English:
[0011] The presence of residual unsaturation within DCPD-based copolymers can render such copolymers relatively unstable. For example, residual double bonds in ethylene- dicyclopentadiene (E/DCPD) copolymers make these materials susceptible to crosslinking, oxidation and other unwanted side reactions during processing and use. Similar problems can arise if the elastomer utilized in combination with E/DCPD in such copolymer compositions to modify the impact properties thereof also contains any residual unsaturation due to the nature of the comonomers used therein. Thus, if economically attractive DCPD- based materials are to be used as the basis for structural polyolefin preparation, the residual unsaturation within such copolymers needs to be eliminated or reduced by means of partial or complete hydrogenation or other derivatization of the residual double bonds within such copolymer structures.
[0026] The ethylene-dicyclopentadiene components used in the process and ultimately, after hydrogenation, in the polymer compositions herein can generally contain from 25 mole % to 65 mole % of the DCPD-derived monomeric units. Or these E/DCPD copolymer components can comprise from 27.5 mole % to 60 mole % of the DCPD-derived units. Alternatively, the DCPD content of the E/DCPD copolymer components used herein can range from 30 mole % to 55 mole %.
[0029] After copolymerization of the ethylene and DCPD comonomers, the resulting copolymer materials will have residual double bonds present in 100 % of the DCPD-derived comonomer units with such E/DCPD copolymers. Instead of being at least partially hydrogenated in accordance with the process disclosed herein, some of these residual double bonds in the DCPD-derived comonomers may instead be functionalized by means of other reactions more fully described hereinafter. If any such functionalization reactions are carried out before the E/DCPD copolymer components are used in the process herein, then less than 100 % of the DCPD-derived comonomer units in the E/DCPD copolymer component will contain double bonds which are available for hydrogenation.
[0034] Whether or not the E/DCPD copolymer components used in the process and compositions herein have been functionalized, the E/DCPD copolymer component, either before or after hydrogenation, can generally have a weight average molecular weight, Mw, of from 50,000 to 1,000,000 g/mole as measured versus polystyrene standards by Gel Permeation Chromatography analysis. Alternatively, the E/DCPD copolymer components herein can have an Mw of from 75,000 to 900,000 g/mole, or even from 100,000 to 800,000 g/mole. As noted, weight average molecular weight for these E/DCPD copolymer materials can be determined in standard fashion using Gel Permeation Chromatography such as is described in the Test Methods section hereinafter.
[0039] The glass transition temperature of the various types of polymer components useful in the process and polymer compositions herein can be measured via a variety of techniques as discussed in Introduction to Polymer Science and Technology: An SPE Textbook, by Η. S. Kaufman and J. Falcetta, John Wiley & Sons, 1977, and in Polymer Handbook, 3rd ed., J. Brandup and E. Η. Immergut, Eds., John Wiley & Sons, 1989. The DSC techniques utilized in connection with the present disclosure are well known in the art and, as noted, are described hereinafter in the Test Methods section.
[0047] The E/DCPD copolymer components herein can be produced via a polymerization reaction which takes place by contacting ethylene with a polymerization mixture containing DCPD and any optional comonomers. The polymerization reaction is generally promoted by a selected catalyst or catalyst system and can take place under a selected set of polymerization reaction conditions.
[0053] With respect to apparatus employed in carrying out the polymerization to produce the E/DCPD copolymer components useful herein, the polymerization process can be carried out in a continuous stirred tank reactor, batch reactor or a plug flow reactor, or more than one reactor operated in series or parallel. These reactors may have, or may not have, internal cooling or heating, and the monomer feed may or may not be heated or refrigerated.
[0054] The E/DCPD copolymer materials formed within the polymerization mixture may be recovered therefrom by any suitable conventional separation means to thereby realize the E/DCPD copolymer components herein. For example, the formed copolymer materials can be precipitated from the polymerization reaction mixture using a suitable agent such as methanol and thereafter recovered via filtration. The recovered material can then be further washed, re -precipitated, re-filtered and dried to provide the desired copolymer component in a form which is usable in the process herein.
[0061] Another class of useful elastomeric polymers which can be utilized in the process and polymer compositions herein is represented by amorphous or low-crystalline flexible olefinic copolymers comprising at least two components selected from the group consisting of an ethylene component, a propylene component, and an α-olefm components having 4 to 20 carbon atoms. Such copolymers are in general ethylene-propylene copolymer rubbers (EPR), ethylene-α-olefm copolymer rubbers and propylene-α-olefin copolymer rubbers. The α-olefm in such copolymer rubbers can be selected, for example, from 1-butene, 1-pentene, 1-hexene, 4-methyl- 1-pentene, 1-octene and 1-decene.
[0064] The ethylene, propylene, and α-olefm copolymer rubbers hereinbefore described may also be graft-modified in conventional fashion with, for example, from 0.01 wt % to 5 wt %, or even from 0.1 wt % to 4 wt %, of graft monomers selected from unsaturated carboxylic acids or derivatives thereof. Examples of the unsaturated carboxylic acids and derivatives thereof which can used for modification of the ethylene -propylene-α-olefin copolymer rubbers herein can include such unsaturated carboxylic acids as acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, and nadic acid® (e/?<io-czs-bicyclo[2,2,l]hept-5-ene-2,3-dicarboxylic acid), and derivatives thereof such as acid halides, amides, imides, anhydrides, and esters. Specific examples of these acid derivatives include malenyl chloride, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, and glycidyl maleate. Among these materials, unsaturated dicarboxylic acids and derivatives thereof such as acid anhydrides thereof are especially useful. Maleic acid, nadic acid,® and anhydrides thereof are specific examples of this type of acid materials.
[0065] Another class of useful elastomeric polymers which can be utilized in the process and polymer compositions herein is represented by flexible olefϊn/nonconjugated diene copolymers comprising a nonconjugated diene component and at least two components selected from the group consisting of an ethylene component, a propylene component, and α- olefin components having 4 to 20 carbon atoms. Such copolymers are in general ethylene- propylene-diene monomer (EPDM) copolymer rubbers, ethylene-α-olefm-diene copolymer rubbers and propylene-α-olefm-diene copolymer rubbers. Examples of α-olefins which can be used in these olefin-diene copolymers include the same materials listed hereinbefore for the ethylene and propylene copolymer rubbers.
[0069] Another class of useful elastomeric polymers which can be utilized in the process and polymer compositions herein is represented by flexible diene/aromatic vinyl copolymers selected from the group consisting of random copolymers and block copolymers, each said copolymer comprising a conjugated diene component and an aromatic vinyl hydrocarbon component, as well as the hydrogenation products of these copolymers. Such copolymers are most commonly represented by styrene -butadiene block copolymer rubbers, (d) styrene- butadiene-styrene block copolymer rubbers, (e) styrene-isoprene block copolymer rubbers, (f) styrene-isoprene-styrene block copolymer rubbers, (g) hydrogenated styrene-butadiene- styrene block copolymer rubbers, (h) hydrogenated styrene-isoprene-styrene block copolymer rubbers, and (i) maleated or otherwise functionalized and/or grafted derivatives of such copolymer rubbers.
[0079] Such suitable inert organic solvents can include aromatic hydrocarbons such as benzene, toluene, xylenes, benzonitrile, chlorobenzene, o-dichlorobenzene, 1,2,4- trichlorobenzene, nitrobenzene, anisole, and phenyl nonane; saturated aliphatic hydrocarbons having from about 6 to about 20 carbons, such as cyclohexane; halogenated hydrocarbons such as methylene chloride, 1 ,2-dichloroethane, tetrachloroethane, chloroform, and carbon tetrachloride; and, particularly in cases involving functional E/DCPD copolymer derivatives, aliphatic ethers such as tetrahydrofuran. Mixtures or blends of diluents or solvents may also be utilized herein to form the common liquid reaction medium. Especially desirable organic solvents for use herein include o-dichlorobenzene, toluene, cyclohexane, tetrachloroethane, chlorobenzene, and mixtures thereof.
[0080] The process disclosed herein is one by which the desired polymer compositions herein can be prepared form the two types of olefinic polymer components hereinbefore described. As the first steps in such a process, both the E/DCPD copolymer component and the elastomeric polymer component are co-dissolved in the common liquid reaction medium hereinbefore described. This liquid reaction medium with the two polymer components dissolved therein is then subjected to hydrogenation conditions to hydrogenate some or all of the unsaturated materials within the reaction medium. Upon completion of the hydrogenation step, the resulting hydrogenated polymer materials can then be co-precipitated from the liquid reaction medium in the form of the desired polymeric compositions herein.
[0081] Within the common liquid reaction medium, the E/DCPD copolymer component and the elastomeric polymer will be added in accordance with the process herein in amounts relative to each other which depend on the desired properties and intended use of the hydrogenated polymer composition which is eventually co-precipitated out of the liquid reaction medium. For hydrogenated co-precipitated polymer combinations which are useful as or in impact-modified structural polyolefins, the weight ratio of the E/DCPD copolymer component to the elastomeric polymer component can generally range from 99:1 to 50:50, within the common liquid reaction medium. Alternatively, the weight ratio of E/DCPD copolymer component to elastomeric polymer component can range from 95:5 to 60:40, within the common liquid reaction medium.
[0090] In the simplified process herein for preparing blends of DCPD-based copolymers with elastomeric polymers, the precursor E/DCPD material and the desired elastomer are advantageously co-dissolved in a solvent prior to hydrogenation of the E/DCPD copolymer. The E/DCPD copolymer is then hydrogenated in the presence of the elastomer (or concurrently along with some or all of any olefin units present in the elastomer), and the two materials are efficiently coprecipitated in a manner similar to solution-blending. No added dissolution or precipitation steps are required for the solution-blending process over and above those of the hydrogenation process. In contrast, a traditional solution-blending protocol would involve separate steps for the hydrogenation of the E/DCPD copolymer and the solution-blending of the resultant hydrogenated E/DCPD (H-E/DCPD) copolymer with the elastomeric polymer.
[0093] Compositions having an appropriate ratio of E/DCPD copolymer component to elastomeric polymer component therein are suitable for molding into useful materials such as structural polyolefm materials having desirable thermal and impact resistance. Such mixtures of polymers will generally exhibit two distinct glass transition temperatures. For example, such compositions can have a first Tg which ranges from -80 0C to 0 0C and a second Tg which can range from 85 0C to 190 0C. It should be noted that in some cases, these separate Tgs may not be experimentally observable by DSC techniques due to weakness. Within such compositions, the weight ratio of E/DCPD copolymer component to elastomeric polymer component can generally range from 99: 1 to 50:50. Alternatively, the weight ratio of these two components within the polymer compositions herein can range from 95:5 to 60:40.
[00103] Chemical composition distribution (CCD) analysis was measured using a model 200 PolymerChar S. A. Crystallization Analysis Fractionation (CRYSTAF) instrument. The polymer sample (20-30 mg) was dissolved in 30 mL ODCB (stabilized with 0.125 g/L 2,6-di- t-butyl-4-methylphenol) at 160 0C for 60 minutes and equilibrated at 100 0C for 45 minutes, followed by cooling to 30 0C at a rate of 0.2 K/min (analysis time ~ 9 hours). A two- wavelength infrared detector was used to measure polymer concentration during crystallization (3.5 μm, 2853 cm"1 sym. stretch) and to compensate for baseline drifts (3.6 μm) during analysis. The solution polymer concentration was monitored at intervals yielding a cumulative concentration curve. The derivative of this curve with respect to temperature represents the weight fraction of crystallized polymer at each temperature ("% soluble by CRYSTAF"). EXAMPLES
[00105] A lO g portion of an E/DCPD copolymer containing 40.0 mole % DCPD by 1H NMR (57.4 mmol DCPD units; further characterization given in Table 1) was dissolved in 140 mL anhydrous o-dichlorobenzene (ODCB) at room temperature overnight in a glass liner for a 300 mL Parr reactor. Separately, Rh(PPh3)3Cl (Wilkinson's catalyst, 95 mg, 0.103 mmol, 560:1 diene:Rh) and PPh3 (928 mg, 3.54 mmol, 34.5:1 P:Rh) were each dissolved in 5 mL ODCB and added to the polymer solution. The reactor was quickly assembled, charged to 800 psig (5515.8 kPa) H2, and heated to 105 0C for 22 hours with stirring. Subsequently, the reactor was vented, cooled, and opened to the atmosphere. The contents of the liner were added to an excess of methanol to precipitate the polymer. This hydrogenation procedure was repeated five times with five additional 1O g portions of the E/DCPD copolymer, and the combined materials were re-dissolved twice in tetrachloroethane (TCE, ca. 3/5 original volume of ODCB) at 80-85 0C, filtered to remove decomposed catalyst particles, and reprecipitated into warm methanol followed by agitation of the precipitated polymer/methanol mixture in a Waring blender. No residual DCPD olefin resonances were seen by 1H NMR. The white hydrogenated polymer was dried for 60 hours in a vacuum oven at 60 0C (58.3 g, 96 %). Full characterization of the E/DCPD precursor and the hydrogenated H-E/DCPD product is given in Table 1. TABLE 1
[00110] A glass liner for a 300 cc Hasteloy C Parr reactor was charged with 35 mL ODCB, a stirbar, 2.4 g of the E/DCPD copolymer described in Comparative Example Cl (13.77 mmol DCPD units), and 0.6 g E/P/ENB elastomer (0.211 mmol ENB units) (full characterization is given in Table 4). The solution was stirred overnight at room temperature to effect dissolution of the polymers. The stirbar was then removed and the liner was inserted into the Parr reactor. Separately, 23 mg (Ph3P)3RhCl (0.0249 mmol, 561 :1 total olefϊn:Rh) and 227 mg Ph3P (0.865 mmol, 34.7:1 P:Rh) were each dissolved in 5 mL ODCB. Both solutions were added to the polymer solution (final polymer concentration 6.67 wt/vol %) and the reactor was assembled. After mechanical stirring was initiated, the reactor was pressurized to 200 psig (1379.0 kPa) H2 and vented three times, followed by repressurization to 800 psig (5515.8 kPa) H2 (single charge). The temperature was raised to 1050C and the contents of the reactor were stirred at 105 0C overnight (20-22 h). The reactor was cooled and vented, and its contents were precipitated into 200 mL methanol. After manually cutting large solids into smaller pieces, the entire polymer solution (precipitate + solvents) was agitated in a Waring blender. The shredded polymer was collected by filtration, rinsed with methanol, and then redissolved in 133 mL TCE (2.25 wt/vol % polymer) at room temperature, reprecipitated into 470 mL methanol, and re-shredded in a Waring blender. After collection by filtration, the white, flexible, cohesive crumb was dried at 60 0C overnight (3.043 g; theo. yield of both components 3.030 g; quantitative). [00111] Both 1H and 13C NMR analysis of the product showed the presence of both blend components (via propylene CH3 resonances) indicating successful coprecipitation, and complete hydrogenation of both DCPD and 5-ethylidene-2-norbornene olefin units to produce a blend of H-E/DCPD (similar to the H-E/DCPD produced similarly in Comparative Example Cl) and an ethylene/propylene/5-ethyl-2-norbornene copolymer. DSC analysis showed the following features in the 2nd heat: Tg 136.3 0C (H-E/DCPD); Tm 43.3 0C, br (hydrogenated E/P/ENB); Tm 122.1 0C, small (ΔHf 0.27 J/g; minor homo-polyethylene present in E/DCPD). The expected Tg for hydrogenated E/P/ENB at ~ -40 0C was not observed, which may be due to weakness of the transition. A thin film of the blend was pressed at 245 0C for three minutes between two aluminum-coated plates using a PHI Company QL-433-6-M2 press, and then pressed at 7°C in the cooling part of the press for 3 minutes. The film obtained from this un-optimized procedure was inhomogeneous but showed flexibility.
[00114] Both 1H and 13C NMR analysis of the product showed the presence of both blend components (via 1-octene CH3 resonances) indicating successful coprecipitation, and complete hydrogenation of both DCPD and 4-vinyl-l-cyclohexene olefin units to produce a blend of H-E/DCPD (similar to the H-E/DCPD produced similarly in Comparative Example Cl) and an ethylene/propylene/vinylcyclohexane copolymer. DSC analysis showed the following features in the 2nd heat: Tg -40.4 0C (hydrogenated E/O/VCH); Tg 137.6 0C (H- E/DCPD); Tm 124.5 0C, small (ΔHf 0.25 J/g; minor homo-polyethylene present in E/DCPD). A thin film of the blend was pressed at 245 0C for three minutes in the manner described in Example 1. The film obtained from this un-optimized procedure was inhomogeneous and tore easily, but showed some flexibility (to a lesser extent than the film prepared in Example
[00117] A procedure similar to the repeat (20 g-scale) hydrogenation procedure given in Comparative Example C4 was carried out in a linerless 2 L Parr reactor using 16.0 g of the E/DCPD copolymer described in Comparative Example C4 (91.25 mmol DCPD units) and 4.0 g of the E/P/ENB terpolymer described in Example 1 (1.408 mmol ENB units). The polymers were first dissolved overnight in 200 mL ODCB to give a cloudy solution (some gels); subsequently, 152 mg (Ph3P)3RhCl) (0.164 mmol; 565:1 total olefϊn:Rh) and 1.494 g Ph3P (5.69 mmol, 34.7:1 P:Rh) were each dissolved in 33 mL ODCB and added to the polymer solution, which was diluted to a final volume of 300 mL (final polymer concentration 6.7 wt/vol %). After hydrogenation, the polymer solution was added to 1300 mL methanol to precipitate the product blend, which was collected by filtration after agitation in a Waring blender, re -precipitated from 900 mL TCE into 3.0 L methanol, re-collected, and dried in a vacuum oven at 600C (19.36 g). 1H NMR analysis indicated the presence of residual TCE solvent. The blend material was then re-precipitated from 800 mL cyclohexane into 2.0 L acetone, re-collected, and re-dried to give 18.33 g of a lightweight flexible white crumb (91%; theo. yield 20.196 g). The 1H NMR spectra of the blend indicated only trace amounts of olefins and showed the presence of both polymer components in a similar manner to Example 1. DSC analysis showed the following features in the 2nd heat: Tg 147.5°C (H- E/DCPD); Tm 44.00C, br (hydrogenated E/P/ENB); Tg -40.3 0C (hydrogenated E/P/ENB). Example 4. Preparation of compression-molded samples of H-E/DCPD / E/P/ENB rubber blend made by tandem solution-blending / hydrogenation.
[00118] The isolated blend material of Example 3 was compression-molded into specimens for room temperature and 00C Izod impact tests. Compression molding was chosen for sample preparation so as to most obviously demonstrate the success of the tandem solution-blending / hydrogenation technique in producing impact-modified materials (while compression molding typically produces less satisfactory specimens than injection-molding, injection-molding by necessity involves a pre-melt-mixing step). The blend material was compression-molded into rectangular impact bars of dimension 63 x 12 x 3 mm at 265°C using a PHI company QL-433-6-M2 model hydraulic press equipped with separate heating and cooling platforms and a stainless steel mold. The upper and lower press plates were covered with TeflonTM-coated aluminum foil, and halocarbon aerosol mold release agent (Miller- Stephenson MS-122DF) was sprayed onto the mold and press plates prior to pressing. The following multistage procedure was used after pre -heating the press plates to 265°C: (1) 5 minutes at temperature with a slight (2 ton) overpressure followed by release; (2) 60 seconds at temperature and 10 tons followed by release; (3) 60 seconds at temperature and 20 tons followed by release; (4) 60 seconds at temperature and 30 tons followed by release; (5) 4 minutes at temperature and 30 tons followed by release; (6) 3 minutes at 7°C (cooling platform) and 30 tons followed by release. A second set of bars was prepared at 2500C, using 8 minute periods for the initial (2 ton / 2500C) and, optionally, the final (30 ton / 2500C) press steps. All of the bars were opaque and light beige in color with some small voids appearing at the surface. The bars were individualy weighed to provide additional relative characterization of quality, although no consistent relationships were observed between bar weight (greater weight = fewer voids) and impact strength.
[00119] A procedure similar to Example 3 was carried out in a linerless 2 L Parr reactor using 16.0 g of the E/DCPD copolymer described in Comparative Example C4 (91.25 mmol DCPD units) and 4.0 g of the E/O/VCH terpolymer described in Example 2 (8.572 mmol VCH units). The hydrogenation catalyst components used were 166 mg (PhsP^RhCl) (0.179 mmol; 558:1 total olefm:Rh) and 1.630 g Ph3P (6.21 mmol, 34.7:1 P:Rh). A crude yield of 18.74 g was obtained; re-precipitation from cyclohexane / acetone gave 17.89 g of the blend material as fluffy white granular pads / crumb (89%; theo. yield 20.208 g). 1H NMR analysis of the blend indicated only trace amounts of olefins and showed the presence of both polymer components in a similar manner to Example 2. DSC analysis showed the following features in the 2nd heat: Tg 145.1 0C (H-E/DCPD). A Tg for the hydrogenated E/O/VCH terpolymer was not seen in the 2nd heat; however, a very weak Tg at -41.6 0C was seen in the 1st heat and assigned to the hydrogenated E/O/VCH terpolymer.
[00122] The sample bars prepared in Examples 4, 6, and C5 were subjected to Notched Izod impact tests at room temperature and 0 0C using a TMI Izod Impact Tester (ASTM D256; 45° notch; 2.028 ft-lb pendulum). Bars used for 00C tests were pre-conditioned at 00C for 1 hour. All bars showed complete break upon impact. Results are summarized in Table 6. The test bars of neat H-E/DCPD were so brittle that data could not be generated (noted as 0 ft-lb/in in Table 6). As a secondary comparative, room temperature impact data for the neat H-E/DCPD test samples given in Comparative Example C3 (prepared by injection-molding and therefore of higher quality) are included in Table 6.
[00123] The data shown in Table 6 indicate that blends of H-E/DCPD copolymers with elastomers prepared by tandem solution-blending / hydrogenation demonstrate improved impact properties, even in an extreme case when no subsequent melt-mixing occurs. The room temperature and 00C Izod impact of the compression-molded samples of the H- E/DCPD / E/P/ENB and H-E/DCPD / E/O/VCH blends are superior to those for neat H- E/DCPD. In fact, the Izod impact values of these samples are superior to the room temperature impact value for injection-molded samples of neat H-E/DCPD. The E/P/ENB elastomer provided greater enhancement of impact strength at both room temperature and 00C.

中文:
[0011]在DCPD基共聚物内存在残留的不饱和度可使得这种共聚物相对不稳定。例如,在乙烯-二环戊二烯(E/DCPD)共聚物内的残留双键使得这些材料在加工和使用过程中对交联、氧化和其他不想要的副反应敏感。若在这种共聚物内为了改性其冲击性能,与E/DCPD结合使用的弹性体还含有任何残留的不饱和度,则可产生类似的问题,这是其内所使用的共聚单体的性质导致的。因此,若经济上吸引人的DCPD-基材料用作结构聚烯烃制备的基础材料,则需要通过部分或完全氢化这种共聚物结构内的残留双键或者其他衍生化,消除或者降低在这种共聚物内的残留的不饱和度。
[0026]在该方法中和最终在氢化最后,在此处的聚合物组合物中所使用的乙烯-二环戊二烯组分通常可含有25mol%至65mol�PD衍生的单体单元。或者这些E/DCPD共聚物组分可包括27.5mol%至60mol�PD衍生的单元。或者,此处所使用的E/DCPD共聚物组分中的DCPD含量范围可以是30mol%至55mol%。
[0029]在共聚乙烯和DCPD共聚单体之后,所得共聚物材料在100�PD衍生的共聚单体单元和这种E/DCPD共聚物内存在残留的双键。与根据此处公开的方法至少部分氢化不同,在DCPD衍生的共聚单体内这些残留双键中的一些可通过下文更加充分地描述的其他反应官能化。若在此处的方法中使用E/DCPD共聚物组分之前,进行任何这种官能化反应,则在E/DCPD共聚物组分内小于100�PD衍生的共聚单体单元含有可供氢化的双键。
[0034]不管此处的方法和组合物中所使用的E/DCPD共聚物组分官能化与否,在氢化之前或之后,E/DCPD共聚物组分的重均分子量Mw通常可以是50,000-1,000,000g/mol,这通过凝胶渗透色谱法分析,相对于聚苯乙烯来测量。或者,此处的E/DCPD共聚物组分的Mw可以是75,000至900,000g/mol,或者甚至100,000至800,000g/mol。正如所述的,可使用凝胶渗透色谱法,例如下文的试验方法部分所述的凝胶渗透色谱法,以标准方式测定这些E/DCPD共聚物材料的重均分子量。
[0039]可通过在H.S.Kaufman和J.Falcetta的Introductionto Polymer Science and Technology:An SPE Textbook,John Wiley& Sons,1977,和在Polymer Handbook,第3版,J.Brandup和E.H.Immergut,Eds.,John Wiley & Sons,1989中所述的各种技术,测量在此处的方法和聚合物组合物中有用的各类聚合物组分的玻璃化转变温度。结合本发明公开内容所使用的DSC技术是本领域众所周知的,且正如下文的试验方法部分中所述。
[0047]可通过聚合反应,生产此处的E/DCPD共聚物组分,所述聚合反应通过接触乙烯与含DCPD和任何任选的共聚单体的聚合混合物而发生。通常通过选择催化剂或催化剂体系加速该聚合反应,且该聚合反应可在选择的一组聚合反应条件下发生。
[0053]关于在进行聚合生产此处有用的E/DCPD共聚物组分中所使用的装置,可在连续的搅拌罐反应器、间歇反应器或活塞流反应器或在串联或平行地操作的大于一个反应器内进行聚合工艺。这些反应器可具有或者可以不具有内部冷却或加热,和单体原料可以加热或制冷或者可以没有。
[0054]可通过任何合适的常规分离方式,从中回收在聚合混合物内形成的E/DCPD共聚物材料,于是实现此处的E/DCPD共聚物组分。例如,可使用合适的试剂,例如甲醇,从聚合反应混合物中沉淀所形成的共聚物材料,之后通过过滤回收。然后可进一步洗涤回收的材料,再过滤和干燥,提供可在此处的方法中使用的所需共聚物组分形式。
[0061]可在此处的方法和组合物中使用的另一组有用的弹性体聚合物以含选自乙烯组分、丙烯组分和具有4-20个碳原子的α-烯烃组分中的至少两种组分的无定形或低结晶柔性的烯属共聚物为代表。一般地,这种共聚物是乙烯-丙烯共聚物橡胶(EPR)、乙烯-α-烯烃共聚物橡胶和丙烯-α-烯烃共聚物橡胶。在这种共聚物橡胶内的α-烯烃可例如选自1-丁烯、1-戊烯、1-己烯、4-甲基-1-戊烯、1-辛烯和1-癸烯。
[0064]前面所述的乙烯、丙烯和α-烯烃共聚物橡胶也可按照常规方式例如采用0.01wt%至5wt%,或甚至0.1wt%至4wt%选自不饱和羧酸或其衍生物中的接枝单体接枝改性。改性此处的乙烯-丙烯-α-烯烃共聚物橡胶可使用的不饱和羧酸及其衍生物的实例可包括这种不饱和羧酸,例如丙烯酸、马来酸、富马酸、四氢邻苯二甲酸、衣康酸、柠康酸、巴豆酸、异巴豆酸和4-降冰片烯-1,2-(内-顺式-双环[2,2,1])庚-5-烯-2,3-二羧酸)及其衍生物,例如酰卤、酰胺、酰亚胺、酸酐和酯。这些酸衍生物的具体实例包括马来酰氯、马来酰亚胺、马来酸酐、柠康酸酐、马来酸单甲酯、马来酸二甲酯和马来酸缩水甘油酯。在这些材料当中,不饱和二羧酸及其衍生物,例如其酸酐是特别有用的。马来酸、4-降冰片烯-1,2-及其酸酐是这类酸材料的具体实例。
[0065]可在此处的方法和聚合物组合物中使用的另一组有用的弹性体聚合物以含非共轭二烯烃组分和选自乙烯组分、丙烯组分和具有4-20个碳原子的α-烯烃中的至少两种组分的柔性烯烃/非共轭二烯烃共聚物为代表。这种共聚物一般地是乙烯-丙烯-二烯烃单体(EPDM)的共聚物橡胶、乙烯-α-烯烃-二烯烃共聚物橡胶和丙烯-α-烯烃-二烯烃共聚物橡胶。可在这些烯烃-二烯烃共聚物中使用的α-烯烃的实例包括前面针对乙烯和丙烯共聚物橡胶中列出的相同的材料。
[0069]可在此处的方法和聚合物组合物中使用的另一组有用的弹性体聚合物以选自无规共聚物和嵌段共聚物中的柔性二烯烃/芳族乙烯基共聚物为代表,其中每一种所述的共聚物包括共轭二烯烃组分和芳族乙烯基烃组分,以及这些共聚物的氢化产物。这种共聚物最常见地以苯乙烯-丁二烯嵌段共聚物橡胶,(d)苯乙烯-丁二烯-苯乙烯嵌段共聚物橡胶,(e)苯乙烯-异戊二烯嵌段共聚物橡胶,(f)苯乙烯-异戊二烯-苯乙烯嵌段共聚物橡胶,(g)氢化苯乙烯-丁二烯-苯乙烯嵌段共聚物橡胶,(h)氢化苯乙烯-异戊二烯-苯乙烯嵌段共聚物橡胶,和(i)这些共聚物橡胶的马来酸化或其他官能化和/或接枝的衍生物。
[0079]这种合适的惰性有机溶剂可包括芳烃,例如苯、甲苯、二甲苯、苄腈、氯苯、邻二氯苯、1,2,4-三氯苯、硝基苯、茴香醚和苯基壬烷;具有约6-约20个碳原子的饱和脂族烃,例如环己烷、卤代烃,例如二氯甲烷、1,2-二氯乙烷、四氯乙烷、氯仿和四氯化碳;和尤其在牵涉官能E/DCPD共聚物衍生物的情况下,脂族醚,例如四氢呋喃。此处也可使用稀释剂或溶剂的混合物或共混物,形成常见的液体反应介质。此处使用的特别理想的有机溶剂包括邻二氯苯、甲苯、环己烷、四氯乙烷、氯苯及其混合物。
[0080]此处公开的方法是其中可由前面所述的两类烯属聚合物组分制备此处所需的聚合物组合物的方法。作为这一方法的第一步,E/DCPD共聚物组分和弹性体聚合物组分二者共溶解在前面所述的常见的液体反应介质内。然后将在其内溶解了这两种聚合物组分的这一液体反应介质置于氢化条件下,以氢化反应介质内的一些或所有的不饱和材料。一旦完成氢化步骤,则可从液体反应介质中以此处所需的聚合物组合物形式共沉淀所得氢化聚合物材料。
[0081]根据此处的方法,在常见的液体反应介质内添加E/DCPD共聚物组分和弹性体聚合物组分,其中相对于彼此,其用量取决于最终从液体反应介质中共沉淀出来的氢化聚合物组合物所需的性能和打算的用途。对于作为冲击改性的结构聚烯烃或在其内有用的氢化共沉淀聚合物的结合物来说,在常见的液体反应介质内E/DCPD共聚物组分与弹性体聚合物组分的重量比范围通常可以是99∶1-50∶50。或者,在常见的液体反应介质内E/DCPD共聚物组分与弹性体聚合物组分的重量比范围可以是95∶5-60∶40。
[0090]在此处制备DCPD基共聚物与弹性体聚合物的共混物的简化方法中,有利地在氢化E/DCPD共聚物之前,在溶剂内共溶解前体E/DCPD材料和所需的弹性体。然后在弹性体(或与弹性体内存在的一些或所有任何烯属单元一起)存在下,氢化E/DCPD共聚物,并以与溶液共混类似的方式有效地共沉淀这两种材料。对于溶液共混工艺来说,除了氢化工艺的那些步骤以外,不要求外加的溶解或沉淀步骤。相反,常规的溶液共混方案牵涉氢化E/DCPD共聚物和溶液共混所得氢化的E/DCPD(H-E/DCPD)共聚物与弹性体聚合物的单独的步骤。
[0093]具有此处合适的E/DCPD共聚物组分与弹性体聚合物组分之比的组合物适合于模塑成有用的材料,例如具有所需的耐热性和抗冲击性的结构聚烯烃材料。这种聚合物混合物通常显示出两种不同的玻璃化转变温度。例如,这一组合物可具有范围为-80°C到0°C的第一Tg和范围可以是85°C-190°C的第二Tg。应当注意,在一些情况下,这些单独的Tg不可能通过实验,通过DSC技术观察到,因为比较弱。在这一组合物内,E/DCPD共聚物组分与弹性体聚合物组分的重量比范围通常可以是99∶1-50∶50。或者,在聚合物组合物内的这两种组分的重量比范围可以是95∶5-60∶40。
[00103]使用型号200PolymerChar S.A.结晶分析分极(CRYSTAF)仪器,测量化学组成分布(CCD)分析。在160°C下将聚合物样品(20-30mg)经60分钟溶解在30ml ODCB(它用0.125g/L的2,6-二叔丁基-4-甲基苯酚稳定)内,并在100°C下平衡45分钟,接着在0.2K/min下冷却到30°C(分析时间~9小时)。在结晶过程中,使用双波长红外检测仪,测量聚合物浓度(3.5μm,2853cm-1对称拉伸),并在分析过程中补偿基线的漂移(3.6μm)。在一定的时间间隔处监控溶液聚合物的浓度,从而得到累积的浓度曲线。这一曲线相对于温度的导数代表在每一温度下结晶的聚合物的重量分数(“%通过CRYSTAF可溶”)。
[00105]在室温下,在300ml Parr反应器的玻璃套管内,将10g通过1H NMR测定含40.0mol�PD的E/DCPD共聚物部分(57.4mmolDCPD单元;表1中给出了进一步的表征特征)在140ml无水邻二氯苯(ODCB)内溶解过夜。独立地将Rh(PPh3)3Cl(Wilkinson催化剂,95mg,0.103mmol,560∶1二烯烃∶Rh)和PPh3(928mg,3.54mmol,34.5∶1P∶Rh)各自溶解在5mL ODCB内,并加入到聚合物溶液中。快速组装反应器,引入800psig(5515.8kPa)H2,并在搅拌下,经22小时加热到105°C。随后,放空反应器,冷却并朝大气打开。将套管的内容物加入到过量甲醇中,沉淀聚合物。采用5种额外的10g一部分的E/DCPD共聚物,这一氢化工序反复5次,在四氯乙烷(TCE,ODCB的起始体积的约3/5)内,在80-85°C下再溶解结合的材料,过滤,除去分解的催化剂颗粒,并在温热的甲醇内再沉淀,接着在Waring共混器内搅拌沉淀的聚合物/甲醇混合物。通过1H NMR,没有观察到残留的DCPD烯烃共振。在真空烘箱内,在60°C下干燥白色的氢化聚合物60小时(58.3g,96%)。表1给出了E/DCPD前体和氢化的H-E/DCPD产品的全面表征。
[00110]向300cc Hasteloy C Parr反应器的玻璃套管内引入35mlODCB、搅拌棒、2.4g对比例C1中所述的E/DCPD共聚物(13.77mmolDCPD单元)和0.6g E/P/ENB弹性体(0.211mmol ENB单元)(表4中给出了全部表征特征)。在室温下搅拌该溶液过夜,进行聚合物的溶解。然后取出搅拌棒,并将套管插入到Parr反应器内。独立地将23mg(Ph3P)3RhCl(0.0249mmol,561∶1全部烯烃∶Rh)和227mgPh3P(0.865mmol,34.7∶1 P∶Rh)各自溶解在5mL ODCB内。将这两种溶液都加入到聚合物溶液中(最终聚合物浓度为6.67wt/vol%),并组装该反应器。在开始机械搅拌之后,给反应器加压到200psig(1379.0kPa)H2并放空三次,接着再加压到800psig(5515.8kPa)H2(单次引入)。升温到105°C并在105°C下搅拌反应器内容物过夜(20-22h)。冷却反应器并放空,和在200ml甲醇内沉淀其内容物。在将大的固体人工切割成小片之后,在Waring共混器内搅拌全部聚合物溶液(沉淀+溶剂)。通过过滤收集粉碎的聚合物,用甲醇漂洗,然后在室温下再溶解在133ml TCE(2.25wt/vol%聚合物)内,在470ml甲醇内再沉淀,和在Waring共混器内再粉碎。在通过过滤收集之后,在60°C下干燥白色、柔性的粘附团块过夜(3.043g;两种组分的理论产量3.030g;定量)。
[00114]产物的1H和13C NMR分析均表明存在这两种共混物组分(通过1-辛烯的CH3共振),从而表明成功地共沉淀,和DCPD与4-乙烯基-1-环己烯中的烯烃单元均完全氢化,产生了H-E/DCPD(类似于与对比例C1类似地生产的H-E/DCPD)和乙烯/丙烯/乙烯基环己烷共聚物的共混物。DSC分析表明在第二次加热中的下述特征:Tg-40.4°C(氢化E/O/VCH);Tm137.6°C(H-E/DCPD);Tm124.5°C;小(ΔHf0.25J/g;在E/DCPD内存在微量均聚乙烯)。以与实施例1所述的方式在245°C下挤压共混物的薄膜3分钟。由这一未优化的工序获得的膜不均匀且容易撕裂,但显示出一些柔性(其程度低于实施例1制备的膜)。
[00117]在无套管的2L Parr反应器内,使用16.0g对比例C4中所述的E/DCPD共聚物(91.25mmol DCPD单元)和4.0g实施例1中所述的E/P/ENB三元共聚物(1.408mmol ENB单元),进行与重复对比例C4中给出的氢化工序(20g规模)类似的工序。首先在200ml ODCB内溶解聚合物过夜,得到浑浊溶液(一些凝胶);随后,将152mg(Ph3P)3RhCl(0.164mmol;565∶1全部烯烃∶Rh)和1.494gPh3P(5.69mmol,34.7∶1 P∶Rh)各自溶解在33ml ODCB内并加入到该聚合物溶液中,稀释到最终体积300ml(最终聚合物浓度6.7wt/vol%)。在氢化之后,将该聚合物溶液加入到1300L甲醇中,使聚合物共混物沉淀,在Waring共混器内搅拌之后,通过过滤收集。从900ml TCE中再沉淀到3.0L甲醇内,再收集,在真空烘箱内在60°C下干燥(19.36g)。1H NMR分析表明存在残留的TCE溶剂。然后从800ml环己烷中再沉淀共混物材料到2.01丙酮内,再收集和再干燥,得到18.33g轻质柔性白色团块(91%,理论产量20.196g)。以与实施例1类似的方式,共混物的1H NMR光谱表明仅仅痕量的烯烃且表明存在这两种聚合物组分。DSC分析表明在第二次加热中的下述特征:Tg147.5°C(H-E/DCPD);Tm44.0°C,br(氢化E/P/ENB);Tg-40.3°C(氢化E/P/ENB)。
[00118]对于室温和0°C伊佐德冲击试验来说,将实施例3的独立的共混物材料压塑成样品。对于样品的制备来说,选择压塑,以便最显而易见地证明在生产冲击改性的材料中,级联溶液共混/氢化技术是成功的(尽管压塑典型地产生不如注塑满意的样品,注塑必然牵涉预熔体混合步骤)。在265°C下,使用PHI公司的配有单独的加热和冷却平台和不锈钢模具的型号QL-433-6-M2的液压机,将共混物材料压塑成尺寸为63×12×3mm的矩形冲击棒材。用TeflonTM涂布的铝箔覆盖上部和下部压板,并在挤压之前,在模具和压板上喷洒卤代烃脱模剂(Miller-Stephenson MS-122DF)。在预热压板到265°C之后,使用下述多步工序:(1)在该温度和轻微(2吨)的过压下5分钟,接着剥离;(2)在该温度和10吨下60秒,接着剥离;(3)在该温度和20吨下60秒,接着剥离;(4)在该温度和30吨下60秒,接着剥离;(5)在该温度和30吨下4分钟,接着剥离;(6)在7°C(冷却平台)和30吨下3分钟,接着剥离。对于起始(2吨/250°C)和任选地最终(30吨/250°C)的挤压步骤来说,使用8分钟的时间段,在250°C下制备第二组棒材。所有棒材不透明且为浅琥珀色,并在表面上出现一些小的孔隙。独立地称重棒材,提供质量的额外的相对表征,但在棒材重量之间没有观察到一致的关系(较大的重量=较少的孔隙)和冲击强度。
[00119]在无套管的2L Parr反应器内,使用16.0g对比例C4中所述的E/DCPD共聚物(91.25mmol DCPD单元)和4.0g实施例2中所述的E/O/VCH三元共聚物(8.572mmol VCH单元),进行与实施例3类似的工序。所使用的氢化催化剂组分是166mg(Ph3P)3RhCl((0.179mmol;558∶1全部烯烃∶Rh)和1.630g Ph3P(6.21mmol,34.7∶1 P∶Rh)。获得18.74g的粗产量;从环己烷/丙酮中再沉淀,得到17.89g絮状白色颗粒垫料(pad)/团块形式的共混物材料(89%;理论产量20.208g)。以与实施例2类似的方式,1H NMR分析该共混物,表明仅仅痕量的烯烃且表明存在这两种共聚物组分。DSC分析表明在第二次加热中的下述特征:Tg145.1°C(H-E/DCPD)。在第二次加热中没有观察到氢化E/O/VCH三元共聚物的Tg;然而,在第一次加热中在-41.6°C处观察到非常弱的Tg且归因于氢化E/O/VCH三元共聚物。
[00122]在室温和0°C下,使用TMI Izod Impact Tester(ASTMD256;45°缺口;2.028ft-lb摆锤),对实施例4、6和C5制备的样品棒材进行缺口伊佐德冲击试验。0°C试验所使用的棒材在0°C下预调节1小时。所有棒材当冲击时显示出完全断裂。表6中概述了结果。纯H-E/DCPD的试验棒材如此脆,以致于不可能生成数据(表6中以0ft-lb/in描述)。作为辅助对比,表6中包括了在对比例C3中给出的纯H-E/DCPD试样(通过注塑制备和因此质量较高)的室温冲击数据。
[00123]表6所示的数据表明级联溶液共混/氢化制备的H-E/DCPD共聚物与弹性体的共混物显示出改进的冲击性能,甚至在其中没有发生随后的熔体混合的极端情况下。H-E/DCPD/E/P/ENB和H-E/DCPD/E/O/VCH共混物的压塑样品的室温和0°C伊佐德冲击优于纯H-E/DCPD。事实上,对于纯H-E/DCPD的注塑样品来说,这些样品的伊佐德冲击值优于室温冲击值。在室温和0°C下,E/P/ENB弹性体均提供冲击强度的较大提高。