English:
[0035] In one aspect, the thermoformed film and/or sheet of the invention contain no polycarbonate.
[0044] In one aspect, a process of making thermoformed film and/or sheet of the invention is provided wherein the step of drying the sheets and/or films prior to thermoforming is eliminated.
[0047] In one aspect, the polyesters useful in the thermoformed film and/or sheet of the invention can be amorphous or semicrystalline. In one aspect, certain polyesters useful in the thermoformed film or sheet of the invention can have a relatively low crystallinity. Certain polyesters useful in the thermoformed film or sheet of the invention can thus have a substantially amorphous morphology, meaning that the polyesters comprise substantially unordered regions of polymer.
[0048] In other aspects, the film and/or sheet of the invention includes thermoformed film or sheet.
[0049] Figure 1 is a graph showing the effect of comonomer on the fastest crystallization half-times of modified PCT copolyesters.
[0051] Figure 3 is a graph showing the effect of 2,2,4,4-tetramethyl-i ,3- cyclobutanediol composition on the glass transition temperature (Tg) of the copolyester.
[0052] The present invention may be understood more readily by reference to the following detailed description of certain embodiments of the invention and the working examples. In accordance with the purpose(s) of this invention, certain embodiments of the invention are described in the Summary of the Invention and are further described herein below. Also, other embodiments of the invention are described herein.
[0084] In certain embodiments, terephthalic acid, or an ester thereof, such as, for example, dimethyl terephthalate, or a mixture of terephthalic acid and an ester thereof, makes up most or all of the dicarboxylic acid component used to form the polyesters useful in the thermoformed film or sheet of the invention. In certain embodiments, terephthalic acid residues can make up a portion or all of the dicarboxylic acid component used to form the present polyester at a concentration of at least 70 mole %, such as at least 80 mole %, at least 90 mole%, at least 95 mole%, at least 99 mole%, or 100 mole %. In certain embodiments, polyesters with higher amounts of terephthalic acid can be used in order to produce higher impact strength properties. For purposes of this disclosure, the terms "terephthalic acid" and "dimethyl terephthalate are used interchangeably herein. In one embodiment, dimethyl terephthalate is part or all of the dicarboxylic acid component used to make the polyesters useful in the present invention. In all embodiments, ranges of from 70 to 100 mole %; or 80 to 100 mole %; or 90 to 100 mole %; or 99 to 100 mole %; or 100 mole % terephthalic acid and/or dimethyl terephthalate and/or mixtures thereof may be used.
[00101] In another embodiment, certain polyesters useful in the thermoformed film and/or sheet of the invention can exhibit an increase in notched Izod impact strength when measured at 0 0 C of at least 3% or at least 5% or at least 10% or at least 15% as compared to the notched Izod impact strength when measured at -5 0 C with a 10-mil notch in a 1/8-inch thick bar determined according to ASTM D256. In addition, certain other polyesters can also exhibit a retention of notched Izod impact strength within plus or minus 5% when measured at 0°C through 30 0 C with a 10-mil notch in a 1/8-inch thick bar determined according to ASTM D256.
[00102] In yet another embodiment, certain polyesters useful in the thermoformed film and/or sheet of the invention can exhibit a retention in notched Izod impact strength with a loss of no more than 70% when measured at 23°C with a 10-mil notch in a 1/4-inch thick bar determined according to ASTM D256 as compared to notched Izod impact strength for the same polyester when measured at the same temperature with a 10-mil notch in a 1/8-inch thick bar determined according to ASTM D256.
[00108] In some embodiments, use of the polyester compositions useful in the film and/or sheet of the invention minimizes and/or eliminates the drying step prior to melt processing and/or thermoforming.
[00109] Although the polyesters useful in the thermoformed film and/or sheet of the invention can have any moisture content, in one embodiment, they can have a moisture content of 0.02 to 1.0 weight percent of the total weight of the polyester prior to melt processing.
[00111] The polyesters useful in the thermoformed film and/or sheet of the invention can be made by processes known from the literature such as, for example, by processes in homogenous solution, by transesterification processes in the melt, and by two phase interfacial processes. Suitable methods include, but are not limited to, the steps of reacting one or more dicarboxylic acids with one or more glycols at a temperature of 100°C to 315°C at a pressure of 0.1 to 760 mm Hg for a time sufficient to form a polyester. See U.S. Patent No. 3,772,405 for methods of producing polyesters, the disclosure regarding such methods is hereby incorporated herein by reference.
[00118] Polycarbonates useful in the thermoformed film and/or sheet of the invention may be prepared according to known procedures, for example, by reacting the dihydroxyaromatic compound with a carbonate precursor such as phosgene, a haloformate or a carbonate ester, a molecular weight regulator, an acid acceptor and a catalyst. Methods for preparing polycarbonates are known in the art and are described, for example, in U.S. Patent 4,452,933, where the disclosure regarding the preparation of polycarbonates is hereby incorporated by reference herein.
[00123] The polycarbonates useful in the polyester compositions of the thermoformed film and/or sheet of the invention also may be copolyestercarbonates such as those described in U.S. Patents 3,169,121 ; 3,207,814; 4,194,038; 4,156,069; 4,430,484, 4,465,820, and 4,981 ,898; where the disclosure regarding copolyestercarbonates from each of the U.S. Patents is incorporated by reference herein.
[00125] In addition, the polyester compositions and the polymer blend compositions containing the polyesters useful in the thermoformed film and/or sheet of the invention may also contain from 0.01 to 25% by weight or 0.01 to 20% by weight or 0.01 to 15% by weight or 0.01 to 10% by weight or 0.01 to 5% by weight of the total weight of the polyester composition of common additives such as colorants, dyes, mold release agents, flame retardants, plasticizers, nucleating agents, stabilizers, including but not limited to, UV stabilizers, thermal stabilizers and/or reaction products thereof, fillers, and impact modifiers. Examples of typical commercially available impact modifiers well known in the art and useful in this invention include, but are not limited to, ethylene/propylene terpolymers; functionalized polyolefins,such as those containing methyl acrylate and/or glycidyl methacrylate; styrene-based block copolymeric impact modifiers; and various acrylic core/shell type impact modifiers. For example, UV additives can be incorporated into articles of manufacture through addition to the bulk, through application of a hard coat, or through coextrusion of a cap layer. Residues of such additives are also contemplated as part of the polyester composition useful in the film or sheet of the invention.
[00129] In another embodiment, the invention further relates to articles of manufacture comprising the thermoformed films and/or sheets containing polyester compositions described herein.
[00155] For purposes of this example, the samples had sufficiently similar inherent viscosities thereby effectively eliminating this as a variable in the crystallization rate measurements.
[00158] As shown in Table 1 and Figure 1 , 2,2,4,4-tetramethy!~1 ,3- cyclobutanediol is more effective than other comonomers, such ethylene glycol and isophthalic acid, at increasing the crystallization half-time, i.e., the time required for a polymer to reach half of its maximum crystallinity. By decreasing the crystallization rate of PCT (increasing the crystallization half-time), amorphous articles based on 2,2,4,4-tetramethyl-1 ,3-cyclobutanediol-modified PCT as described herein may be fabricated by methods known in the art. As shown in Table 1 , these materials can exhibit higher glass transition temperatures and lower densities than other modified PCT copolyesters. [00159] Preparation of the polyesters shown on Table 1 is described below.
[00161] A mixture of 56.63 g of dimethyl terephthalate, 55.2 g of 1 ,4-cyclohexanedimethanol, 14.16 g of dimethyl isophthalate, and 0.0419 g of dibutyl tin oxide was placed in a 500-milliliter flask equipped with an inlet for nitrogen, a metal stirrer, and a short distillation column. The flask was placed in a Wood's metal bath already heated to 210°C. The stirring speed was set to 200 RPM throughout the experiment. The contents of the flask were heated at 210 0 C for 5 minutes and then the temperature was gradually increased to 290 0 C over 30 minutes. The reaction mixture was held at 290 0 C for 60 minutes and then vacuum was gradually applied over the next 5 minutes until the pressure inside the flask reached 100 mm of Hg. The pressure inside the flask was further reduced to 0.3 mm of Hg over the next 5 minutes. A pressure of 0.3 mm of Hg was maintained for a total time of 90 minutes to remove excess unreacted diols. A high melt viscosity, visually clear and colorless polymer was obtained with a glass transition temperature of 87.5°C and an inherent viscosity of 0.63 dl/g. NMR analysis showed that the polymer was composed of 100 mol% 1 ,4-cyclohexanedimethanol residues and 20.2 mol% dimethyl isophthalate residues.
[00163] A mixture of 77.68 g of dimethyl terephthalate, 50.77 g of 1 ,4-cyclohexanedimethanol, 27.81 g of ethylene glycol, and 0.0433 g of dibutyl tin oxide was placed in a 500-milliliter flask equipped with an inlet for nitrogen, a metal stirrer, and a short distillation column. The flask was placed in a Wood's metal bath already heated to 200 0 C. The stirring speed was set to 200 RPM throughout the experiment. The contents of the flask were heated at 200 0 C for 60 minutes and then the temperature was gradually increased to 210 0 C over 5 minutes. The reaction mixture was held at 210 0 C for 120 minutes and then heated up to 280 0 C in 30 minutes. Once at 280 0 C, vacuum was gradually applied over the next 5 minutes until the pressure inside the flask reached 100 mm of Hg. The pressure inside the flask was further reduced to 0.3 mm of Hg over the next 10 minutes. A pressure of 0.3 mm of Hg was maintained for a total time of 90 minutes to remove excess unreacted diols. A high melt viscosity, visually clear and colorless polymer was obtained with a glass transition temperature of 87.7°C and an inherent viscosity of 0.71 dl/g. NMR analysis showed that the polymer was composed of 19.8 mol% ethylene glycol residues.
[00169] A mixture of 81.3 g of dimethyl terephthalate, 42.85 g of 1 ,4-cyclohexanedimethanol, 34.44 g of ethylene glycol, and 0.0419 g of dibutyl tin oxide was placed in a 500-milliliter flask equipped with an inlet for nitrogen, a metal stirrer, and a short distillation column. The flask was placed in a Wood's metal bath already heated to 200 0 C. The stirring speed was set to 200 RPM throughout the experiment. The contents of the flask were heated at 200 0 C for 60 minutes and then the temperature was gradually increased to 210 0 C over 5 minutes. The reaction mixture was held at 210 0 C for 120 minutes and then heated up to 280 0 C in 30 minutes. Once at 280 0 C, vacuum was gradually applied over the next 5 minutes until the pressure inside the flask reached 100 mm of Hg. The pressure inside the flask was further reduced to 0.3 mm of Hg over the next 10 minutes. A pressure of 0.3 mm of Hg was maintained for a total time of 90 minutes to remove excess unreacted diols. A high melt viscosity, visually clear and colorless polymer was obtained with a glass transition temperature of 82.1 0 C and an inherent viscosity of 0.64 dl/g. NMR analysis showed that the polymer was composed of 34.5 mol% ethylene glycol residues.
[00180] The data shows that adding 2,2 ,4,4-tetramethyM ,3- cyclobutanediol to PCT lowers T bd and improves the toughness, as compared to ethylene glycol, which increases T b d of PCT.
[00185] The polyesters described in Example 3B to Example 3D were prepared following a procedure similar to the one described for Example 3A. The composition and properties of these polyesters are shown in Table 3.
[00187] The polyester described in Example 3F was prepared following a procedure similar to the one described for Example 3A. The composition and properties of this polyester are shown in Table 3.
[00188] The polyester described in Example 3G was prepared following a procedure similar to the one described for Example 3A. The composition and properties of this polyester are shown in Table 3.
[00189] 21.24 Ib (49.71 gram-mol) dimethyl terephthalate, 12.61 Ib (39.77 gram-mol) 1 ,4-cyclohexanedimethanol, and 6.30 Ib (19.88 gram-mol) 2,2,4,4- tetramethyl-1 ,3-cyclobutanediol were reacted together in the presence of 200 ppm of the catalyst butyltin tris(2-ethylhexanoate). The reaction was carried out under a nitrogen gas purge in an 18-gallon stainless steel pressure vessel fitted with a condensing column, a vacuum system, and a HELICONE-type agitator. With the agitator running at 25 RPM, the reaction mixture temperature was increased to 250°C and the pressure was increased to 20 psig. The reaction mixture was held for 2 hours at 250 0 C and 20 psig pressure. The pressure was then decreased to 0 psig at a rate of 3 psig/minute. The temperature of the reaction mixture was then increased to 270 0 C and the pressure was decreased to 90 mm of Hg. After a 1 hour hold time at 270°C and 90 mm of Hg, the agitator speed was decreased to 15 RPM, the reaction mixture temperature was increased to 290°C, and the pressure was decreased to <1 mm of Hg. The reaction mixture was held at 290 0 C and at a pressure of <1 mm of Hg for 12 minutes. The pressure of the pressure vessel was then increased to 1 atmosphere using nitrogen gas. The molten polymer was then extruded from the pressure vessel. The cooled, extruded polymer was ground to pass a 6-mm screen. The polymer had an inherent viscosity of 0.590 dL/g and a Tg of 106 0 C. NMR analysis showed that the polymer was composed of 77.1 mol% 1 ,4- cyclohexane-dimethanol residues and 22.9 mol% 2,2,4,4-tetramethyl-1 ,3- cyclobutanediol residues. The polymer had color values of: L*= 83.27, a*= -1.34, and b*= 5.08.
[00190] 21.24 Ib (49.71 gram-mol) dimethyl terephthalate, 12.61 Ib (39.77 gram-mol) 1 ,4-cyclohexanedimethanol, and 6.30 Ib (19.88 gram-mol) 2,2,4,4- tetramethyl-1 ,3-cyclobutanediol were reacted together in the presence of 200 ppm of the catalyst butyltin tris(2-ethylhexanoate). The reaction was carried out under a nitrogen gas purge in an 18-gallon stainless steel pressure vessel fitted with a condensing column, a vacuum system, and a HELICONE-type agitator. With the agitator running at 25 RPM, the reaction mixture temperature was increased to 250 0 C and the pressure was increased to 20 psig.The reaction mixture was held for 2 hours at 25O 0 C and 20 psig pressure. The pressure was then decreased to 0 psig at a rate of 3 psig/minute. The temperature of the reaction mixture was then increased to 270°C and the pressure was decreased to 90 mm of Hg. After a 1 hour hold time at 270°C and 90 mm of Hg, the agitator speed was decreased to 15 RPM, the reaction mixture temperature was increased to 290 0 C, and the pressure was decreased to 4 mm of Hg. The reaction mixture was held at 290 0 C and at a pressure of 4 mm of Hg for 30 minutes. The pressure of the pressure vessel was then increased to 1 atmosphere using nitrogen gas. The molten polymer was then extruded from the pressure vessel. The cooled, extruded polymer was ground to pass a 6-mm screen. The polymer had an inherent viscosity of 0.531 dL/g and a Tg of 105 0 C. NMR analysis showed that the polymer was composed of 76.9 mol% 1 ,4- cyclohexane-dimethanol residues and 23.1 mol% 2,2,4,4-tetramethyl-1 ,3- cyclobutanediol residues. The polymer had color values of: L*= 80.42, a*= -1.28, and b*= 5.13.
[00191] 21.24 Ib (49.71 gram-moi) dimethyl terephthalate, 12.61 Ib (39.77 gram-mol) 1 ,4-cyclohexaneclimethanol, and 6.30 Ib (19.88 gram-mol) 2,2,4,4- tetramethyl-1 ,3-cyclobutanediol were reacted together in the presence of 200 ppm of the catalyst butyltin tris(2-ethylhexanoate). The reaction was carried out under a nitrogen gas purge in an 18-gallon stainless steel pressure vessel fitted with a condensing column, a vacuum system, and a HELICONE-type agitator. With the agitator running at 25 RPM, the reaction mixture temperature was increased to 25O 0 C and the pressure was increased to 20 psig. The reaction mixture was held for 2 hours at 250°C and 20 psig pressure. The pressure was then decreased to 0 psig at a rate of 3 psig/minute. The temperature of the reaction mixture was then increased to 270 0 C and the pressure was decreased to 90 mm of Hg. After a 1 hour hold time at 270 0 C and 90 mm of Hg, the agitator speed was decreased to 15 RPM, the reaction mixture temperature was increased to 290 0 C, and the pressure was decreased to 4 mm of Hg. When the reaction mixture temperature was 290 0 C and the pressure was 4 mm of Hg, the pressure of the pressure vessel was immediately increased to 1 atmosphere using nitrogen gas. The molten polymer was then extruded from the pressure vessel. The cooled, extruded polymer was ground to pass a 6-mm screen. The polymer had an inherent viscosity of 0.364 dL/g and a Tg of 98 0 C. NMR analysis showed that the polymer was composed of 77.5 mol% 1 ,4-cyclohexane- dimethanol residues and 22.5 mol% 2,2,4 ,4-tetramethyl~1 ,3-cyclobutanediol residues. The polymer had color values of: L*= 77.20, a*= -1.47, and b*= 4.62.
[00195] 21.24 Ib (49.71 gram-mol) dimethyl terephthalate, 11.82 Ib (37.28 gram-mol) 1 ,4-cyclohexanedimethanol, and 6.90 Ib (21.77 gram-mol) 2,2,4,4- tetramethyl-1 ,3-cyclobutanediol were reacted together in the presence of 200 ppm of the catalyst butyltin tris(2-ethylhexanoate). The reaction was carried out under a nitrogen gas purge in an 18-gallon stainless steel pressure vessel fitted with a condensing column, a vacuum system, and a HELICONE-type agitator. With the agitator running at 25 RPM, the reaction mixture temperature was increased to 250 0 C and the pressure was increased to 20 psig. The reaction mixture was held for 2 hours at 250°C and 20 psig pressure. The pressure was then decreased to 0 psig at a rate of 3 psig/minute. The temperature of the reaction mixture was then increased to 270 0 C and the pressure was decreased to 90 mm of Hg. After a 1 hour hold time at 270 0 C and 90 mm of Hg, the agitator speed was decreased to 15 RPM, the reaction mixture temperature was increased to 29O 0 C, and the pressure was decreased to <1 mm of Hg. The reaction mixture was held at 290 0 C and at a pressure of <1 mm of Hg until the power draw to the agitator no longer increased (50 minutes). The pressure of the pressure vessel was then increased to 1 atmosphere using nitrogen gas. The molten polymer was then extruded from the pressure vessel. The cooled, extruded polymer was ground to pass a 6-mm screen. The polymer had an inherent viscosity of 0.714 dL/g and a Tg of 113 0 C. NMR analysis showed that the polymer was composed of 73.3 mol% 1 ,4-cyclohexane-dimethanol residues and 26.7 mol% 2,2,4 ,4-tetramethyl-1 ,3-cyclobutanediol residues.
[00196] The polyester of Example 4B was prepared following a procedure similar to the one described for Example 4A. The composition and properties of this polyester are shown in Table 4.
[00200] 21.24 Ib (49.71 gram-mol) dimethyl terephthalate, 8.84 Ib (27.88 gram-mol) 1 ,4-cyclohexanedimethanol, and 10.08 Ib (31.77 gram-mol) 2,2,4,4- tetramethyl-1 ,3-cyclobutanediol were reacted together in the presence of 200 ppm of the catalyst butyltin tris(2-ethylhexanoate). The reaction was carried out under a nitrogen gas purge in an 18-gallon stainless steel pressure vessel fitted with a condensing column, a vacuum system, and a HELICONE-type agitator. With the agitator running at 25 RPM, the reaction mixture temperature was increased to 25O 0 C and the pressure was increased to 20 psig. The reaction mixture was held for 2 hours at 250 0 C and 20 psig pressure. The pressure was then decreased to 0 psig at a rate of 3 psig/minute. Then the agitator speed was decreased to 15 RPM, the temperature of the reaction mixture was then increased to 29O 0 C and the pressure was decreased to 2 mm of Hg. The reaction mixture was held at 290°C and at a pressure of 2 mm of Hg until the power draw to the agitator no longer increased (80 minutes). The pressure of the pressure vessel was then increased to 1 atmosphere using nitrogen gas. The molten polymer was then extruded from the pressure vessel. The cooled, extruded polymer was ground to pass a 6-mm screen. The polymer had an inherent viscosity of 0.657 dL/g and a Tg of 119 0 C. NMR analysis showed that the polymer was composed of 56.3 mol% 1 ,4-cyclohexane-dimethanol residues and 43.7 mol% 2,2,4,4-tetramethyl-1 ,3-cyclobutanediol residues. The polymer had color values of: L*= 75.04, a*=-1.82, and b*= 6.72.
[00211] The resulting polymers were recovered from the flask, chopped using a hydraulic chopper, and ground to a 6 mm screen size. Samples of each ground polymer were submitted for inherent viscosity in 60/40 (wt/wt) phenol/ tetrachloroethane at a concentration of 0.5 g/100 ml at 25 0 C, catalyst level (Sn) by x-ray fluorescence, and color (L*, a*, b*) by transmission spectroscopy. Polymer composition was obtained by 1 H NMR. Samples were submitted for thermal stability and melt viscosity testing using a Rheometrics Mechanical Spectrometer (RMS-800).
[00212] The table below shows the experimental data for the polyesters of this example. The data shows that an increase in the level of 2,2,4,4-tetramethyl~1 ,3-cyclobutanediol raises the glass transition temperature in an almost linear fashion, for a constant inherent viscosity. Figure 3 also shows the dependence of Tg on composition and inherent viscosity.
[00216] The table below shows the experimental data for the polyesters of this example. Figure 3 also shows the dependence of Tg on composition and inherent viscosity. The data shows that an increase in the level of 2,2,4,4-tetramethyl-1 ,3-cyclobutanediol raises the glass transition temperature in an almost linear fashion, for a constant inherent viscosity.
[00218] These polyesters were prepared by carrying out the ester exchange and polycondensation reactions in separate stages. The ester exchange experiments were conducted in a continuous temperature rise (CTR) reactor. The CTR was a 3000 ml glass reactor equipped with a single shaft impeller blade agitator, covered with an electric heating mantle and fitted with a heated packed reflux condenser column. The reactor was charged with 777g of dimethyl terephthalate, 375g of 2,2,4,4-tetramethyl-1 ,3,-cyclobutanediol, 317g of cyclohexane dimethanol and 1.12g of butyltin tris-2-ethylhexanoate (such that there will be 200ppm tin metal in the final polymer). The heating mantle was set manually to 100 % output. The set points and data collection were facilitated by a Camile process control system. Once the reactants were melted, stirring was initiated and slowly increased to 250 rpm. The temperature of the reactor gradually increased with run time. The weight of methanol collected was recorded via balance. The reaction was stopped when methanol evolution stopped or at a pre-selected lower temperature of 260°C. The oligomer was discharged with a nitrogen purge and cooled to room temperature. The oligomer was frozen with liquid nitrogen and broken into pieces small enough to be weighed into a 500 ml round bottom flask.
[00219] In the polycondensation reactions, a 500 ml round bottom flask was charged with 15O g of the oligomer prepared above. The flask was equipped with a stainless steel stirrer and polymer head. The glassware was set up on a half mole polymer rig and the Camile sequence was initiated. The stirrer was positioned one full turn from the flask bottom once the oligomer melted. The temperature/pressure/stir rate sequence controlled by the Camile software for these examples is reported in the following table, unless otherwise specified below.
[00221] For Example C, the same sequence in the preceding table was used, except the time was 50 min in Stage 7.
[00222] The resulting polymers were recovered from the flask, chopped using a hydraulic chopper, and ground to a 6 mm screen size. Samples of each ground polymer were submitted for inherent viscosity in 60/40 (wt/wt) phenol/ tetrachloroethane at a concentration of 0.5 g/100 ml at 25 0 C, catalyst level (Sn) by x-ray fluorescence, and color (L*, a*, b*) by transmission spectroscopy. Polymer composition was obtained by 1 H NMR. Samples were submitted for thermal stability and melt viscosity testing using a Rheometrics Mechanical Spectrometer (RMS-800).
[00225] For Example D, the stirrer was turned to 25 rpm with 95 min left in Stage 7.
[00227] For Example K, the same sequence in the preceding table was used, except the time was 75 min in Stage 7.
[00233] The table below shows the experimental data for the polyesters of this example. The data shows that an increase in the level of 2,2,4,4-tetramethyl-1 ,3-cyclobutanediol raises the glass transition temperature in an almost linear fashion, for a constant inherent viscosity. Figure 3 also shows the dependence of Tg on composition and inherent viscosity.
[00244] Sheets consisting of Kelvx 201 were produced using a 3.5 inch single screw extruder. A sheet was extruded continuously, gauged to a thickness of 177 mil and then various sheets were sheared to size. The glass transition temperature was measured on one sheet and was 100 0 C. Sheets were then conditioned at 100% relative humidity and 25 0 C for 2 weeks. Sheets were subsequently thermoformed into a female mold having a draw ratio of 2.5:1 using a Brown thermoforming machine. The thermoforming oven heaters were set to 60/40/40% output using top heat only. Sheets were left in the oven for various amounts of time in order to determine the effect of sheet temperature on the part quality as shown in the table below. Part quality was determined by measuring the volume of the thermoformed part, calculating the draw, and visually inspecting the thermoformed part. The draw was calculated as the part volume divided by the maximum part volume achieved in this set of experiments (Example H). The thermoformed part was visually inspected for any blisters and the degree of blistering rated as none (N), low (L), or high (H). The results below demonstrate that these thermoplastic sheets with a glass transition temperature of 100 0 C can be thermoformed under the conditions shown below, as evidenced by the production of sheets having greater than 95% draw and no blistering, without predrying the sheets prior to thermoforming.
[00245] Sheets consisting of PCTG 25976 (100 mole % terephthalic acid residues, 62 mole % 1 ,4-cyclohexanedimethanol residues, and 38 mole % ethylene glycol residues) were produced using a 3.5 inch single screw extruder. A sheet was extruded continuously, gauged to a thickness of 118 mil and then various sheets were sheared to size. The glass transition temperature was measured on one sheet and was 87°C. Sheets were then conditioned at 50% relative humidity and 60°C for 4 weeks. The moisture level was measured to be 0.17 wt%. Sheets were subsequently thermoformed into a female mold having a draw ratio of 2.5:1 using a Brown thermoforming machine. The thermoforming oven heaters were set to 70/60/60% output using top heat only. Sheets were left in the oven for various amounts of time in order to determine the effect of sheet temperature on the part quality as shown in the table below. Part quality was determined by measuring the volume of the thermoformed part, calculating the draw, and visually inspecting the thermoformed part. The draw was calculated as the part volume divided by the maximum part volume achieved in this set of experiments (Example A). The thermoformed part was visually inspected for any blisters and the degree of blistering rated as none (N), low (L), or high (H). The results below demonstrate that these thermoplastic sheets with a glass transition temperature of 87 0 C can be thermoformed under the conditions shown below, as evidenced by the production of sheets having greater than 95% draw and no blistering, without predrying the sheets prior to thermoforming.
[00246] A miscible blend consisting of 20 wt% Teijin L-1250 polycarbonate (a bisphenol-A polycarbonate), 79.85 wt% PCTG 25976, and 0.15 wt% Weston 619 was produced using a 1.25 inch single screw extruder. Sheets consisting of the blend were then produced using a 3.5 inch single screw extruder. A sheet was extruded continuously, gauged to a thickness of 118 mil and then various sheets were sheared to size. The glass transition temperature was measured on one sheet and was 94°C. Sheets were then conditioned at 50% relative humidity and 60 0 C for 4 weeks. The moisture level was measured to be 0.25 wt%. Sheets were subsequently thermoformed into a female mold having a draw ratio of 2.5:1 using a Brown thermoforming machine. The thermoforming oven heaters were set to 70/60/60% output using top heat only. Sheets were left in the oven for various amounts of time in order to determine the effect of sheet temperature on the part quality as shown in the table below. Part quality was determined by measuring the volume of the thermoformed part, calculating the draw, and visually inspecting the thermoformed part. The draw was calculated as the part volume divided by the maximum part volume achieved in this set of experiments (Example A). The thermoformed part was visually inspected for any blisters and the degree of blistering rated as none (N), low (L), or high (H). The results below demonstrate that these thermoplastic sheets with a glass transition temperature of 94°C can be thermoformed under the conditions shown below, as evidenced by the production of sheets having greater than 95% draw and no blistering, without predrying the sheets prior to thermoforming.
[00247] A miscible blend consisting of 30 wt% Teijin L-1250 polycarbonate, 69.85 wt% PCTG 25976, and 0.15 wt% Weston 619 was produced using a 1.25 inch single screw extruder. Sheets consisting of the blend were then produced using a 3.5 inch single screw extruder. A sheet was extruded continuously, gauged to a thickness of 118 mil and then various sheets were sheared to size. The glass transition temperature was measured on one sheet and was 99°C. Sheets were then conditioned at 50% relative humidity and 60 0 C for 4 weeks. The moisture level was measured to be 0.25 wt%. Sheets were subsequently thermoformed into a female mold having a draw ratio of 2.5:1 using a Brown thermoforming machine. The thermoforming oven heaters were set to 70/60/60% output using top heat only. Sheets were left in the oven for various amounts of time in order to determine the effect of sheet temperature on the part quality as shown in the table below. Part quality was determined by measuring the volume of the thermoformed part, calculating the draw, and visually inspecting the thermoformed part. The draw was calculated as the part volume divided by the maximum part volume achieved in this set of experiments (Example A). The thermoformed part was visually inspected for any blisters and the degree of blistering rated as none (N), low (L), or high (H). The results below demonstrate that these thermoplastic sheets with a glass transition temperature of 99°C can be thermoformed under the conditions shown below, as evidenced by the production of sheets having greater than 95% draw and no blistering, without predrying the sheets prior to thermoforming.
[00248] A miscible blend consisting of 40 wt% Teijin L-1250 polycarbonate, 59.85 wt% PCTG 25976, and 0.15 wt% Weston 619 was produced using a 1.25 inch single screw extruder. Sheets consisting of the blend were then produced using a 3.5 inch single screw extruder. A sheet was extruded continuously, gauged to a thickness of 118 mil and then various sheets were sheared to size. The glass transition temperature was measured on one sheet and was 105 0 C. Sheets were then conditioned at 50% relative humidity and 60 0 C for 4 weeks. The moisture level was measured to be 0.265 wt%. Sheets were subsequently thermoformed into a female mold having a draw ratio of 2.5:1 using a Brown thermoforming machine. The thermoforming oven heaters were set to 70/60/60% output using top heat only. Sheets were left in the oven for various amounts of time in order to determine the effect of sheet temperature on the part quality as shown in the table below. Part quality was determined by measuring the volume of the thermoformed part, calculating the draw, and visually inspecting the thermoformed part. The draw was calculated as the part volume divided by the maximum part volume achieved in this set of experiments (Examples 8A to 8E). The thermoformed part was visually inspected for any blisters and the degree of blistering rated as none (N), low (L), or high (H). The results below demonstrate that these thermoplastic sheets with a glass transition temperature of 105°C can be thermoformed under the conditions shown below, as evidenced by the production of sheets having greater than 95% draw and no blistering, without predrying the sheets prior to thermoforming.
[00249] A miscible blend consisting of 50 wt% Teijin L-1250 polycarbonate, 49.85 wt% PCTG 25976, and 0.15 wt% Weston 619 was produced using a 1.25 inch single screw extruder. A sheet was extruded continuously, gauged to a thickness of 118 mil and then various sheets were sheared to size. The glass transition temperature was measured on one sheet and was 111°C. Sheets were then conditioned at 50% relative humidity and 60 0 C for 4 weeks. The moisture level was measured to be 0.225 wt%. Sheets were subsequently thermoformed into a female mold having a draw ratio of 2.5:1 using a Brown thermoforming machine. The thermoforming oven heaters were set to 70/60/60% output using top heat only. Sheets were left in the oven for various amounts of time in order to determine the effect of sheet temperature on the part quality as shown in the table below. Part quality was determined by measuring the volume of the thermoformed part, calculating the draw, and visually inspecting the thermoformed part. The draw was calculated as the part volume divided by the maximum part volume achieved in this set of experiments (Examples A to D). The thermoformed part was visually inspected for any blisters and the degree of blistering rated as none (N), low (L), or high (H). The results below demonstrate that these thermoplastic sheets with a glass transition temperature of 111 0 C can be thermoformed under the conditions shown below, as evidenced by the production of sheets having greater than 95% draw and no blistering, without predrying the sheets prior to thermoforming.
[00250] A miscible blend consisting of 60 wt% Teijin L-1250 polycarbonate, 39.85 wt% PCTG 25976, and 0.15 wt% Weston 619 was produced using a 1.25 inch single screw extruder. Sheets consisting of the blend were then produced using a 3.5 inch single screw extruder. A sheet was extruded continuously, gauged to a thickness of 118 mil and then various sheets were sheared to size. The glass transition temperature was measured on one sheet and was 117°C. Sheets were then conditioned at 50% relative humidity and 60 0 C for 4 weeks. The moisture level was measured to be 0.215 wt%. Sheets were subsequently thermoformed into a female mold having a draw ratio of 2.5:1 using a Brown thermoforming machine. The thermoforming oven heaters were set to 70/60/60% output using top heat only. Sheets were left in the oven for various amounts of time in order to determine the effect of sheet temperature on the part quality as shown in the table below. Part quality was determined by measuring the volume of the thermoformed part, calculating the draw, and visually inspecting the thermoformed part. The draw was calculated as the part volume divided by the maximum part volume achieved in this set of experiments (Example A). The thermoformed part was visually inspected for any blisters and the degree of blistering rated as none (N), low (L), or high (H). The results below demonstrate that these thermoplastic sheets with a glass transition temperature of 117°C cannot be thermoformed under the conditions shown below, as evidenced by the inability to produce sheets having greater than 95% draw and no blistering, without predrying the sheets prior to thermoforming.
[00251] A miscible blend consisting of 65 wt% Teijin L-1250 polycarbonate, 34.85 wt% PCTG 25976, and 0.15 wt% Weston 619 was produced using a 1.25 inch single screw extruder. Sheets consisting of the blend were then produced using a 3.5 inch single screw extruder. A sheet was extruded continuously, gauged to a thickness of 118 mil and then various sheets were sheared to size. The glass transition temperature was measured on one sheet and was 12O 0 C. Sheets were then conditioned at 50% relative humidity and 6O 0 C for 4 weeks. The moisture level was measured to be 0.23 wt%. Sheets were subsequently thermoformed into a female mold having a draw ratio of 2.5:1 using a Brown thermoforming machine. The thermoforming oven heaters were set to 70/60/60% output using top heat only. Sheets were left in the oven for various amounts of time in order to determine the effect of sheet temperature on the part quality as shown in the table below. Part quality was determined by measuring the volume of the thermoformed part, calculating the draw, and visually inspecting the thermoformed part. The draw was calculated as the part volume divided by the maximum part volume achieved in this set of experiments (Example A). The thermoformed part was visually inspected for any blisters and the degree of blistering rated as none (N), low (L), or high (H). The results below demonstrate that these thermoplastic sheets with a glass transition temperature of 12O 0 C cannot be thermoformed under the conditions shown below, as evidenced by the inability to produce sheets having greater than 95% draw and no blistering, without predrying the sheets prior to thermoforming.
[00252] A miscible blend consisting of 70 wt% Teijin L-1250 polycarbonate, 29.85 wt% PCTG 25976, and 0.15 wt% Weston 619 was produced using a 1.25 inch single screw extruder. Sheets consisting of the blend were then produced using a 3.5 inch single screw extruder. A sheet was extruded continuously, gauged to a thickness of 118 mil and then various sheets were sheared to size. The glass transition temperature was measured on one sheet and was 123°C. Sheets were then conditioned at 50% relative humidity and 60 0 C for 4 weeks. The moisture level was measured to be 0.205 wt%. Sheets were subsequently thermoformed into a female mold having a draw ratio of 2.5:1 using a Brown thermoforming machine. The thermoforming oven heaters were set to 70/60/60% output using top heat only. Sheets were left in the oven for various amounts of time in order to determine the effect of sheet temperature on the part quality as shown in the table below. Part quality was determined by measuring the volume of the thermoformed part, calculating the draw, and visually inspecting the thermoformed part. The draw was calculated as the part volume divided by the maximum part volume achieved in this set of experiments (Examples A and B). The thermoformed part was visually inspected for any blisters and the degree of blistering rated as none (N), low (L), or high (H). The results below demonstrate that these thermoplastic sheets with a glass transition temperature of 123°C cannot be thermoformed under the conditions shown below, as evidenced by the inability to produce sheets having greater than 95% draw and no blistering, without predrying the sheets prior to thermoforming.
[00254] It can be clearly seen from a comparison of the data in the above relevant working examples that the polyesters of the present invention offer a definite advantage over the commercially available polyesters with regard to glass transition temperature, density, slow crystallization rate, melt viscosity, and toughness.
[00255] The invention has been described in detail with reference to the embodiments disclosed herein, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention.

中文:
[0035]在一个方面中,本发明的热成形的薄膜和/或薄板不包含聚碳酸酯。
[0044]在一个方面中,提供了制备本发明的热成形的薄膜和/或薄板的方法,其中消除了在热成形前干燥薄板和/或薄膜的步骤。
[0047]在一个方面中,可用于本发明的热成形的薄膜和/或薄板的聚酯可以是无定形的或半结晶的。在一个方面中,可用于本发明的热成形的薄膜或者薄板的某些聚酯可以具有较低的结晶度。可用于本发明的热成形的薄膜或者薄板的某些聚酯因而可能具有基本上无定形的形态,意味着聚酯包括聚合物的基本上无序区域。
[0048]在其它方面中,本发明的薄膜和/或薄板包括热成形的薄膜或者薄板。
[0049]图1是显示共聚单体对改性PCT共聚酯的最快结晶半衰期的影响的图。
[0051]图3是显示2,2,4,4-四甲基-1,3-环丁二醇组成对共聚酯的玻璃化转变温度(Tg)的影响的图。
[0052]通过参考下面本发明的某些实施方案的详细说明和工作实施例可以更容易地理解本发明。根据本发明的目的,本发明的某些实施方案描述于发明内容中并且进一步在下文中进行描述。同样,本文中描述了本发明的其它实施方案。
[0084]在某些实施方案中,对苯二甲酸或其酯,例如对苯二甲酸二甲酯,或者对苯二甲酸和其酯的混合物,构成了用于形成可用于本发明的热成形的薄膜或者薄板的聚酯的二羧酸组分的大部分或者全部。在某些实施方案中,对苯二甲酸残基可以构成一部分或者全部的用于形成本发明的聚酯的二羧酸组分,其浓度为至少70mol%,如至少80mol%,至少90mol%,至少95mol%,至少99mol%或100mol%。在某些实施方案中,可以使用具有较高量的对苯二甲酸的聚酯以便获得较高的冲击强度性能。就本公开内容的目的而言,术语“对苯二甲酸”和“对苯二甲酸二甲酯”在本文中可互换使用。在一个实施方案中,对苯二甲酸二甲酯是用于制备可用于本发明的聚酯的二羧酸组分的一部分或全部。在所有的实施方案中,可以使用70-100mol%;或80-100mol%;或90-100mol%;或99-100mol%;或100mol%的对苯二甲酸和/或对苯二甲酸二甲酯和/或其混合物。
[00101]在另一实施方案中,可用于本发明的热成形的薄膜和/或薄板的某些聚酯,与在-5°C测量时以10-密耳切口在1/8-in厚试条中根据ASTM D256测定的切口伊佐德冲击强度相比,可以显示出在0°C测量时的切口伊佐德冲击强度增加了至少3%或者至少5%或者至少10%或者至少15%。另外,某些其它聚酯还可以显示出根据ASTM D256在1/8-in厚试条中以10-密耳切口测定的在0°C-30°C测量时的在正或负5%以内的切口伊佐德冲击强度的保持。
[00102]在又一实施方案中,可用于本发明的热成形的薄膜和/或薄板的某些聚酯可以显示出根据ASTM D256在1/8-in厚试条中以10-密耳切口测定的在23°C测量时的切口伊佐德冲击强度的保持的损失不大于70%,相比于根据ASTM D256在1/8-in厚试条中以10-密耳切口测定的在相同温度测量时的相同聚酯的切口伊佐德冲击强度来说。
[00108]在一些实施方案中,使用可用于本发明的薄膜和/或薄板的聚酯组合物最小化和/或消除了在熔融加工和/或热成形之前的干燥步骤。
[00109]虽然可用于本发明的热成形的薄膜和/或薄板的聚酯可以具有任何水分含量,在一种实施方案中,它们的水分含量可以为0.02-1.0wt%的熔融加工前的聚酯的总重量。
[00111]可用于本发明的热成形的薄膜和/或薄板的聚酯可以通过文献中已知工艺制备,例如通过在均质溶液中的工艺、通过熔体中的酯交换工艺和通过双相界面工艺。合适的方法包括但不限于使一种或多种二羧酸与一种或多种二醇在100°C-315°C的温度和0.1-760mmHg的压力下反应足以形成聚酯的时间的步骤。对于生产聚酯的方法,参见美国专利3,772,405,这种方法的公开内容引入本文作为参考。
[00118]可用于本发明的热成形的薄膜和/或薄板的聚碳酸酯可以根据已知方法制备,例如通过使二羟基芳族化合物与碳酸酯前体如光气、卤代甲酸酯或碳酸酯、分子量调节剂、受酸体和催化剂反应。用于制备聚碳酸酯的方法是本领域已知的并且例如描述于美国专利4,452,933中,其中关于聚碳酸酯制备的公开内容在此引入本文作为参考。
[00123]对本发明的热成形的薄膜和/或薄板的聚酯组合物有用的聚碳酸酯还可能是共聚酯碳酸酯,如描述于以下美国专利中的那些:3,169,121;3,207,814;4,194,038;4,156,069;4,430,484、4,465,820和4,981,898;其中各篇美国专利有关共聚酯碳酸酯的公开内容引入本文作为参考。
[00125]另外,包含可用于本发明的热成形的薄膜和/或薄板的聚酯的聚酯组合物和聚合物共混物组合物还可包含聚酯组合物总重量的0.01-25wt%或0.01-20wt%或0.01-15wt%或0.01-10wt%或0.01-5wt%的常用添加剂如着色剂、染料、脱模剂、阻燃剂、增塑剂、成核剂、稳定剂(包括但不限于紫外稳定剂、热稳定剂和/或其反应产物)、填料和耐冲击性改进剂。本领域众所周知的且可用于本发明的典型的市售可得的耐冲击性改进剂的实例包括但不局限于,乙烯/丙烯三元共聚物;官能化聚烯烃,如包含丙烯酸甲酯和/或甲基丙烯酸缩水甘油酯的那些;基于苯乙烯的嵌段共聚物耐冲击性改进剂;和各种丙烯酸系的核/壳型耐冲击性改进剂。例如,通过经施加硬膜或者经共挤压盖层而添加到本体中,可以将UV添加剂结合到制品中。也预期将这种添加剂的残余物作为对本发明薄膜或者薄板有用的聚酯组合物的一部分。
[00129]在另一实施方案中,本发明还涉及制品,其包含热成形的薄膜和/或薄板,该热成形的薄膜和/或薄板包含本文中所述的聚酯组合物。
[00155]对本实施例而言,各样品具有足够相似的比浓对数粘度,因而在结晶速率测量中实际上排除此作为变量。
[00158]如表1和图1所示,在提高结晶半衰期(即聚合物达到其最大结晶度一半所需的时间)方面,2,2,4,4-四甲基-1,3-环丁二醇比其它共聚单体如乙二醇和间苯二甲酸更有效。通过降低PCT的结晶速率(提高结晶半衰期),可以通过本领域已知的方法制造基于如本文所述的2,2,4,4-四甲基-1,3-环丁二醇改性的PCT的无定形制品。如表1所示,这些材料可以显示出比其它改性PCT共聚酯更高的玻璃化转变温度和更低的密度。
[00161]将56.63g对苯二甲酸二甲酯、55.2g 1,4-环己烷二甲醇、14.16g间苯二甲酸二甲酯和0.0419g氧化二丁锡的混合物置于装配有氮气进气口、金属搅拌器和短蒸馏柱的500毫升烧瓶中。将烧瓶置于已经加热到210°C的伍德合金浴(Wood′s metal bath)中。在整个实验过程中搅拌速度设定为200RPM。将烧瓶中的内容物在210°C加热5分钟并随后在30分钟内逐渐将温度升高到290°C。反应混合物在290°C保持60分钟,然后在接下来的5分钟内逐渐施加真空直到烧瓶内压力达到100mmHg。在接下来的5分钟内再将烧瓶内压力降低到0.3mmHg。保持0.3mmHg的压力总共90分钟以除去过量未反应的二醇。得到高熔体粘度、视觉上透明且无色的聚合物,玻璃化转变温度为87.5°C,比浓对数粘度为0.63dl/g。NMR分析表明聚合物包含100mol%1,4-环己烷二甲醇残基和20.2mol%间苯二甲酸二甲酯残基。
[00163]将77.68g对苯二甲酸二甲酯、50.77g1,4-环己烷二甲醇、27.81g乙二醇和0.0433g氧化二丁锡的混合物置于装配有氮气进气口、金属搅拌器和短蒸馏柱的500毫升烧瓶中。将烧瓶置于已经加热到200°C的伍德合金浴中。在整个实验过程中搅拌速度设定为200RPM。将烧瓶中的内容物在200°C加热60分钟并随后在5分钟内逐渐将温度升高到210°C。反应混合物在210°C保持120分钟并随后在30分钟内加热到280°C。一旦处于280°C,在接下来的5分钟内逐渐施加真空直到烧瓶内压力达到100mmHg。在接下来的10分钟内再将烧瓶内压力降低到0.3mmHg。保持0.3mmHg的压力总共90分钟以除去过量未反应的二醇。得到高熔体粘度、视觉上透明且无色的聚合物,玻璃化转变温度为87.7°C,比浓对数粘度为0.71dl/g。NMR分析表明聚合物包含19.8mol%乙二醇残基。
[00169]将81.3g对苯二甲酸二甲酯、42.85g 1,4-环己烷二甲醇、34.44g乙二醇和0.0419g氧化二丁锡的混合物置于装配有氮气进气口、金属搅拌器和短蒸馏柱的500毫升烧瓶中。将烧瓶置于已经加热到200°C的伍德合金浴中。在整个实验过程中搅拌速度设定为200RPM。将烧瓶中的内容物在200°C加热60分钟并随后在5分钟内逐渐将温度升高到210°C。反应混合物在210°C保持120分钟并随后在30分钟内加热到280°C。一旦处于280°C,在接下来的5分钟内逐渐施加真空直到烧瓶内压力达到100mmHg。在接下来的10分钟内再将烧瓶内压力降低到0.3mmHg。保持0.3mmHg的压力总共90分钟以除去过量未反应的二醇。得到高熔体粘度、视觉上透明且无色的聚合物,玻璃化转变温度为82.1°C,比浓对数粘度为0.64dl/g。NMR分析表明聚合物包含34.5mol%乙二醇残基。
[00180]数据表明,与提高PCT的Tbd的乙二醇相比,向PCT中加入2,2,4,4-四甲基-1,3-环丁二醇降低了Tbd并且改善了韧性。
[00185]实施例3B-实施例3D中所述的聚酯按照与实施例3A所述程序的相似程序制备。这种聚酯的组成和性能示于表3中。
[00187]实施例3F中所述的聚酯按照与实施例3A所述程序的相似程序制备。这种聚酯的组成和性能示于表3中。
[00188]实施例3G中所述的聚酯按照与实施例3A所述程序的相似程序制备。这种聚酯的组成和性能示于表3中。
[00189]在200ppm催化剂三(2-乙基己酸)丁基锡存在下,使21.24lb(49.71gram-mol)对苯二甲酸二甲酯、12.61lb(39.77gram-mol)1,4-环己烷二甲醇、6.30lb(19.88gram-mol)2,2,4,4-四甲基-1,3-环丁二醇一起反应。反应在氮气吹扫下在配有冷凝柱、真空系统和HELICONE型搅拌器的18加仑不锈钢压力容器中进行。随着搅拌器以25RPM运转,反应混合物温度升高到250°C,压力升高到20psig。反应混合物在250°C和20psig压力下保持2小时。然后以3psig/min的速率将压力降至0psig。然后将反应混合物的温度升至270°C并将压力降至90mmHg。在270°C和90mmHg下的1小时的保持时间后,将搅拌器速度降至15RPM,反应混合物温度升高到290°C和将压力降至<1mmHg。反应混合物在290°C和<1mmHg的压力下保持12分钟。然后使用氮气将压力容器的压力升高到1个大气压。随后从压力容器中挤出熔融聚合物。研磨冷却的、挤出的聚合物以便通过6-mm筛。聚合物的比浓对数粘度为0.590dL/g,Tg为106°C。NMR分析表明聚合物包含77.1mol%1,4-环己烷二甲醇残基和22.9mol%2,2,4,4-四甲基-1,3-环丁二醇残基。聚合物的色值为L*=83.27;a*=-1.34;和b*=5.08。
[00190]在200ppm催化剂三(2-乙基己酸)丁基锡存在下,使21.24lb(49.71gram-mol)对苯二甲酸二甲酯、12.61lb(39.77gram-mol)1,4-环己烷二甲醇、6.30lb(19.88gram-mol)2,2,4,4-四甲基-1,3-环丁二醇一起反应。反应在氮气吹扫下在配有冷凝柱、真空系统和HELICONE型搅拌器的18加仑不锈钢压力容器中进行。随着搅拌器以25RPM运转,反应混合物温度升高到250°C,压力升高到20psig。反应混合物在250°C和20psig压力下保持2小时。然后以3psig/min的速率将压力降至0psig。然后将反应混合物的温度升至270°C并将压力降至90mmHg。在270°C和90mmHg下的1小时的保持时间后,将搅拌器速度降至15RPM,反应混合物温度升高到290°C,和将压力降至4mmHg。反应混合物在290°C和4mmHg的压力下保持30分钟。然后使用氮气将压力容器的压力升高到1个大气压。随后从压力容器中挤出熔融聚合物。研磨冷却的、挤出的聚合物以便通过6-mm筛。聚合物的比浓对数粘度为0.531dL/g,Tg为105°C。NMR分析表明聚合物包含76.9mol%1,4-环己烷二甲醇残基和23.1mol%2,2,4,4-四甲基-1,3-环丁二醇残基。聚合物的色值为L*=80.42,a*=-1.28,和b*=5.13。
[00191]在200ppm催化剂三(2-乙基己酸)丁基锡存在下,使21.24lb(49.71gram-mol)对苯二甲酸二甲酯、12.61lb(39.77gram-mol)1,4-环己烷二甲醇、6.30lb(19.88gram-mol)2,2,4,4-四甲基-1,3-环丁二醇一起反应。反应在氮气吹扫下在配有冷凝柱、真空系统和HELICONE型搅拌器的18加仑不锈钢压力容器中进行。随着搅拌器以25RPM运转,反应混合物温度升高到250°C,压力升高到20psig。反应混合物在250°C和20psig压力下保持2小时。然后以3psig/min的速率将压力降至0psig。然后将反应混合物的温度升至270°C并将压力降至90mmHg。在270°C和90mmHg下的1小时的保持时间后,将搅拌器速度降至15RPM,反应混合物温度升高到290°C,和将压力降至4mmHg。当反应混合物温度是290°C并且压力是4mmHg时,使用氮气立即将压力容器的压力增加到1个大气压。随后从压力容器中挤出熔融聚合物。研磨冷却的、挤出的聚合物以便通过6-mm筛。聚合物的比浓对数粘度为0.364dL/g,Tg为98°C。NMR分析表明聚合物包含77.5mol%1,4-环己烷二甲醇残基和22.5mol%2,2,4,4-四甲基-1,3-环丁二醇残基。聚合物的色值为L*=77.20,a*=-1.47,和b*=4.62。
[00195]在200ppm催化剂三(2-乙基己酸)丁基锡存在下,使21.24lb(49.71gram-mol)对苯二甲酸二甲酯、11.82lb(37.28gram-mol)1,4-环己烷二甲醇和6.90lb(21.77gram-mol)2,2,4,4-四甲基-1,3-环丁二醇一起反应。反应在氮气吹扫下在配有冷凝柱、真空系统和HELICONE型搅拌器的18加仑不锈钢压力容器中进行。随着搅拌器以25RPM运转,反应混合物温度升高到250°C,压力升高到20psig。反应混合物在250°C和20psig压力下保持2小时。然后以3psig/min的速率将压力降至0psig。然后将反应混合物的温度升至270°C并将压力降至90mmHg。在270°C和90mmHg下的1小时的保持时间后,将搅拌器速度降至15RPM,反应混合物温度升高到290°C和将压力降至<1mmHg。将反应混合物保持在290°C和<1mmHg的压力下直到搅拌器的功率不再升高(50分钟)。然后使用氮气将压力容器的压力升高到1个大气压。随后从压力容器中挤出熔融聚合物。研磨冷却的、挤出的聚合物以便通过6-mm筛。聚合物的比浓对数粘度为0.714dL/g,Tg为113°C。NMR分析表明聚合物包含73.3mol%1,4-环己烷二甲醇残基和26.7mol%2,2,4,4-四甲基-1,3-环丁二醇残基。
[00196]实施例4B的聚酯按照与实施例4A所述程序的相似程序制备。这种聚酯的组成和性能示于表4中。
[00200]在200ppm催化剂三(2-乙基己酸)丁基锡存在下,使21.24lb(49.71gram-mol)对苯二甲酸二甲酯、8.84lb(27.88gram-mol)1,4-环己烷二甲醇和10.08lb(31.77gram-mol)2,2,4,4-四甲基-1,3-环丁二醇一起反应。反应在氮气吹扫下在配有冷凝柱、真空系统和HELICONE型搅拌器的18加仑不锈钢压力容器中进行。随着搅拌器以25RPM运转,反应混合物温度升高到250°C,压力升高到20psig。反应混合物在250°C和20psig压力下保持2小时。然后以3psig/min的速率将压力降至0psig。然后将搅拌器速度降至15RPM,然后将反应混合物的温度升至290°C,和将压力降至2mmHg。将反应混合物保持在290°C和2mmHg的压力下直到搅拌器的功率不再升高(80分钟)。然后使用氮气将压力容器的压力升高到1个大气压。随后从压力容器中挤出熔融聚合物。研磨冷却的、挤出的聚合物以便通过6-mm筛。聚合物的比浓对数粘度为0.657dL/g,Tg为119°C。NMR分析表明聚合物包含56.3mol%1,4-环己烷二甲醇残基和43.7mol%2,2,4,4-四甲基-1,3-环丁二醇残基。聚合物的色值为L*=75.04;a*=-1.82;和b*=6.72。
[00211]从烧瓶中回收所得聚合物,使用液压切碎机切碎,并研磨至6mm筛孔尺寸。对各研磨的聚合物的样品进行如下测试:在25°C以0.5g/100ml的浓度在60/40(wt/wt)苯酚/四氯乙烷中测定比浓对数粘度、通过X射线荧光测量催化剂水平(Sn)和通过透射光谱获得颜色(L*、a*、b*)。通过1H NMR获得聚合物组成。使用Rheometrics MechanicalSpectrometer(RMS-800)对样品进行热稳定性和熔体粘度的测试。
[00212]下表显示了本实施例的聚酯的实验数据。数据表明,对于恒定的比浓对数粘度,2,2,4,4-四甲基-1,3-环丁二醇水平的增加以几乎线性的方式提高玻璃化转变温度。图3还显示了Tg对组成和比浓对数粘度的依赖性。
[00216]下表显示了本实施例的聚酯的实验数据。图3还显示了Tg对组成和比浓对数粘度的依赖性。数据表明,对于恒定的比浓对数粘度,2,2,4,4-四甲基-1,3-环丁二醇水平的增加以几乎线性的方式提高玻璃化转变温度。
[00218]这些聚酯通过在分开的阶段进行酯交换和缩聚反应而制备。酯交换实验是在连续升温(CTR)反应器中进行的。CTR是装配有单轴叶轮片搅拌器、罩有电热套和配有加热的填充回流冷凝柱的3000ml玻璃反应器。反应器填装有777g的对苯二甲酸二甲酯、375g的2,2,4,4-四甲基-1,3-环丁二醇、317g的环己烷二甲醇和1.12g的三(2-乙基己酸)丁基锡(使得在最终聚合物中将存在200ppm锡金属)。手动设置加热套为100%输出。采用Camile过程控制系统使得设定点和数据采集变得方便。一旦反应物熔融,就开始搅拌并缓慢提高至250rpm。随着运转时间,反应器的温度逐渐升高。借助天平记录所收集的甲醇的重量。当甲醇逸出停止或处于预选的260°C的较低温度下时,停止反应。采用氮气吹扫排出低聚物并冷却到室温。采用液氮冷冻低聚物并破碎成足够小的小块,以经过称量后装入500ml圆底烧瓶中。
[00219]在缩聚反应中,500ml圆底烧瓶填装有150g的以上所制备的低聚物。该烧瓶装备有不锈钢搅拌器和聚合物盖。将玻璃器皿设置在半摩尔聚合物成套设备上并启动Camile序列。一旦低聚物熔融,将搅拌器定位为距离烧瓶底部一个完整的翻转。对于这些实施例的由Camile软件控制的温度/压力/搅动速率序列报告于下表中,除非以下另作说明。
[00221]对于实施例C,使用上表中的相同序列,但是在阶段7中的时间为50分钟。
[00222]从烧瓶中回收所得聚合物,使用液压切碎机切碎,并研磨至6mm筛孔尺寸。对各研磨的聚合物的样品进行如下测试:在25°C以0.5g/100ml的浓度在60/40(wt/wt)苯酚/四氯乙烷中测定比浓对数粘度、通过X射线荧光测量催化剂水平(Sn)和通过透射光谱获得颜色(L*、a*、b*)。通过1H NMR获得聚合物组成。使用Rheometrics MechanicalSpectrometer(RMS-800)对样品进行热稳定性和熔体粘度的测试。
[00225]对于实施例D,在阶段7中搅拌器被调至25rpm,进行95分钟。
[00227]对于实施例K,使用上表中的相同序列,但是在阶段7中的时间为75分钟。
[00233]下表显示了本实施例的聚酯的实验数据。数据表明,对于恒定的比浓对数粘度,2,2,4,4-四甲基-1,3-环丁二醇水平的增加以几乎线性的方式提高玻璃化转变温度。图3还显示了Tg对组成和比浓对数粘度的依赖性。
[00244]使用3.5英寸单螺杆挤出机生产由Kelvx 201组成的薄板。连续挤出薄板,测量厚度为177密耳,然后将各种薄板剪切到合适尺寸。对一个薄板测量玻璃化转变温度,其为100°C。然后将薄板在100%相对湿度和25°C下调理2周。随后使用Brown热成形机将薄板热成形到拉伸比为2.5∶1的阴模中。仅使用顶端加热,将热成形烘箱加热器设定为60/40/40%输出。将薄板留在烘箱中达不同的时间,以便测定薄板温度对部件质量的影响,如下表中所示。部件质量通过测量热成形部件的体积、计算拉伸和目视检查热成形部件来测定。拉伸是这样计算的:部件体积除以在该组实验中获得的最大部件体积(实施例H)。目视检查热成形部件的任何起泡,并将起泡程度分级为无(N)、低(L)或高(H)。以下结果证明,这些玻璃化转变温度为100°C的热塑性薄板可以在以下所示的条件下热成形,如由在热成形前未预干燥薄板的情况下,生产的薄板具有大于95%的拉伸和未起泡所证明的。
[00245]使用3.5英寸单螺杆挤出机生产由PCTG 25976(100mol%对苯二甲酸残基、62mol%1,4-环己烷二甲醇残基和3 8mol%乙二醇残基)组成的薄板。连续挤出薄板,测量厚度为118密耳,然后将各种薄板剪切到合适尺寸。对一个薄板测量玻璃化转变温度,其为87°C。然后将薄板在50%相对湿度和60°C下调理4周。水分含量的测量结果为0.17wt%。随后使用Brown热成形机将薄板热成形到拉伸比为2.5∶1的阴模中。仅使用顶端加热,将热成形烘箱加热器设定为70/60/60%输出。将薄板留在烘箱中达不同的时间,以便测定薄板温度对部件质量的影响,如下表中所示。部件质量通过测量热成形部件的体积、计算拉伸和目视检查热成形部件来测定。拉伸是这样计算的:部件体积除以在该组实验中获得的最大部件体积(实施例A)。目视检查热成形部件的任何起泡,并将起泡程度分级为无(N)、低(L)或高(H)。以下结果证明,这些玻璃化转变温度为87°C的热塑性薄板可以在以下所示的条件下热成形,如由在热成形前未预干燥薄板的情况下,生产的薄板具有大于95%的拉伸和未起泡所证明的。
[00246]使用1.25英寸单螺杆挤出机生产由20wt%Teijin L-1250聚碳酸酯(双酚A聚碳酸酯)、79.85wt%PCTG 25976和0.15wt%Weston 619组成的可混共混物。然后使用3.5英寸单螺杆挤出机生产由该共混物组成的薄板。连续挤出薄板,测量厚度为118密耳,然后将各种薄板剪切到合适尺寸。对一个薄板测量玻璃化转变温度,其为94°C。然后将薄板在50%相对湿度和60°C下调理4周。水分含量的测量结果为0.25wt%。随后使用Brown热成形机将薄板热成形到拉伸比为2.5∶1的阴模中。仅使用顶端加热,将热成形烘箱加热器设定为70/60/60%输出。将薄板留在烘箱中达不同的时间,以便测定薄板温度对部件质量的影响,如下表中所示。部件质量通过测量热成形部件的体积、计算拉伸和目视检查热成形部件来测定。拉伸是这样计算的:部件体积除以在该组实验中获得的最大部件体积(实施例A)。目视检查热成形部件的任何起泡,并将起泡程度分级为无(N)、低(L)或高(H)。以下结果证明,这些玻璃化转变温度为94°C的热塑性薄板可以在以下所示的条件下热成形,如由在热成形前未预干燥薄板的情况下,生产的薄板具有大于95%的拉伸和未起泡所证明的。
[00247]使用1.25英寸单螺杆挤出机生产由30wt%Teijin L-1250聚碳酸酯、69.85wt%PCTG 25976和0.15wt%Weston 619组成的可混共混物。然后使用3.5英寸单螺杆挤出机生产由该共混物组成的薄板。连续挤出薄板,测量厚度为118密耳,然后将各种薄板剪切到合适尺寸。对一个薄板测量玻璃化转变温度,其为99°C。然后将薄板在50%相对湿度和60°C下调理4周。水分含量的测量结果为0.25wt%。随后使用Brown热成形机将薄板热成形到拉伸比为2.5∶1的阴模中。仅使用顶端加热,将热成形烘箱加热器设定为70/60/60%输出。将薄板留在烘箱中达不同的时间,以便测定薄板温度对部件质量的影响,如下表中所示。部件质量通过测量热成形部件的体积、计算拉伸和目视检查热成形部件来测定。拉伸是这样计算的:部件体积除以在该组实验中获得的最大部件体积(实施例A)。目视检查热成形部件的任何起泡,并将起泡程度分级为无(N)、低(L)或高(H)。以下结果证明,这些玻璃化转变温度为99°C的热塑性薄板可以在以下所示的条件下热成形,如由在热成形前未预干燥薄板的情况下,生产的薄板具有大于95%的拉伸和未起泡所证明的。
[00248]使用1.25英寸单螺杆挤出机生产由40wt%Teijin L-1250聚碳酸酯、59.85wt%PCTG 25976和0.15wt%Weston 619组成的可混共混物。然后使用3.5英寸单螺杆挤出机生产由该共混物组成的薄板。连续挤出薄板,测量厚度为118密耳,然后将各种薄板剪切到合适尺寸。对一个薄板测量玻璃化转变温度,其为105°C。然后将薄板在50%相对湿度和60°C下调理4周。水分含量的测量结果为0.265wt%。随后使用Brown热成形机将薄板热成形到拉伸比为2.5∶1的阴模中。仅使用顶端加热,将热成形烘箱加热器设定为70/60/60%输出。将薄板留在烘箱中达不同的时间,以便测定薄板温度对部件质量的影响,如下表中所示。部件质量通过测量热成形部件的体积、计算拉伸和目视检查热成形部件来测定。拉伸是这样计算的:部件体积除以在该组实验中获得的最大部件体积(实施例8A-8E)。目视检查热成形部件的任何起泡,并将起泡程度分级为无(N)、低(L)或高(H)。以下结果证明,这些玻璃化转变温度为105°C的热塑性薄板可以在以下所示的条件下热成形,如由在热成形前未预干燥薄板的情况下,生产的薄板具有大于95%的拉伸和未起泡所证明的。
[00249]使用1.25英寸单螺杆挤出机生产由50wt%Teijin L-1250聚碳酸酯、49.85wt%PCTG 25976和0.15wt%Weston 619组成的可混共混物。连续挤出薄板,测量厚度为118密耳,然后将各种薄板剪切到合适尺寸。对一个薄板测量玻璃化转变温度,其为111°C。然后将薄板在50%相对湿度和60°C下调理4周。水分含量的测量结果为0.225wt%。随后使用Brown热成形机将薄板热成形到拉伸比为2.5∶1的阴模中。仅使用顶端加热,将热成形烘箱加热器设定为70/60/60%输出。将薄板留在烘箱中达不同的时间,以便测定薄板温度对部件质量的影响,如下表中所示。部件质量通过测量热成形部件的体积、计算拉伸和目视检查热成形部件来测定。拉伸是这样计算的:部件体积除以在该组实验中获得的最大部件体积(实施例A-D)。目视检查热成形部件的任何起泡,并将起泡程度分级为无(N)、低(L)或高(H)。以下结果证明,这些玻璃化转变温度为111°C的热塑性薄板可以在以下所示的条件下热成形,如由在热成形前未预干燥薄板的情况下,生产的薄板具有大于95%的拉伸和未起泡所证明的。
[00250]使用1.25英寸单螺杆挤出机生产由60wt%Teijin L-1250聚碳酸酯、39.85wt%PCTG 25976和0.15wt%Weston 619组成的可混共混物。然后使用3.5英寸单螺杆挤出机生产由该共混物组成的薄板。连续挤出薄板,测量厚度为118密耳,然后将各种薄板剪切到合适尺寸。对一个薄板测量玻璃化转变温度,其为117°C。然后将薄板在50%相对湿度和60°C下调理4周。水分含量的测量结果为0.215wt%。随后使用Brown热成形机将薄板热成形到拉伸比为2.5∶1的阴模中。仅使用顶端加热,将热成形烘箱加热器设定为70/60/60%输出。将薄板留在烘箱中达不同的时间,以便测定薄板温度对部件质量的影响,如下表中所示。部件质量通过测量热成形部件的体积、计算拉伸和目视检查热成形部件来测定。拉伸是这样计算的:部件体积除以在该组实验中获得的最大部件体积(实施例A)。目视检查热成形部件的任何起泡,并将起泡程度分级为无(N)、低(L)或高(H)。以下结果证明,这些玻璃化转变温度为117°C的热塑性薄板不能在以下所示的条件下热成形,如由在热成形前未预干燥薄板的情况下,不能生产出具有大于95%的拉伸和未起泡的薄板所证明的。
[00251]使用1.25英寸单螺杆挤出机生产由65wt%Teijin L-1250聚碳酸酯、34.85wt%PCTG 25976和0.15wt%Weston 619组成的可混共混物。然后使用3.5英寸单螺杆挤出机生产由该共混物组成的薄板。连续挤出薄板,测量厚度为118密耳,然后将各种薄板剪切到合适尺寸。对一个薄板测量玻璃化转变温度,其为120°C。然后将薄板在50%相对湿度和60°C下调理4周。水分含量的测量结果为0.23wt%。随后使用Brown热成形机将薄板热成形到拉伸比为2.5∶1的阴模中。仅使用顶端加热,将热成形烘箱加热器设定为70/60/60%输出。将薄板留在烘箱中达不同的时间,以便测定薄板温度对部件质量的影响,如下表中所示。部件质量通过测量热成形部件的体积、计算拉伸和目视检查热成形部件来测定。拉伸是这样计算的:部件体积除以在该组实验中获得的最大部件体积(实施例A)。目视检查热成形部件的任何起泡,并将起泡程度分级为无(N)、低(L)或高(H)。以下结果证明,这些玻璃化转变温度为120°C的热塑性薄板不能在以下所示的条件下热成形,如由在热成形前未预干燥薄板的情况下,不能生产出具有大于95%的拉伸和未起泡的薄板所证明的。
[00252]使用1.25英寸单螺杆挤出机生产由70wt%Teijin L-1250聚碳酸酯、29.85wt%PCTG 25976和0.15wt%Weston 619组成的可混共混物。然后使用3.5英寸单螺杆挤出机生产由该共混物组成的薄板。连续挤出薄板,测量厚度为118密耳,然后将各种薄板剪切到合适尺寸。对一个薄板测量玻璃化转变温度,其为123°C。然后将薄板在50%相对湿度和60°C下调理4周。水分含量的测量结果为0.205wt%。随后使用Brown热成形机将薄板热成形到拉伸比为2.5∶1的阴模中。仅使用顶端加热,将热成形烘箱加热器设定为70/60/60%输出。将薄板留在烘箱中达不同的时间,以便测定薄板温度对部件质量的影响,如下表中所示。部件质量通过测量热成形部件的体积、计算拉伸和目视检查热成形部件来测定。拉伸是这样计算的:部件体积除以在该组实验中获得的最大部件体积(实施例A和B)。目视检查热成形部件的任何起泡,并将起泡程度分级为无(N)、低(L)或高(H)。以下结果证明,这些玻璃化转变温度为123°C的热塑性薄板不能在以下所示的条件下热成形,如由在热成形前未预干燥薄板的情况下,不能生产出具有大于95%的拉伸和未起泡的薄板所证明的。
[00254]从以上相关工作实施例中的数据的比较能够清楚地看出,在玻璃化转变温度、密度、慢的结晶速率、熔体粘度和韧性方面,与市售可得的聚酯相比,本发明的聚酯提供了明显的优点。
[00255]本发明已经参考本文所公开的实施方案进行了详细描述,但是应该理解,在本发明的精神和范围内可以进行变化和改变。