Testing Materials (ASTM) test methods, and the following specific methods were used:
Ring & ball Softening point ASTM D-36 Melt Viscosity ASTM D-3236 Tensile Properties ASTM D-412
Example 1
[0026] Various controlled distribution block copolymers of the present invention were prepared according to the process disclosed in copending patent application Serial Number 60/355,210 referenced above, including it's continuing application filed concurrently. All polymers were selectively hydrogenated AB or ABA block copolymers where the A blocks were polystyrene blocks and the B block prior to hydrogenation was a styrene butadiene controlled distribution block having terminal regions that are rich in butadiene units and a center region that was rich in styrene units. The various polymers are shown in Table 1 below. These polymers were then used in the various applications described in the other Examples. Step I MW is the molecular weight of the first A block, Step II MW is the molecular weight of the AB blocks and Step III MW is the molecular weight of the ABA blocks. The polymers were hydrogenated such that greater than about 95% of the diene double bonds have been reduced. [0027]
Table 1. Controlled Distribution Polymers
Figure imgf000014_0001
where "MW(k)" = molecular weight in thousands and "PSC(%)" = wt % of styrene in the final polymer. "Styrene Blockiness" is for just the B block.
Accordingly, Polymer #25 is a linear ABA tri-block copolymer having number average block mol weights of 9,500 - 80,000 - 9,500; Polymer #27 is a linear ABA tri-block copolymer having block mol weights of 7,500 - 62,600 - 7,300; Polymer #28 is an AB di-block copolymer having block mol weights of 7,800 - 31,500; and Polymer #26 is a linear ABA tri-block copolymer having block mol weights of 7,300 - 35,800 - 7,300. Example 2
[0028] Example 2 shows the use of the novel CD Polymer #25 in oil gels. Samples #2-1, 202 and 2-3 show the properties of gels based on a conventional hydrogenated SBC, SEBS #1. SEBS #1 is a selectively hydrogenated SBS block copolymer having polystyrene end blocks of about 10,000 and a hydrogenated polybutadiene mid block of about 50,000. Results show that the polymer content increases, softening point and tensile properties improve and melt viscosity increases. Samples #2-4, 2-5, and 2-6 show that the same trend is found using CD Polymer #25. Surprisingly, however, CD Polymer #25 gives the gel higher tensile strength and higher elongation than the conventional hydrogenated polymer. DRAKEOL 34 is available from Penreco and is a paraffinic processing oil have a Tg of -64° C.
Table 2
Composition, %w #2-1 #2-2 #2-3 #2-4 #2-5 #2-6
DRAKEOL 34 90 85 80 90 85 80
SEBS #1 10 15 20
CD Polymer #25 10 15 20
Melt Vis @ 149oC, 185 750 3,870 235 2210 17,500 mPa . s (cps)
R&B Softening Pt, 85 96 106 89 104 117
°C
Tensile Strength, too 117 352 too 128 545 kPa (psi) soft (17) (51) soft (18. 5) (79)
Elongation @ Break, 280 540 460 760

Claims

1. An oil gel composition comprising 100 parts by weight of at least one hydrogenated block copolymer having a controlled distribution block of a mono alkenyl arene and conjugated diene, and from 350 to 2000 parts by weight of an extender oil, wherein said hydrogenated block copolymer has at least one polymer block A and at least one polymer block B, and wherein (a.) prior to hydrogenation each A block independently is a mono alkenyl arene homopolymer block and each B block independently is a controlled distribution copolymer block of at least one conjugated diene and at least one mono alkenyl arene; (b.) subsequent to hydrogenation from 0-10 % of the arene double bonds have been reduced, and at least 90% of the conjugated diene double bonds have been reduced; (c.) each A block having a number average molecular weight between 3,000 and 60,000 and each B block having a number average molecular weight between 30,000 and 300,000; (d.) each B block comprises terminal regions adjacent to the A blocks that are rich in conjugated diene units and one or more regions not adjacent to the A blocks that are rich in mono alkenyl arene units;
(e.) the total amount of mono alkenyl arene in the hydrogenated block copolymer is from 20 to 80 percent weight; and (f.) the weight percent of mono alkenyl arene in each B block is between 10 and 75 percent.
2. The oil gel composition according to Claim 1 wherein said mono alkenyl arene is styrene and said conjugated diene is selected from isoprene and butadiene.
3. The oil gel composition according to Claim 1 or 2 wherein said conjugated diene is butadiene, and wherein 20 to 80 mol percent of the condensed butadiene units in block B have 1, 2-configuration.
4. The oil gel composition according to any one of Claims 1 to 3 wherein the styrene blockiness of the block B is less than 40 mol percent percent, said styrene blockiness index being defined to be the proportion of styrene units in the block B having two styrene neighbors on the polymer chain.
5. The oil gel composition according to any one of Claims 1 to 4 wherein the weight percent of styrene in each B block is between 10 percent and 30 percent, and the styrene blockiness index of each block B is less than 10.
6. The oil gel composition according to any one of Claims 1 to 5 wherein said hydrogenated block copolymer is an ABA, (A-B)n, (A-B)nA, or (A-B)nX block copolymer where n is an integer from 2 to 30, X is the coupling agent residue, said block copolymer having a total molecular weight of 40,000 to 140,000 and wherein each B block has between 10 and 30 weight percent styrene.
7. The oil gel composition according to any one of Claims 1 to 6 wherein said extender oil is a petroleum-based white oil having low volatility and less than 50% aromatic content .
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