CROSSLINKING COMPOUNDS FOR HIGH GLASS TRANSITION TEMPERATURE POLYMERS |
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申请号 | EP11788752.1 | 申请日 | 2011-11-18 | 公开(公告)号 | EP2780392B1 | 公开(公告)日 | 2016-06-29 |
申请人 | Greene, Tweed & Co.; | 发明人 | BURGOYNE, William Franklin Jr.; NORDQUIST, Andrew Francis; DRAKE, Kerry A.; SONG, Le; | ||||
摘要 | |||||||
权利要求 | |||||||
说明书全文 | The present invention is directed to crosslinking compositions and mixtures for forming crosslinked high glass transition polymer systems. High glass transition temperature polymers have been useful for a number of high temperature applications. Crosslinking generally improves high temperature performance, strength and chemical resistance compared to the base polymer. However, crosslinking of high glass temperature polymers to form polymers having the desired high temperature properties is generally not known in the art. For example, in previous attempts to crosslink high glass transition temperature (Tg) polymers the thermal stability of the polymer is compromised. This is particularly true for those high Tg polymers wherein the desired temperature for reaction (cure) may range from 200-450° C. Crosslinking has been recognized as one way to address the requirements of high performance polymeric materials. Past attempts have used various different approaches for crosslinking polymers. One such attempt is described, for example, in International Patent Application Publication The references The references International Patent Application Publication International Patent Application Publication International Patent Application Publication There is a need in the art for polymeric materials with thermal stability at high temperatures, such as temperatures up to 500° C. A method and composition that crosslinks high glass transition polymers to form thermally stable, crosslinked polymer systems, would be desirable in the art. In an exemplary embodiment, the disclosure includes a composition having a crosslinking compound that has the following structure: wherein R is OH, NH2, halide, ester, amine, ether, or amide, and x is 2-6 and A is an arene moiety having a molecular weight of less than about 10,000. In another exemplary embodiment, the disclosure includes a mixture that includes a composition and a polymer. The composition includes a crosslinking compound having the following structure: wherein R is OH, NH2, halide, ester, amine, ether, or amide, and x is 2-6 and A is an arene moiety having a molecular weight of less than about 10,000. The polymer is a polymer containing at least one aromatic group. The mixture is a substantially homogenous blend of the composition and the polymer. In another exemplary embodiment, the disclosure includes a method for making a polymer blend. The method includes providing a composition including a crosslinking compound having the following structure: wherein R is OH, NH2, halide, ester, amine, ether, or amide, and x is 2-6 and A is an arene moiety having a molecular weight of less than about 10,000. A polymer is provided wherein the polymer contains at least one aromatic group. The composition and the polymer are combined to form a substantially homogenous mixture. In another exemplary embodiment, the disclosure includes a crosslinked polymer. The crosslinked polymer is a reaction product of a composition and a polymer. The polymer includes a crosslinking compound having the following structure: wherein R is OH, NH2, halide, ester, amine, ether, or amide, and x is 2-6 and A is an arene moiety having a molecular weight of less than about 10,000. The polymer is a polymer containing at least one aromatic group.
Provided are polymeric materials with thermal stability at high temperatures and a method and composition that crosslinks high glass transition polymers to form thermally stable, crosslinked polymer systems. In particular, the composition of the present disclosure crosslinks high glass transition polymers that were difficult to crosslink or previously believed to be uncrosslinkable. The crosslinked high glass transition temperature polymers according to the present disclosure are thermally stable at temperatures greater than 260° C, greater than 400° C or up to about or greater than 500° C. The composition according to the present disclosure is useable with unmodified polymers. Polymers with thermal stability up to 500 °C provide opportunities in manufactured articles in terms of utility in scope of application. There are numerous product applications which require a polymer part, which has thermal stability up to 500 °C. Certain embodiments of the present disclosure include a high crosslink density. By having a high crosslink density, the glass transition temperature of the polymer formed inherently increases, and the susceptibility to swell decreases, when exposed to solvents. There is an advantage to adding a crosslinking additive to an unmodified polymer to achieve crosslinking, compared to modification of the polymer by grafting a crosslinking moiety to the polymer. For example, unlike in the method according to the present disclosure, modification of the polymer generally requires dissolving the polymer into an appropriate solvent, so that chemical grafting of a crosslinking moiety to the polymer can be performed. In certain embodiments of the present disclosure, a curing composition includes a multi(9H-fluoren-9-ol-9-yl) arene derivative crosslinking compound that can be used for crosslinking aromatic group containing polymers, such as high glass transition temperature (Tg) polymers. Examples of high glass transition temperature (Tg) polymers include polysulfones, polyimides, polyamides, poly(etherketones), polyureas, polyurethanes, polyphthalamides, polyamide-imides, aramid, poly(benzimidazole). The crosslinks formed are preferably thermally stable to temperatures up to about 500° C. The crosslinking compounds for crosslinking the high Tg polymers includes the following structure: wherein R is OH, NH2, halide, ester, amine, ether, or amide, and x is 2-6 and A is an arene moiety having a molecular weight of less than about 10,000. A molecular weight of less than about 10,000 permits the overall structure to be more miscible with the polymer, and permits uniformly distribution (with few or no domains) within the blend of polymer and crosslinking agent. A suitable compound for inclusion in the curing composition includes a crosslinking compound having the following structure: wherein x is 2-6 and A is an arene moiety having a molecular weight of less than about 10,000. Other suitable structures for crosslinking present in the composition include, but are not limited to, one or more of the following structures: and While not so limited, in order to produce the crosslinking compound according to embodiments of the present disclosure, for example, a halogenated arene can be treated with an alkyllithium in order to exchange the halogen with lithium, then 9-fluorenone is then added. After addition of acid, the crosslinking compound is formed. This exemplary method of forming the crosslinking compound is shown below: In an embodiment of the present disclosure, a crosslinked high glass transition temperature polymer is formed from a mixture of a composition containing a crosslinking compound and a thermally stable high Tg aromatic polymer. The composition is mixed with the polymer to form a homogenous mixture. The polymer contains at least one aromatic group and may be selected from one or more of a poly(arylene ether) polymer including polymer repeat units of the following structure: -(O-Ar1-O-Ar2-)m-(-O-Ar3-O-Ar4-)n where Ar1, Ar2, Ar3, and Ar4 are identical or different aryl radicals, m is 0 to 1, n is 1-m; a polysulfone; a polyimide; a polyamide; a poly(etherketone); a polyurea; a polyurethane; a polyphthalamide; a polyamide-imide; an aramid; and a poly(benzimidazole); . Blending of the crosslinking compounds into the polymer can be performed in various ways. One such way is dissolving both the polymer and crosslinking compound in a common solvent, then removing the solvent via evaporation or addition of a non-solvent to cause coprecipitation of polymer and crosslinking compound. For example, in the case of poly(arylene ether)s as the polymer and Diol-1(see Examples below) as the crosslinking compound a suitable common solvent to both is tetrahydrofuran, a non-solvent would be water. In some cases a common solvent may not exist or be convenient, in those cases alternate blending procedures are required, such as blending in an extruder, ball mill, or cyrogrinder. The mixing process is preferably accomplished at a temperature during mixing that does not exceed about 250 °C, so that premature curing does not occur during the mixing process. In mechanical mixing, the mixture resulting is homogeneous in order to get uniform crosslinking. The mixture is cured by exposing the mixture to temperatures greater than 250° C, for example, from about 250 °C to about 500° C. While not wishing to be bound by theory, it is believed at temperatures greater than 250° C, the hydroxyl functionality of the crosslinking compound is dissociated from the remainder of the additive to afford a carbocation which then can undergo a Friedel-Crafts alkyation of the aromatic polymer, resulting in bond formation. The process is repeated with other hydroxyl moieties in the additive to form crosslinks and is shown below: A 41.82 g (0. 1275 mol.) portion of (4-bromophenyl) ether is dissolved into 750 mL of tetrahydrofuran (THF) and is cooled to -78° C with a dry ice/acetone bath. The solution is maintained under a static nitrogen blanket. A 300 mL (0.51 mol.) portion of 1.7 M tert-bulyllithium in pentane solution is added so that the temperature is maintained at less than -64° C. After addition, the solution is stirred at -78° C. The cooling bath is removed and a 45.95 g (0.255 mol.) portion of 9-fluorenenone is added. The solution is stirred overnight. A 10 mL portion of glacial acetic acid is then added. The gels in the solution are removed via vacuum filtration. The solvent is removed from the solution at 40° C with the aid of a rotoevaporator. The residual oil is dissolved in 300 mL of acetone, then added to 2800 mL of hexanes. The product precipitate is isolated via filtration. Isolated yield is 64.27 g (95%). The general reaction that results is shown below: The Diol 1 (C38H26O3 compound shown above) formed affords the 13C NMR as shown in A 26.52 g (0.085 mol) portion of 4,4'-bromobiphenyl is dissolved into 500 mL of tetrahydrofuran (THF) and is cooled to -78° C with a dry ice/acetone bath. The solution is maintained under a static nitrogen blanket. A 200 mL (0.34 mol) portion of 1.7 M tert-butyllithium in pentane solution is added so that the temperature is maintained at less than -64° C. After addition, the solution is stirred at -78° C. The cooling bath is removed and a 30.63 g (0.17 mol) portion of 9-fluorenenone is added. The solution is stirred overnight. A 10 mL portion of glacial acetic acid is then added. The gels in the solution are removed via vacuum filtration. The solvent is removed from the solution at 40° C with the aid of a rotoevaporator. The residual oil is dissolved in 200 mL of acetone, then added to 1400 mL of hexanes. Isolated yield after recrystalization in cyclohexanone, the product precipitate is isolated via filtration, affording 43.74 g (95% yield). The general reaction that results is shown below: The Diol 2 (the C38H26O2 compound shown above) affords the 13C NMR as shown in Blends of Diol 1 crosslinking compound and polymers were prepared at the concentrations indicated in Table 1. The general procedure used was the Diol 1 crosslinking compound and polymers were dissolved in the indicated solvent, the solvent was removed as indicated in Table 1. After complete dissolution, the as-prepared polymer/Diol 1 THF solution was precipitated in deionized water at 1: 4 volume ratio using blender. The precipitated particles were collected by vacuum filtration using Whatman 1 filter paper. The collected particles were dried in a vacuum oven at 120°C/17 hours under vacuum. Cure procedure 1: as-prepared blend in DSC cell under N2 environment at cure cycle: Heat/Cool/Heat at 20/10/20 °C rate from RT-400° C, glass transition Tg was determined in the 2nd heat. Cure procedure 2: Cold-pressed pellet from the as-prepared blend in the parallel plate of AR-2000 rheometer under N2 purge, heat cycle: 320-400 °C at a 5 °C/min ramp, and hold 30 minutes at 400° C, sample was taken out immediately for DSC analysis using the same protocol aforementioned. Cure procedure 3: as-prepared blend was compression molded under the following condition: An 8 g portion of polymer / crosslinker blend was put into a mold 13.97cm (5.5 inches) long by 1.27cm (0.5 inches) wide, and is compressed to 0.3 tons pressure. The molding starts at ambient temperature and is taken to 398.88 °C (750 °F) the pressure is increased to 0.5 tons @ 650 °F and held until temp reaches 750 °F then cooled down under 0.7 tons pressure in a cold press until mold reaches 550°F. The final compressed thickness is approx. 0.317 cm (0.125 inches). Glass transition of as-molded bar was determined by DMA test using AR-2000 (determined by tan δ, RT-350° C at 5° C/min ramp under N2 environment) and by OSC using the same protocol aforementioned. Blends of Diol 1 crosslinking compound and polymers were prepared at the concentrations indicated in Table 3. The general procedure used for blending was the Diol 1 crosslinking compound and polymers were combined in a cryoblender (6870 Freezer/mill from Spex) using following grinding protocol: Cycle: 3, Precool: 10 minutes, Run time: 3 minutes, Cool time: 2 minutes, Rate: 12 CPS. Properties of cured blends are summarized in Table 4. Cure procedure 1: as-prepared blend in DSC cell under N2 environment at cure cycle: Heat/Cool/Heat at 20/10/20 °C rate from RT-400° C, glass transition Tg was determined in the 2nd heat. Cure procedure 2: Cold-pressed pellet from the as-prepared blend in the parallel plate of AR-2000 rheometer under N2 purge, heat cycle: 320-400 °C at a 5 °C/min ramp, and hold 30 minutes at 400° C, sample was taken out immediately for DSC analysis using the same protocol aforementioned. Cure procedure 3: as-prepared blend was compression molded under the following condition: An 8 g portion of polymer / crosslinker blend was put into a mold 13.97cm ( 5.5 inches ) long by 1.27cm ( 0.5 inches ) wide, and is compressed to 0.3 tons pressure. The molding starts at ambient temperature and is taken to 398.88 °C ( 750 °F ) the pressure is increased to 0.5 tons @ 650 °F and held until temp reaches 750 °F then cooled down under 0.7 tons pressure in a cold press until mold reaches 550°F. The final compressed thickness is approx. 0.317 cm (0.125 inches). Glass transition of as-molded bar was determined by DMA test using AR-2000 (determined by tan δ, RT-350° C at 5° C/min ramp under N2 environment) and by OSC using the same protocol aforementioned. Blends of Diol 2 crosslinking compound and polymers were prepared at the concentrations indicated in Table 5. The general procedure used for blending was the Diol 2 crosslinking compound and polymers were combined in a cryoblender (6870 Freezer/mill from Spex) using the following grinding protocol: Cycle: 3, Precool: 10 minutes, Run time: 3 minutes, Cool time: 2 minutes, Rate: 12CPS. Properties of cured blends are summarized in Table 6. Cure procedure 1: as-prepared blend in DSC cell under N2 environment at cure cycle: Heat/Cool/Heat at 20/10/20 °C rate from RT-400° C, glass transition Tg was determined in the 2nd heat. Cure procedure 2: Cold-pressed pellet from the as-prepared blend in the parallel plate of AR-2000 rheometer under N2 purge, heat cycle: 320-400 °C at a 5 °C/min ramp, and hold 30 minutes at 400° C, sample was taken out immediately for DSC analysis using the same protocol aforementioned. Cure procedure 3: as-prepared blend was compression molded under the following condition: An 8 g portion of polymer / crosslinker blend was put into a mold 13.97cm ( 5.5 inches ) long by 1.27cm ( 0.5 inches ) wide, and is compressed to 0.3 tons pressure. The molding starts at ambient temperature and is taken to 398.88 °C ( 750 °F ) the pressure is increased to 0.5 tons @ 650 °F and held until temp reaches 750 °F then cooled down under 0.7 tons pressure in a cold press until mold reaches 550°F. The final compressed thickness is approx. 0.317 cm (0.125 inches). Glass transition of as-molded bar was determined by DMA test using AR-2000 (determined by tan δ, RT-350° C at 5° C/min ramp under N2 environment) and by OSC using the same protocol aforementioned. While the invention has been described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed as the best mode contemplated for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims. |