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    • 专利摘要:
    Butyl polymers with improved processability are described along with their preparation. The butyl polymer may comprise (i) a monomer mixture comprising C 4 to C 7 monoolefin monomers (preferably isobutylene) and C 4 to C 14 multiolefin monomers (preferably isofene); (ii) multiolefin crosslinkers (preferably divinyl benzene); And (iii) a chain transfer agent (preferably diisobutylene (2,4,4-trimethyl-1-pentene)). These butyl polymers have a harmonious improvement in low temperature flow, filler dispersion, extrusion rate and die expansion.
    公开号:KR20030031990A
    申请号:KR10-2003-7002611
    申请日:2001-08-21
    公开日:2003-04-23
    发明作者:가버 카스자스
    申请人:바이엘 인크.；
    IPC主号:
    专利说明:

    Butyl rubber with improved processability and its manufacturing method {Improved Processability Butyl Rubber and Process for Production
    [1] One aspect of the present invention relates to a butyl polymer with improved processability. Another aspect of the present invention relates to a method for preparing the butyl polymer.
    [2] Butyl polymers or rubbers are known in the art and are used in particular for tire production.
    [3] The terms butyl polymer and butyl rubber are terms known in the art and used interchangeably and relate to copolymers of isoolefins and conjugated dienes as described in more detail below. Commercially available butyl polymers are generally prepared by low temperature cation polymerization processes using Lewis acid-type catalysts, the typical examples of which are aluminum trichloride. The most widely used method uses methyl chloride as the diluent for the reaction mixture, and the polymerization is carried out at a temperature on the order of less than -90 ° C, as a result of which the polymer is prepared in a slurry of diluent. Or diluents (eg, hydrocarbons such as pentane, hexane, heptane, etc.) which serve as solvents for the polymers. The product polymer can be recovered using conventional techniques of rubber polymer recovery.
    [4] Elastomers undergo a number of manipulations in the process for making rubber articles. It is exposed to various shear rates and stresses during operations such as storage, mixing, milling, calendering, extrusion, injection molding and forming. The rheological properties of the elastomer in pure or blended form are important in view of processability. These rheological properties are ultimately determined by the structural properties of the elastomer. As for the processability problem of the polymer and its relation to the rheological and structural properties, for example, J. L. J. L. White and Y. N. Tokita, J. Applied Polymer Science, vol. 11, pp. 321-334 (1967) or Jay. White, Rubber Chem. Technol, vol. 50, pp 163-185 (1976).
    [5] Requirements at different stages of processing often contradict each other. For example, the polymer is required to have a certain strength to prevent cold flow during storage or transportation. Higher elastic or wet strength may also be beneficial to prevent excessive flow of the compound being formed or formed in the forming operation. In this respect high viscosity materials exhibiting high elastic memory are preferred. It is generally recognized that the low temperature flow protection can be improved by raising the molecular weight of the polymer or increasing the long chain branching. In contrast, during extrusion or injection molding, it is often desirable for the polymer to have low viscosity and reduced elasticity to ensure high extrusion speed and dimensional stability. Rapid relaxation of stress during these operations is also desirable so that the shape of the extruded article does not change during handling after extrusion of the material. Increasing molecular weight or long chain branching can have a negative impact on these manipulations because they increase elasticity. Very high elastic memory can also make it difficult to incorporate filler into the mixer or mill.
    [6] In addition to molecular weight and long chain branching, the molecular weight distribution (MWD) of the elastomer is also important. For example, narrow molecular weight distributions are believed to cause the elastomer to break in mills or mixers. Expanding MWD can help solve these problems. However, as the MWD becomes wider, the elasticity of the polymer will increase, resulting in increased die expansion or compound shrinkage.
    [7] Dynamic tests are often used to analyze rheological and processability properties of polymers. The main figures resulting from the dynamic tests are storage modulus (G '), loss modulus (G ") and tan delta (tan δ). Storage modulus is a measure of stored energy or elasticity. The tangential delta is the ratio of the two modulus (tan δ = G ″ / G ′). Higher tan δ indicates that the sample will flow under stress rather than storing the energy it is exposed to. Conversely, lower tan δ values will result in increased elasticity without the sample flowing. Plotting the logarithm of tan δ as a function of angular frequency (ω) provides very important information about the rheological properties of the polymer. The slope of this curve may also be related to the molecular weight distribution and long chain branching of the polymer. In general, it is believed that this decrease in slope indicates an increase in long chain branching or broadening the molecular weight distribution. As the degree of branching increases, the slope decreases and eventually goes to zero. The polymer is known to have a frequency dependent tan delta at or near the gel point. To get more information, for example H. H. H. H. Winter, "Gel Point" in Encyclopedia of Polymer Science and Engineering, Supplement Volume, John Wiley & Sons, Inc. pp. 343-351 (1989)], H. H .. Seed. H. C. Booji, Kautschuk and Gummi Kunststoffe, Vol. 44, No. 2, pp. 128-130 (1991).
    [8] The prior art includes many examples of improving processability of elastomers. As noted above, increasing long chain branching can reduce cold flow. One way to increase long chain branching is to introduce polyvalent monomers such as divinyl benzene (DVB) into the polymer mixture. Addition of DVB to the polymer mixture will cause branching of the straight chain and broaden the molecular weight distribution. The use of very low concentrations of DVB will form an almost straight chain with only a few hanging vinyl aromatic groups. However, some growing chain will react with these hanging groups and the chain will grow, resulting in the formation of X-type molecules. This will also double the molecular weight of the resulting polymer and broaden the molecular weight distribution as the linear and X-type polymers coexist. As the DVB concentration rises, more chains will participate in this branching reaction and the increase in their number will allow them to react with one or more hanging groups. This process will cause several explosions in molecular weight, with each explosion creating a new “population”. However, because of the statistical nature of the polymerization reaction, the final product is not uniform and will be a mixture of these various “pops”. There will still be a straight chain in the final product along with Form X and other “populations” that exhibit higher degrees of branching. Increasing the amount of DVB further will form a gel. The gel content will depend on the amount of DVB added to the polymerization mixture.
    [9] US Patent No. 2,781,334 (Welch et al. (Welch # 1)) teaches the use of divinyl benzene in the preparation of butyl polymers to improve the wet strength of the polymers produced. In particular, Welch # 1 teaches the addition of a small amount of DVB (0.1-0.8% by weight, preferably 0.4-0.8% by weight) to the polymerization system to yield an oil soluble, low gel, interpolymer. The physical properties are intentionally improved by reducing the polymer cold flow. However, a decrease in extrusion speed and an increase in die expansion were also observed. This may be due to the increase in molecular weight and the long chain branching caused by the DVB incorporation.
    [10] U.S. Patent No. 2,729,626 [Welch et al. (Welch # 2) teaches the preparation of substantially insoluble terpolymers using 0.8-4 weight percent DVB in monomer feeds. This terpolymer can be used intentionally to produce vulcanized products with improved physical properties for modulus values. It has also been claimed that copolymers comprising up to about 4% DVB have an extrusion rate high enough to allow extrusion to be practically carried out.
    [11] US Pat. No. 2,671,744 (McCracken et al. (Macraken)) teaches the preparation of products made using 4-10% by weight of DVB in monomer feeds. The product comprises at least 80% gel. The mclagen teaches that the cold flow of these products is significantly reduced. Extrusion rates that can be achieved are much higher than unmodified polymers and die expansion is reduced. The mclaken also teaches that blends of product terpolymers with isoolefin-multiolefin copolymers are also very useful. However, the presence of gels in the polymer also leads to degradation of the curing properties (see Table II of McLaken). For example, tensile strength and elongation of hardened rubber are reduced. This is not surprising because partially crosslinked rubber does not mix homogeneously with the curing agent and filler. In general, the presence of gels, especially in large amounts, in interpolymers, such as butyl polymers, is undesirable because it may make it difficult to uniformly disperse the fillers and hardeners commonly used during vulcanization. This increases the likelihood of uncured or excessively hardened parts inside the rubber article, making the physical properties inferior and unpredictable.
    [12] These examples show that cold flow can be reduced by increasing long chain branching by the use of polyvalent monomers. However, this has a negative effect on other aspects of processability, and gels can form during the polymerization. High gel content leads to inferior properties of the product. In certain cases the use of polyhydric polymers is mentioned in an undesirable way. For example, British Patent No. 1,143,690 teaches that reducing cold flow with a chemical crosslinker having a multivalent group inevitably leads to deterioration of rubber product performance and sometimes to a significant decrease in processability. This is confirmed by the comparative example in which DVB is used. The product obtained with DVB shows an improved low temperature flow but its millability is significantly lowered.
    [13] U.S. Patent No. 5,071,13 (Powers et al. (Powers)) indicates that well- harmonized processing characteristics (reduced low temperature flow and high extrusion rate) can be achieved by adding an effective amount of a working reagent to the polymerization mixture. Teach The reagents are selected from the group consisting of polymers and copolymers comprising functional groups capable of copolymerizing or forming chemical bonds with the resulting polymer—see column 16, line 24 to column 17, 19 of the above Powers. The Powers mentioned prior art related to DVB-modified butyl rubber and were characterized as defective because the prior art relates to polymers having a high gel content in the polymer product. Powers especially prefers reagents, such as cationic activators, which do not contain active branching (crosslinking) functional groups, ie they cannot proceed further when the growing butyl chain is attached to the reaction site of the additive. See lines 15 and 14. The Powers did not teach or suggest using a crosslinker during the manufacture of the butyl polymer and in the examples preferred polymer modifiers which tend to terminate the chain after attachment.
    [14] Despite advances in the art, cold flow (reduced) at high shear rates, (higher) wet strength, (faster) filler incorporation, (higher) filler dispersion, (higher) stress relaxation rates And butyl rubber with harmonically improved melt viscosity (lower).
    [15] It is an object of the present invention to solve or alleviate one or more of the above disadvantages of the prior art.
    [16] Another object of the present invention is to provide a novel butyl polymer.
    [17] Another object of the present invention is to provide a novel process for preparing butyl polymer.
    [18] Another object of the present invention is to provide a method for preventing gel formation when a multivalent crosslinker is used in the polymerization.
    [19] It is another object of the present invention to provide a method of intentionally altering the rheological properties of butyl polymer to achieve optimum performance in a given set of processing equipment.
    [20] Accordingly, one aspect of the present invention is to provide a butyl polymer having improved processability, wherein the butyl polymer
    [21] (i) monomer mixtures comprising C 4 to C 7 monoolefin monomers and C 4 to C 14 multiolefin monomers or β-pinene;
    [22] (ii) multiolefin crosslinkers; And
    [23] (iii) derived from a reaction mixture comprising a chain transfer agent.
    [24] Another aspect of the present invention is to provide a method for producing a butyl polymer with improved processability, the method
    [25] (a) a monomer mixture comprising C 4 to C 7 monoolefin monomers and C 4 to C 14 multiolefin monomers or β-pinene;
    [26] (b) multiolefin crosslinkers;
    [27] (c) chain transfer agents; And
    [28] (d) contacting the reaction mixture comprising the catalyst system.
    [29] Therefore, the present invention relates to a butyl rubber polymer. The terms "butyl rubber", "butyl polymer" and "butyl rubber polymer" are used interchangeably throughout this specification and refer to C 4 to C 7 monoolefin monomers and C 4 to C 14 multiolefin monomers or β-pinene, respectively. It refers to a polymer prepared by reacting a monomer mixture comprising. The butyl polymer can be halogenated or nonhalogenated. In addition, the monomer mixture may comprise small amounts of one or more polymerizable comonomers.
    [30] It has been surprisingly found that by adding multiolefin crosslinkers and chain transfer agents to monomer mixtures, butyl rubber can be obtained in harmonically improved wet strength, filler incorporation and stress relaxation rates. The resulting butyl polymer has overall improved processability. More specifically, the butyl polymer very preferably has harmonized rheological properties. On the one hand, at very low shear rates the viscosity and elasticity of the butyl polymer is higher than the corresponding copolymers of isoolefins and conjugated dienes, so that the butyl polymer of the present invention is more prevented from cold flow. On the other hand, at high shear rates, the viscosity and elasticity of the butyl polymer is lower than the corresponding copolymers of isoolefins and conjugated dienes, so that the mixed properties of the butyl polymers of the present invention are improved, the extrusion rate is raised, and die expansion is reduced. Done. These improved properties are believed to result from the combination of monomer mixtures, multiolefin crosslinkers and chain transfer agents.
    [31] The present invention therefore provides a method for intentionally altering the rheological properties of a polymer. It has been found that this can be achieved by controlling the amount of crosslinker added to the process and the strength of the chain transfer reaction. Control of the chain transfer reaction strength can be achieved by addition of the chain transfer agent to the desired concentration or by change in the polymerization temperature. Chain transfer in the cationic polymerization process is known to be highly influenced by temperature.
    [32] Careful control of the crosslinking and chain transfer reactions changes the slope of the log tan delta-log frequency curve. Slope reduction means improved processing properties over conventional straight chain polymers,
    [33] 1.The tan delta at high frequencies must be greater than the straight chain polymer,
    [34] 2. The tan delta at low frequencies should be smaller than the straight chain polymer,
    [35] 3. The polymer obtained should be suitable for compounding and curing. That is, they must have sufficient molecular weight or elasticity for conventional rubber handling processes.
    [36] The first two points mean that the log tangent delta-log frequency curves of the straight and branched chain polymers must have intersections.
    [37] It has been found that this property can be achieved in the butyl polymer of the present invention. Butyl polymers with widely different tan delta-frequency relationships can be prepared. The intersection between the tan delta curve of the straight chain polymer and the gel point proximity polymer can be shifted. Extremely, gel-free polymers of frequency-dependent tan deltas can be produced and the tan delta values can be changed by control of the polymerization reaction. The polymers obtained can be processed, blended and cured in a conventional manner and they exhibit markedly improved processability.
    [38] Embodiments of the present invention will be described with reference to the accompanying drawings:
    [39] 1 is a double log plot showing the tan delta of conventional butyl polymers with different Mooney viscosity as a function of each frequency.
    [40] FIG. 2 is a double log plot showing the complex viscosity of conventional butyl polymers with different Mooney viscosity as a function of each frequency.
    [41] FIG. 3 is a double log plot of the solubility prepared in the presence of DVB and different amounts of chain transfer agent showing the tan delta of the different polymers as a function of each frequency.
    [42] FIG. 4 is a double log plot showing the complex viscosity of a polymer of different solubility prepared in the presence of DVB and different amounts of chain transfer agent as a function of each frequency.
    [43] FIG. 5 is a double log plot showing the tan delta of a fully soluble polymer prepared in the presence of different amounts of DVB and chain transfer agent as a function of each frequency.
    [44] FIG. 6 is a double log plot showing the complex viscosity of a fully soluble polymer prepared in the presence of different amounts of DVB and chain transfer agent as a function of each frequency.
    [45] FIG. 7 is a plot of torque showing the torque evolution of conventional straight and DVB branched chain samples during mixing with carbon black as a function of time.
    [46] 8 is a plot showing residual stress at 120 s of straight and branched chain samples painted in black as a function of initial slope.
    [47] 9 is a plot showing residual stress at 120 s of straight and branched chain samples painted in black as a function of initial stress.
    [48] FIG. 10 is a plot showing the running die expansion (measured by MPT measurement) of straight and branched chain samples painted in black as a function of initial stress (measured by stress relaxation measurement).
    [49] FIG. 11 is a plot showing relaxed die expansion (measured by MPT measurement) of straight and branched chain samples painted in black as a function of initial stress (measured by stress relaxation measurement).
    [50] 12 is a plot showing the apparent viscosity (measured by MPT measurement) of the straight and branched chain samples painted in black as a function of the initial slope (measured by stress relaxation measurement).
    [51] FIG. 13 is a plot showing the area under the Mooney viscosity relaxation curve of a pure polymer as a function of residual stress at 120 s measured by stress relaxation measurements using a black painted formulation.
    [52] FIG. 14 is a double log plot showing the tan delta of a sample prepared in continuous polymerization as a function of each frequency.
    [53] The butyl polymer of the present invention is therefore derived from monomer mixtures comprising C 4 to C 7 monoolefin monomers and C 4 to C 14 multiolefin monomers or β-pinene, the process of the invention relates to the use of such monomer mixtures. .
    [54] Preferably the monomer mixture comprises about 80 to about 99 weight percent C 4 to C 7 monoolefin monomer and about 1.0 to about 20 weight percent C 4 to C 14 multiolefin monomer or β-pinene. More preferably the monomer mixture comprises about 85 to about 99 weight percent C 4 to C 7 monoolefin monomer and about 1.0 to about 10 weight percent C 4 to C 14 multiolefin monomer or β-pinene. Most preferably the monomer mixture comprises about 95 to about 99 weight percent C 4 to C 7 monoolefin monomer and about 1.0 to about 5.0 weight percent C 4 to C 14 multiolefin monomer or β-pinene.
    [55] Preferred C 4 to C 7 monoolefin monomers include isobutylene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2-butene, 4-methyl-1-pentene and mixtures thereof It may be selected from the group. Most preferred C 4 to C 7 monoolefin monomers include isobutylene.
    [56] Preferred C 4 to C 14 multiolefin monomers are isoprene, butadiene, 2-methylbutadiene, 2,4-dimethylbutadiene, piperiline, 3-methyl-1,3-pentadiene, 2,4-hexadiene, 2-neo Pentylbutadiene, 2-methyl-1,5-hexadiene, 2,5-dimethyl-2,4-hexadiene, 2-methyl-1,4-pentadiene, 2-methyl-1,6-heptadiene, cyclo Pentadiene, methylcyclopentadiene, cyclohexadiene, 1-vinyl-cyclohexadiene and mixtures thereof. Most preferred C 4 to C 14 multiolefin monomers include isoprene.
    [57] As noted above, the monomer mixture comprises a small amount of one or more additional polymerizable comonomers. For example, the monomer mixture may comprise small amounts of styrene monomers.
    [58] Preferred styrene monomers may be selected from the group comprising p-methylstyrene, styrene, α-methylstyrene, p-chlorostyrene, p-methoxystyrene, indene (including indene derivatives) and mixtures thereof. Most preferred styrene monomers may be selected from the group comprising styrene, p-methylstyrene and mixtures thereof.
    [59] If styrene monomer is present, it is preferred to use in amounts up to about 5.0% by weight of the monomer mixture.
    [60] Other monomers may be used in the monomer mixture, of course, it should be able to copolymerize with other monomers in the monomer mixture.
    [61] As noted above, the butyl polymer can be halogenated. Preferably the halogenated butyl polymer is brominated or chlorinated. Preferably the amount of halogen is in the range of about 0.1 to about 8 weight percent, more preferably about 0.5 to about 4 weight percent, and most preferably about 1.0 to about 3.0 weight percent of the polymer weight.
    [62] Halogenated butyl polymers may also be prepared by halogenating pre-made butyl polymers derived from monomer mixtures as described above.
    [63] The reaction mixture used to prepare the butyl polymer of the present invention further comprises a multiolefin crosslinker. The choice of crosslinker is not particularly limited. Preferably the crosslinker comprises a multiolefin hydrocarbon compound. For example, norbornadiene, 2-isopropenylnorbornene, 2-vinyl-norbornene, 1,3,5-hexatriene, 2-phenyl-1,3-butadiene, divinylbenzene , Diisopropenylbenzene, divinyltoluene, divinylxylene and C 1 to C 20 alkyl substituted derivatives thereof. More preferably the multiolefin crosslinker is selected from the group comprising divinyl-benzene, diisopropenylbenzene, divinyltoluene, divinyl-xylene and C 1 to C 20 alkyl substituted derivatives thereof. Most preferably the multiolefin crosslinker comprises divinylbenzene and diisopropenylbenzene.
    [64] The amount of crosslinker used in the reaction mixture depends on the type of multivalent crosslinker used. For example, in the case of DVB, the amount of DVB can range from 0.01 to 3 weight percent (weight percent is defined as DVB / (IB + IP + DVB) * 100). The preferred range is 0.05 to 1% by weight, most preferably 0.1 to 0.4% by weight.
    [65] The reaction mixture used to prepare the butyl polymer of the present invention further comprises a chain transfer agent.
    [66] The chain transfer agent should preferably be a strong chain transfer agent—that is, it must be able to react with the growing polymer chain, terminate its further growth and then start a new polymer chain. The type and amount of chain transfer agent depends on the amount of crosslinker. At low concentrations of crosslinker, small amounts of chain transfer and / or weak transfer may be used. However, as the concentration of the crosslinker is increased, the chain transfer agent concentration must be increased and / or a stronger chain transfer agent must be selected.
    [67] The use of a weak chain transfer agent should be avoided because it can excessively reduce the polarity of the solvent mixture and also make the process uneconomical.
    [68] The strength of the chain transfer agent can be measured conventionally, for example in J. Macromol. Sci.-Chem., A1 (6) pp. 995-1004 (1967)] (Kennedy et al.). The numerical value called the transfer constant indicates its strength. According to the values described in this document, the transfer constant of 1-butene (used in the DVB patent of Exxon) is zero.
    [69] Preferably, the chain transfer agent has a transfer coefficient of at least about 10, more preferably at least about 50. Non-limiting examples of useful chain transfer agents include piperylene, 1-methylcycloheptene, 1-methyl-cyclopentene, 2-ethyl-1-hexene, 2,4,4-trimethyl-1-pentene, indene and mixtures thereof to be. Most preferred chain transfer agent is 2,4,4-trimethyl-1-pentene.
    [70] The amount of chain transfer agent used depends on the amount and type of multivalent crosslinker used. In the case of DVB and 2,4,4-trimethyl-1-pentene (TMP-1), the preferred range is from 0.01 to 1.4% by weight, based on the amount of isobutylene used (TMP-1 / IB * 100). More preferably, it is 0.05 to 0.5 weight%.
    [71] The method includes contacting the reaction mixture with a catalyst system.
    [72] Preferably the process for preparing the butyl polymer is carried out at a temperature which is customary for the production of butyl polymer, for example in the range of about -100 ° C to about + 50 ° C. Butyl polymers can be prepared by solution polymerization or slurry polymerization methods. The polymerization is preferably carried out in suspension (slurry method)-see for example Ullmann's Encyclopedia of Industrial Chemistry (Fifth, Completely Revised Edition, Volume A23; editor Elvers et al.).
    [73] For example, in one embodiment the process comprises an aliphatic hydrocarbon diluent (such as n-hepic acid) and a large amount (about 80 to about 99 mole percent) of a dialkylaluminum halide (such as diethylaluminum chloride), a small amount ( About 1 to about 20 mole percent) of monoalkylaluminum dihalide (eg, isobutylaluminum dichloride) and small amounts (about 0.01 to about 10 ppm) of water, aluminoxanes (eg, methylaluminoxane) and It is carried out in the presence of a catalyst mixture comprising at least one selected from the group comprising the mixture.
    [74] Of course, other catalyst systems commonly used in the manufacture of butyl polymers can be used in the preparation of butyl polymers useful in the present invention—see, eg, “Cationic Polymerization of Olefins: A Critical Inventory” Joseph P. John P. Kennedy (John Wiley & Sons, Inc. 1975).
    [75] If a halogenated butyl polymer is desired, the butyl polymer prepared according to the above method can be halogenated according to a conventional method. See, for example, US Pat. No. 5,886,106. Therefore, the finely divided butyl rubber is treated with a halogenating agent such as chlorine or bromine, or the bromination agent such as N-bromosuccinimide and a pre-fabricated butyl rubber are mixed in a mixing apparatus to produce a brominated butyl rubber. Butyl rubber can be prepared. Alternatively, a halogenated butyl rubber can be prepared by treating a solution or dispersion of a prepared butyl rubber in a suitable organic solvent with the brominating agent. For more details, see Ullmann's Encyclopedia of Industrial Chemistry (Fifth, Completely Revised Edition, Volume A23; editor Elvers et al.). The amount of halogenating agent in this process will be adjusted such that the final terpolymer has the desired amount of halogen as described above.
    [76] Butyl rubber can be used to make vulcanized rubber products. For example, vulcanizates useful by mixing butyl rubber with carbon black, silica and / or other known ingredients (e.g., other fillers, other additives, etc.) and crosslinking the mixture in a conventional manner with conventional curing agents. Can be prepared. Vulcanizates of halogenated butyl rubber can be similarly prepared.
    [77] Embodiments of the invention will be described with reference to the following examples, which should not be used to limit or limit the scope of the invention.
    [78] Example 1
    [79] This example is a comparative example. All polymers are straight chain and made without DVB. The purpose of this example is to show the effect of molecular weight on rheological properties. A small amount of chain transfer agent (2,4,4-trimethyl-pentene (TMP-1)) was added to control the molecular weight.
    [80] A series of batch experiments were performed using 71.5 g isobutylene, 2.04 g isoprene and 879.2 g methyl chloride in a 2000 mL glass reaction flask equipped with a high speed marine impeller. No chain transfer agent was added to the first batch. In the remainder, as shown in Table 1, diisobutylene (2,4,4-trimethyl-1-pentene) (TMP-1) was added while increasing the amount. The reaction mixture was cooled to -93 ° C and polymerization was initiated by addition of a solution of aluminum trichloride in methyl chloride. After 5 minutes 10 mL of ethanol was added to terminate the reaction. The resulting polymer was dissolved in hexane, stabilized by addition of 0.2 phr Irganox-1010 ™ and aggregated in hot water. The sample was dried on a 140 ° C. hot mill to remove residual moisture and monomers. The results are shown in Table 1.
    [81] Experiment numberOne2345TMP-1 (g)00.0350.0710.140.21 AlCl 3 (mg)4342434342 Catalyst Efficiency (g Polymer / g Catalyst)13501280136013501430 Conversion rate (% by weight)79.073.079.278.981.4 Mooney Viscosity (1 + 8 @ 125 ° C)48.846.235.832.422.9 Mooney Viscosity Relaxation (Area Under Curve)7612591177422
    [82] Mooney viscosity and Mooney viscosity relaxation were measured at 125 ° C. The relaxation time was fixed at 8 minutes. The Mooney viscosity values and the area under the curve drawn during relaxation are listed in Table 1. These results clearly demonstrate that TMP-1 is an effective chain transfer agent. The Mooney viscosity decreased from about 49 to about 23 when the amount of TMP-1 increased from 0 to 0.21 g. The results also show that the chain transfer agent did not affect conversion or catalyst efficiency.
    [83] As Mooney viscosity decreased, the area under the curve also decreased, indicating a relaxation or flow performance under increased stress of the sample. This was confirmed by dynamic mechanical testing. The dynamic properties of the samples were measured using an RPA2000 rubber processability analyzer manufactured by Alpha Technology. The measurements were performed at 125 ° C. using 0.72 degree arcs at each frequency range of 0.05-209 rad / s.
    [84] The log tan δ-log ω curve (FIG. 1) shifted downward as Mooney viscosity decreased. There was no intersection and there was a slight slope change due to the difference in MWD.
    [85] The log η-log ω curve (FIG. 2) shows the transition from the low frequency to the Newtonian region. Shear thinning is evident. As the Mooney viscosity decreases, the transition from Newton to shear thinning shifts to higher frequencies.
    [86] Example 2
    [87] This example illustrates how the solubility of DVB crosslinked polymers can be increased when a strong chain transfer agent is added to the polymerization mixture and how to obtain polymers of sufficiently high viscosity.
    [88] A series of batch experiments were performed using 146.6 g isobutylene, 4.15 g isoprene, 4.20 g DVB (81 wt.% Pure) and 879.2 g methyl chloride in a 2000 mL glass reaction flask equipped with a high speed vessel impeller. . DVB used in this example (and the following example) was a mixture of divinylbenzene and ethylvinylbenzene. The composition of the mixture was 57 wt% meta-divinylbenzene (m-DVB), 24 wt% para-divinylbenzene (p-DVB), 9.9 wt% meta-ethylvinylbenzene and 9.1 wt% para- Measured with ethylvinylbenzene.
    [89] No chain transfer agent was added to the first batch. The rest was added while increasing the amount of diisobutylene (2,4,4-trimethyl-1-pentene) (TMP-1) as shown in the table. The reaction mixture was cooled to −92 ° C. and polymerization was initiated by addition of 15 mL of a saturated solution of aluminum chloride in methyl chloride. After 4 minutes, 10 mL of ethanol was added to terminate the reaction.
    [90] Experiment number67891011Control (no DVB) TMP-1 (g)00.200.400.811.632.05- Conversion rate (% by weight)94.182.879.470.678.382.080.9 Solubility (wt%)2728.739.568.775.6100100 Mooney Viscosity (1 + 8 @ 125 ℃)43.644.140.547.526.417.636.5 Mooney Viscosity Relaxation (Area Under Curve)315036202840358014209151090
    [91] The prepared polymer was dissolved in hexane, stabilized by addition of 0.2 phr Irganox-1010 ™ and aggregated in hot water. The sample was dried in a hot mill at 140 ° C. to remove residual moisture and monomers.
    [92] In these experiments the amount of m-DVB and p-DVB in the monomer feed was 2.20% by weight. According to the prior art (Welch # 2), interpolymers which are substantially insoluble at this concentration of DVB should be obtained. In fact the solubility without chain transfer agent was low: only 27% by weight. However, with the introduction of strong chain transfer agents, the solubility increased from 27% to 100% by weight.
    [93] The Mooney viscosity of the polymer sample obtained in this example decreased from about 44 to about 18 with increasing solubility. Elastic materials suitable for blending and curing were obtained even at the highest chain transfer agent concentrations.
    [94] The dynamic properties of the samples were measured as described in Example 1. The effect on the dynamic properties of the resulting polymer of increasing chain transfer agent is illustrated by FIGS. 3 and 4. For comparison purposes, control samples prepared in the absence of DVB and DMP are included in these figures. The change in dynamic properties was significant. All samples have frequency dependent tan delta values. As the amount of chain transfer agent increases, the tan delta shifts to a higher value. At high gel content (27% solubility), the tan delta was smaller at all frequencies than the tan delta of the straight chain control sample. As the solubility increased, the tan delta also increased so that the curve crossed the tan delta of the straight sample. At very low frequencies it was shown that the tan delta of all samples was smaller than that of the straight chain control polymer. Most importantly, two samples (Samples 5 and 6) with significantly lower Mooney viscosity (26.4 and 17.6) compared to the straight chain control sample (Money viscosity 36.5) also showed smaller tan delta values than the control. Based on these results, a significant reduction in cold flow is predicted.
    [95] Without being bound by any particular theory or mode of action, it is believed that the frequency dependent tan delta is achieved by making an elastomer close to the gel point. The polymer at the gel point is a transition state between liquid and solid (Hel., Winter, Gel Point, Encyclopedia of Polymer Science and Engineering, John Wiley & Sons, Supplement Volume, pp. 343). The molecular weight distribution of the polymer is very wide and the molecules range from the smallest unreacted oligomer to the infinite mass. Theoretically, it is expected that the loss tangent of the polymer at the gel point (tan delta = G "/ G ') is independent of the frequency of the dynamic experiment.
    [96] A further important characteristic of DVB-modified samples is that their complex viscosity does not indicate a transition from low frequency to Newtonian fluid properties. This indicates that the law of exponential law is followed over the entire frequency range. All samples have a lower composite viscosity at frequencies above about 10 rad / s. On the other hand, at lower frequencies they have a higher composite viscosity than the control, which results in higher flow protection.
    [97] The composite viscosity obtained from the dynamic test is described by Cox-Merz's law (D. W. Cox and EH Merz), J. Polymer Sci, Vol 28, p619 ( 1958))) can be used to predict the apparent viscosity of capillary perfusion samples. The Cox-Merze law states that the complex viscosity at each given frequency is the same as the apparent viscosity measured at normal shear rate in a capillary viscometer. This was recently confirmed by measuring the viscosity of several elastomers using RPA and MPT (Monsanto Processibility Tester) (Comparison of shear thinning behavior of different elastomers using capillary). and rotorless shear rheometry, Paper No. 50, ACS Rubber Division Meeting Dallas, Texas, April 4-6, 2000].
    [98] Mooney Viscosity Stress Relaxation measurements were also performed using these samples to determine the ability to prevent cold flow of the samples by an independent method. The relaxation time chosen was 8 minutes. Samples were compared using the area under the torque-time curve. Table 2 shows the results. Except for very low Mooney viscosity samples (Mooney viscosity 17.6), all of the DVB modified samples had an area under the curve greater than the straight chain control sample of this example or any straight chain sample prepared in Example 1. 17.6 Mooney Viscosity Samples have area values under the curve very similar to the straight chain controls. The larger the area under the curve, the better the ability to prevent flow at low shear rates, ie to prevent low temperature flow.
    [99] Example 3
    [100] This example shows the effect on the dynamic properties of different degrees of branching.
    [101] A series of batch experiments were performed using 71.5 g isobutylene, 2.04 g isoprene and 1008 g methyl chloride in a 2000 ml glass reaction flask equipped with a high speed marine impeller. The amounts of DVB and TMP-1 added to the reaction mixture are listed in Table 2. The reaction mixture was cooled to −92 ° C. and polymerization was initiated by addition of a solution of approximately 0.30% by weight of aluminum chloride in methyl chloride. After 8 minutes, the reaction was terminated by adding 10 mL of ethanol. The experimental results are shown in Table 3.
    [102] Experiment number12131415161718 DVB (g)1.371.100.820.550.2700 TMP-1 (g)0.990.790.590.400.2000.07 AlCl 3 (mg)50484737364743 Catalyst Efficiency (g Polymer / g Catalyst)1140112012501610165012801360 Conversion rate (% by weight)75.471.478.679.980.581.579.2 Solubility (wt%)102.0101.0101.0101.0101.0100100 Mooney Viscosity (1 + 8 @ 125 ℃)20.229.734.536.845.851.335.8 Mooney Viscosity Relaxation (Area Under Curve)67011901590151016801090117
    [103] In addition to the DVB modified samples, two control samples were also prepared in the absence of DVB. All samples are completely soluble in hexane. Mooney viscosity and Mooney viscosity relaxation measurements clearly show that DVB modified samples can significantly prevent cold flow than straight chain samples. Only very low molecular weight DVB modified samples (Mooney viscosity 20.2) exhibited an area under the relaxation curve smaller than the straight chain samples of significantly higher molecular weight (Mooney viscosity 51.3).
    [104] 5 and 6 show the results of the dynamic test. At low frequencies (1 rad / s or less), the tan delta of the DVB modified sample was measured to be smaller than the straight chain sample. This demonstrates the results of the Mooney Viscosity Relaxation measurement, i.e. they can prevent cold flow more than a straight chain sample.
    [105] All DVB modified samples showed the intersection with tangent delta-frequency curves of the two control samples. At frequencies above about 1 rad / s, all DVB strain samples exhibited larger tan deltas. This indicates that at higher shear rates these samples have less elasticity. Lower elasticity at higher shear rates is desirable to obtain less sensitive and less expanding materials when exiting the die of the extruder.
    [106] Example 4
    [107] In this example, samples were prepared with constant low concentrations of DVB and varying diisobutylene concentrations to prepare samples having the same degree of branching but different Mooney viscosity. Experimental conditions were the same as in the previous example. The experimental results are shown in Table 4 below.
    [108] Experiment number1920212223 DVB (g).27.27.27.27.27 TMP-1 (g)0.14.210.280.350.43 AlCl 3 (mg)7160726871 Catalyst Efficiency (g Polymer / g Catalyst)8801020870960860 Conversion rate (% by weight)84.182.484.187.782.2 Solubility (wt%)100100100100100 Mooney Viscosity (1 + 8 @ 125 ℃)51.936.928.119.116.6 Mooney Viscosity Relaxation (Surface Area)247813196099530
    [109] Mooney viscosity relaxation measurements showed that samples prepared at these low concentrations of DVB could still prevent cold flow more than the corresponding or even greater Mooney viscosity straight chain samples. For example, the 28.1 Mooney Viscosity sample (Experiment 21) of this example had an area under the curve of 609. In contrast, the Mooney viscosity straight chain samples of 32.4, 35.8 and even 46.2 of Example 1 had smaller area values under the curve (see Table 1).
    [110] The sample of Example 4 and the straight chain sample described in Example 1 were combined with 60 phr N660 black to measure mixing properties and to analyze the effect on the rheological properties of the filler. A series of the above experimental results are shown in Tables 5 and 6 below.
    [111] Selected Properties of the Straight Chain Formulated Sample Experiment numberOne2345 Mooney Viscosity (1 + 8 @ 125 ℃)48.846.235.832.422.9 Maximum Temperature During Mixing (℃)81.385.679.781.379.5 Top torque during mixing34.334.233.330.630.8 Sum of torque50406390508054605200 Travel die expansion (1000 1 / s, l / D = 1)104.585.883.876.263.7 Relaxation die expansion (1000 1 / s, l / D = 1)122.3101.410085.171.6 Viscosity @ 1000 1 / s (kPa * s)3.482.842.652.311.84 Low temperature flow by DEFO (residue height after 30 minutes in mm)11.711.310.910.710.5
    [112] Selected Properties of DVB-Modified Compound Samples Experiment number1920212223 Mooney Viscosity (1 + 8 @ 125 ℃)51.936.928.119.116.6 Maximum Temperature During Mixing (℃)88.985.28480.378.7 Torque during mixing3940.936.236.137.4 Sum of torque75106600636056605640 Travel die expansion (10001 / s, l / D = 1)80.874.268.164.855.9 Relaxation die expansion (10001 / s, l / D = 1)92.289.279.277.767.2 Viscosity @ 1000 1 / s (kPa * s)3.172.682.392.121.86 Cold flow by DEFO (residue height after 30 minutes (mm))11.911.310.810.29.6
    [113] As can be seen from the table, the mixing properties of the DVB modified samples were improved. They have higher torque development at similar or even lower pure polymer Mooney viscosity. They also show a pronounced second peak of the torque curve (see FIG. 7). This is an indicator of improved filler dispersion. Butyl rubber is not known to mix well with black. Also no apparent second torque peak is shown.
    [114] The stress-relaxation performance of the blended samples was measured using the stress relaxation program of the RPA 2000 (Rubber Processing Analyzer) device. During this measurement, a constant strain was applied to the sample by the rapid movement of the lower die and the stress was measured on the upper die as a function of time. This measurement was in principle similar to the Mooney viscosity relaxation measure. Therefore, the stresses detected at longer times can be used to characterize the ability to prevent cold flow of the sample. Higher residual stresses are indicative of higher protection against cold flow. Residual stress at 2 minutes was selected for characterization for cold flow prevention of the sample.
    [115] The initial rate of stress decay can measure the performance of a sample that can relax when exposed to large strains in a very short time. For example, extrusion at high shear rates of rubber or combinations thereof through short and narrow dies. Once the rubber enters the die, it is exposed to high strain for a short time. Initial stresses detected immediately after strain application can be used to characterize the die expansion properties of the sample. Lower initial stress values mean that the sample will expand less after leaving the die. To characterize the nature of the sample, the initial slope of the log (stress) -log (time) curve at 0.01-1 second intervals and the stress detected at 1 second were selected.
    [116] Stress relaxation of the formulations described in FIGS. 5 and 6 was measured at 125 ° C. The strain applied was 100%. 8 shows the stress remaining in 2 minutes as a function of initial slope. 9 shows the stress remaining in 2 minutes as a function of the stress detected in 1s. The figures clearly demonstrate the difference between the straight and branched chain samples and the excellent properties of the branched chain samples. For example, at the stress remaining in the same two minutes, the initial relaxation of the branched sample is faster and the initial stress is lower. On the other hand, the stress remaining for a longer time at the same initial slope or initial stress is greater. This suggests that cold flow and extrusion properties can be improved simultaneously.
    [117] Die expansion of the blended samples described in Tables 5 and 6 was measured using a capillary viscometer (Monsanto Process Tester (MPT)). The measurements were performed at 125 ° C. using a die of 1000 1 / s shear rate and L / D ratio of 1/1. The results are shown in Tables 5 and 6. This clearly indicates that branched samples have lower running or relaxation die expansion at the same pure polymer Mooney viscosity. For example, a formulation made using a 48.8 Mooney viscosity straight chain sample had 104.5% run die expansion and 122.3% relaxation die expansion. In contrast, the blend of 51.9 Mooney viscosity branched samples had only 80.8% running die expansion and 92.2% relaxation die expansion.
    [118] 10-13 are provided to illustrate the processability characteristics of the sample by describing the performance figures measured by the stress relaxation measurement. FIG. 10 shows that there is a close correlation between running die expansion and initial stress and this correlation is independent of the structure of the polymer. 11 shows that there is a close correlation between relaxation die expansion and initial stress and this correlation is independent of the structure of the polymer. 12 shows that there is a close correlation between the apparent viscosity and the initial slope of the stress relaxation curve, and this correlation is independent of the structure of the polymer. FIG. 13 shows that there is a close correlation between the area under the curve measured in the Mooney viscosity relaxation measurement performed on the pure polymer and the residual stress measured by the stress relaxation measurement. This correlation is also independent of the structure of the polymer.
    [119] The cold flow properties of the blended samples were measured using the so-called strain (DEFO) measurements. This measurement was performed using compression molded discs of 30 mm diameter and 13 mm height. A load (8N) was applied to this disk and the height of the disk was measured as a function of time. Samples with higher cold flow resistance will maintain their original height higher. Tables 5 and 6 list the residual heights of the samples. According to the results, the residual height of the branched chain samples was higher than the straight chain samples of similar Mooney viscosity. For example, the residual height of the 36.9 Mooney viscosity branched chain sample was 11.3 mm. In contrast, the residual height of the 35.8 Mooney viscosity straight chain sample was 10.9 mm. Only significantly high Mooney viscosity straight chain samples (Mooney viscosity 46.2) were able to prevent cold flow as much as 36.9 Mooney viscosity branched samples.
    [120] Example 5
    [121] This example shows that a combination of improved properties can also be achieved with continuous polymerization.
    [122] To the continuous reactor, a feed comprising 71.2 wt% methylchloride, 28 wt% isobutylene and 0.8 wt% isoprene was added at a rate of 170 kg / min. DVB (purity 63%) and TMP-1 (76% purity) were added to this feed at the rate shown in Table 7. The polymerization was initiated by addition of a 0.1 wt% solution of AlCl 3 dissolved in methylchloride. The polymerization was carried out at -95 ° C. Additional experimental conditions are listed in Table 7.
    [123] Experiment number2425 DVB (g / min)65195 TMP-1 (g / min)2042 AlCl 3 solution (kg / hour)1515 Conversion rate (% by weight)8789 Solubility (wt%)100100
    [124] The Mooney viscosity of the samples is listed in Table 8 along with the area under the measured Mooney viscosity relaxation curve. For comparison, the test results of the straight chain control samples of the same Mooney viscosity are included in Table 8. This sample was also prepared by continuous polymerization. However, the monomer feed did not contain DVB or TMP-1. The elevated cold flow protection is clearly demonstrated by the larger area under the relaxation curve of samples prepared in the presence of DVB and TMP-1.
    [125] Dynamic tests confirmed that the deliberate alteration of rheological properties was successfully achieved even in the continuous polymerization. FIG. 14 shows measurement results performed at 125 ° C. using 0.72 degree arcs at 0.05-209 rad / s angular frequency range. According to this result, the tan delta of the DVB modified sample was smaller than the straight chain sample at low frequency. On the other hand, this was higher at high frequencies and the intersection is clearly present.
    [126] Experiment number2425Control Mooney Viscosity (1 + 8 @ 125 ℃)36.235.636.0 Mooney Viscosity Relaxation (Area Under Curve)350890220 Travel die expansion (10001 / s, l / D = 1)636368 Relaxation die expansion (10001 / s, l / D = 1)677070 Viscosity @ 1000l / s (kPa * s) Cold flow by DEFO (residue height after 30 minutes) (mm)10.811.210.4
    [127] Two samples of Example 5 were combined with 60 phr N660 black along with a straight chain control sample. MPT and cold flow DEFO measurements confirmed that samples prepared in the presence of DVB and TMP-1 had improved combination of processability properties. The rise in cold flow protection is confirmed by higher residual height values. According to the MPT measurement, the elevated low temperature flow protection did not increase die expansion. In fact, the running and relaxation die expansion of the DVB modified sample was determined to be lower.
    [128] Although the present invention has been described with reference to preferred and specifically illustrated embodiments, it will be apparent to those skilled in the art that various modifications to these preferred and specifically illustrated embodiments may be made without departing from the spirit and scope of the present invention. Will be understood. All documents, patents, and patent applications mentioned in this specification are incorporated by reference.
    权利要求:
    Claims (44)
    [1" claim-type="Currently amended] (i) monomer mixtures comprising C 4 to C 7 monoolefin monomers and C 4 to C 14 multiolefin monomers or β-pinene;
    (ii) multiolefin crosslinkers; And
    (iii) butyl polymer with improved processability derived from a reaction mixture comprising a chain transfer agent.
    [2" claim-type="Currently amended] The method of claim 1, wherein the C 4 to C 7 monoolefin monomer is isobutylene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2-butene, 4-methyl-1- Butyl polymer selected from the group comprising pentene and mixtures thereof.
    [3" claim-type="Currently amended] The butyl polymer of claim 2 wherein the C 4 to C 7 monoolefin monomer comprises isobutylene.
    [4" claim-type="Currently amended] The method according to any one of claims 1 to 3, wherein the C 4 to C 14 multiolefin monomer is isoprene, butadiene, 2-methylbutadiene, 2,4-dimethylbutadiene, piperiline, 3-methyl-1,3 -Pentadiene, 2,4-hexadiene, 2-neopentylbutadiene, 2-methyl-1,5-hexadiene, 2,5-dimethyl-2,4-hexadiene, 2-methyl-1,4-penta A butyl polymer selected from the group consisting of dienes, 2-methyl-1,6-heptadiene, cyclopentadiene, methylcyclopentadiene, cyclohexadiene, 1-vinyl-cyclo-hexadiene and mixtures thereof.
    [5" claim-type="Currently amended] 5. The butyl polymer of claim 4 wherein said C 4 to C 14 multiolefin monomer comprises isoprene.
    [6" claim-type="Currently amended] 6. The monomer of claim 1, wherein the monomer mixture is about 80 to about 99 weight percent C 4 to C 7 monoolefin monomer and about 1.0 to about 20 weight percent C 4 to C 14 multiolefin Butyl polymer comprising monomer or β-pinene.
    [7" claim-type="Currently amended] 7. The composition of claim 6, wherein the monomer mixture comprises about 85 to about 99 weight percent C 4 to C 7 monoolefin monomer and about 1.0 to about 15 weight percent C 4 to C 14 multiolefin monomer or β-pinene Butyl polymer.
    [8" claim-type="Currently amended] 8. The composition of claim 7, wherein the monomer mixture comprises about 95 to about 99 weight percent C 4 to C 7 monoolefin monomer and about 1 to about 5.0 weight percent C 4 to C 14 multiolefin monomer or β-pinene Butyl polymer.
    [9" claim-type="Currently amended] 9. The butyl polymer of claim 1 wherein the multiolefin crosslinker comprises a diolefin hydrocarbon compound. 10.
    [10" claim-type="Currently amended] The method of claim 9, wherein the butyl polymer selected from the group comprising the multi-olefinic crosslinking agent, divinylbenzene, di-isopropenyl benzene, divinyl toluene, divinyl xylene and their C 1 to C 20 alkyl-substituted derivatives.
    [11" claim-type="Currently amended] 11. The butyl polymer of claim 10 wherein said multiolefin crosslinker comprises divinylbenzene.
    [12" claim-type="Currently amended] The method of claim 1, wherein the multiolefin crosslinker ranges from about 0.01 to about 3.0 weight percent based on the amount of C 4 to C 7 monoolefin monomer in the monomer mixture in the reaction mixture. Butyl polymer present in an amount of.
    [13" claim-type="Currently amended] 13. The butyl polymer of claim 12 wherein the multiolefin crosslinker is present in the reaction mixture in an amount ranging from about 0.05 to about 1.0 weight percent based on the amount of C 4 to C 10 monoolefin monomer in the monomer mixture.
    [14" claim-type="Currently amended] The butyl polymer of claim 13 wherein the multiolefin crosslinker is present in the reaction mixture in an amount ranging from about 0.1 to about 0.4 weight percent based on the amount of C 4 to C 7 monoolefin monomer in the monomer mixture.
    [15" claim-type="Currently amended] The method according to any one of claims 1 to 14, wherein the chain transfer agent is piperylene, 1-methylcycloheptene, 1-methylcyclo-pentene, 2-ethyl-1-hexene, 2,4,4-trimethyl- Butyl polymer selected from the group comprising 1-pentene, indene and mixtures thereof.
    [16" claim-type="Currently amended] The butyl polymer of claim 15 wherein the chain transfer agent comprises 2,4,4-trimethyl-1-pentene.
    [17" claim-type="Currently amended] The amount of claim 1, wherein the chain transfer agent is in an amount ranging from about 0.01 to about 2.0 weight percent based on the amount of C 4 to C 7 monoolefin monomer in the monomer mixture in the reaction mixture. Butyl polymer present.
    [18" claim-type="Currently amended] 18. The butyl polymer of claim 17 wherein the chain transfer agent is present in the reaction mixture in an amount ranging from about 0.01 to about 1.4 weight percent based on the amount of C 4 to C 7 monoolefin monomer in the monomer mixture.
    [19" claim-type="Currently amended] 19. The butyl polymer of claim 18 wherein the chain transfer agent is present in the reaction mixture in an amount ranging from about 0.05 to about 0.5 weight percent based on the amount of C 4 to C 7 monoolefin monomer in the monomer mixture.
    [20" claim-type="Currently amended] 20. The butyl polymer of any of claims 1 to 19, wherein the polymer comprises a halogenated butyl polymer.
    [21" claim-type="Currently amended] 21. The butyl polymer of claim 20 wherein the polymer is brominated.
    [22" claim-type="Currently amended] The butyl polymer of claim 20 wherein the polymer is chlorinated.
    [23" claim-type="Currently amended] 23. The butyl polymer of any one of claims 20 to 22 wherein the amount of halogen ranges from about 0.1 to about 8 weight percent of the polymer.
    [24" claim-type="Currently amended] The butyl polymer of claim 23 wherein the amount of halogen ranges from about 0.5 to about 4 weight percent of the polymer.
    [25" claim-type="Currently amended] 25. The butyl polymer of claim 24 wherein the amount of halogen ranges from about 1.5 to about 3 weight percent of the polymer.
    [26" claim-type="Currently amended] Monomer mixtures comprising C 4 to C 7 monoolefin monomers and C 4 to C 14 multiolefin monomers;
    Multiolefin crosslinkers;
    Chain transfer agents; And
    A process for preparing butyl polymer with improved processability comprising contacting a reaction mixture comprising a catalyst system.
    [27" claim-type="Currently amended] 27. The method of claim 26, wherein the C 4 to C 7 monoolefin monomer is isobutylene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2-butene, 4-methyl-1- Pentene and mixtures thereof.
    [28" claim-type="Currently amended] The method of claim 27, wherein said C 4 to C 7 monoolefin monomer comprises isobutylene.
    [29" claim-type="Currently amended] 29. The method of claim 26, wherein the C 4 to C 14 multiolefin monomers are isoprene, butadiene, 2-methylbutadiene, 2,4-dimethylbutadiene, piperiline, 3-methyl-1,3 -Pentadiene, 2,4-hexadiene, 2-neopentylbutadiene, 2-methyl-1,5-hexadiene, 2,5-dimethyl-2,4-hexadiene, 2-methyl-1,4-penta Diene, 2-methyl-1,6-heptadiene, cyclopentadiene, methylcyclopentadiene, cyclohexadiene, 1-vinyl-cyclo-hexadiene and mixtures thereof.
    [30" claim-type="Currently amended] 30. The method of claim 29, wherein the C 4 to C 14 multiolefin monomer comprises isoprene.
    [31" claim-type="Currently amended] 31. The method of any of claims 26-30, wherein the monomer mixture is about 80 to about 99 weight percent C 4 to C 7 monoolefin monomer and about 1.0 to about 20 weight percent C 4 to C 14 multiolefin Monomer or β-pinene.
    [32" claim-type="Currently amended] The monomer mixture of claim 31, wherein the monomer mixture comprises about 85 to about 99 weight percent C 4 to C 7 monoolefin monomer and about 1.0 to about 15 weight percent C 4 to C 14 multiolefin monomer or β-pinene How.
    [33" claim-type="Currently amended] 33. The method of claim 32, wherein the monomer mixture comprises about 95 to about 99 weight percent C 4 to C 7 monoolefin monomer and about 1 to about 5.0 weight percent C 4 to C 14 multiolefin monomer or β-pinene How.
    [34" claim-type="Currently amended] 34. The method of any one of claims 26 to 33, wherein the multiolefin crosslinker comprises a diolefin hydrocarbon compound.
    [35" claim-type="Currently amended] 35. The method of claim 34, wherein said multi-olefinic crosslinking agent, divinylbenzene, di-isopropenyl benzene, divinyl toluene, divinyl xylene and their C 1 to one selected from the group consisting of C 20 alkyl-substituted derivatives.
    [36" claim-type="Currently amended] 34. The method of any of claims 26 to 33, wherein the multiolefin crosslinker comprises divinyl-benzene.
    [37" claim-type="Currently amended] 34. The composition of any one of claims 26 to 33, wherein the multiolefin crosslinker ranges from about 0.01 to about 3.0 weight percent based on the amount of C 4 to C 7 monoolefin monomer in the monomer mixture in the reaction mixture. Present in an amount.
    [38" claim-type="Currently amended] 38. The method of claim 37, wherein the multiolefin crosslinker is present in the reaction mixture in an amount ranging from about 0.05 to about 1.0 weight percent based on the amount of C 4 to C 7 monoolefin monomer in the monomer mixture. .
    [39" claim-type="Currently amended] The method of claim 38, wherein the multiolefin crosslinker is present in the reaction mixture in an amount ranging from about 0.1 to about 0.4 weight percent based on the amount of C 4 to C 7 monoolefin monomer in the monomer mixture. .
    [40" claim-type="Currently amended] 40. The chain transfer agent of claim 26 wherein the chain transfer agent is piperylene, 1-methylcycloheptene, 1-methylcyclopentene, 2-ethyl-1-hexene, 2,4,4-trimethyl-1 -Pentene, indene and mixtures thereof.
    [41" claim-type="Currently amended] 34. The method of any of claims 26 to 33, wherein the chain transfer agent comprises 2,4,4-trimethyl-1-pentene.
    [42" claim-type="Currently amended] 34. The amount of claim 26, wherein the chain transfer agent ranges from about 0.01 to about 2.0 weight percent based on the amount of C 4 to C 7 monoolefin monomer in the monomer mixture in the reaction mixture. To be present.
    [43" claim-type="Currently amended] The method of claim 42, wherein the chain transfer agent is present in the reaction mixture in an amount ranging from about 0.05 to about 1.4 weight percent based on the amount of C 4 to C 7 monoolefin monomer in the monomer mixture.
    [44" claim-type="Currently amended] The method of claim 43, wherein the chain transfer agent is present in the reaction mixture in an amount ranging from about 0.1 to about 0.5 weight percent based on the amount of C 4 to C 7 monoolefin monomer in the monomer mixture.
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    同族专利:
    公开号 | 公开日
    US20030187173A1|2003-10-02|
    EP1313777B1|2008-12-24|
    AU8740801A|2002-03-04|
    EP1313777A1|2003-05-28|
    CN1247632C|2006-03-29|
    WO2002016452A1|2002-02-28|
    CA2316741A1|2002-02-24|
    US6841642B2|2005-01-11|
    DE60137136D1|2009-02-05|
    HK1062179A1|2006-11-10|
    JP2004506088A|2004-02-26|
    CN1469886A|2004-01-21|
    RU2277544C2|2006-06-10|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    2000-08-24|Priority to CA2,316,741
    2000-08-24|Priority to CA 2316741
    2001-08-21|Application filed by 바이엘 인크.
    2001-08-21|Priority to PCT/CA2001/001188
    2003-04-23|Publication of KR20030031990A
    优先权:
    申请号 | 申请日 | 专利标题
    CA2,316,741|2000-08-24|
    CA 2316741|CA2316741A1|2000-08-24|2000-08-24|Improved processability butyl rubber and process for production thereof|
    PCT/CA2001/001188|WO2002016452A1|2000-08-24|2001-08-21|Improved processability butyl rubber and process for production thereof|
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