English:
[0020] In one aspect, the polyesters useful in the invention contain no ethylene glycol residues.
[0023] In one aspect, the polyesters useful in the invention contain at least one branching agent without regard to the method or sequence in which it is added.
[0028] Also, in one aspect, use of the polyester compositions of the invention minimizes and/or eliminates the drying step prior to melt processing or thermoforming.
[0030] Figure 1 is a graph showing the effect of comonomer on the fastest crystallization half-times of modified PCT copolyesters.
[0032] Figure 3 is a graph showing the effect of 2,2,4,4-tetramethyl- 1 ,3-cyclobutanediol composition on the glass transition temperature (Tg) of the copolyester.
[0034] 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.
[0035] It is believed that the polyester(s) and/or polyester composition(s) which are included in the ophthalmic product(s) of the invention described herein can have a unique combination of two or more physical properties such as high impact strengths, moderate to high glass transition temperatures, chemical resistance, hydrolytic stability, toughness, low ductile-to-brittle transition temperatures, good color and clarity, low densities, long crystallization half- times, and good processability thereby easily permitting them to be formed into articles. In some of the embodiments of the invention, the polyesters have a unique combination of the properties of good impact strength, heat resistance, chemical resistance, density and/or the combination of the properties of good impact strength, heat resistance, and processability and/or the combination of two or more of the described properties, that have never before been believed to be present in ophthalmic product(s) comprising the polyester compositions which comprise the polyester(s) as disclosed herein.
[0036] Ophthalmic product" as used herein, refers to prescription eyeglass lenses, nonprescription eyeglass lenses, sunglass lenses, and eyeglass and sunglass frames.
[0079] The glass transition temperature (Tg) of the polyesters useful in the invention was determined using a TA DSC 2920 from Thermal Analyst Instrument at a scan rate of 20°C/min.
[0081] In one embodiment, an "amorphous" polyester can have a crystallization half-time of greater than 5 minutes at 17O 0 C or greater than 10 minutes at 17O 0 C or greater than 50 minutes at 17O 0 C or greater than 100 minutes at 170 0 C. In one embodiment, of the invention, the crystallization half- times are greater than 1 ,000 minutes at 17O 0 C. In another embodiment of the invention, the crystallization half-times of the polyesters useful in the invention are greater than 10,000 minutes at 17O 0 C. The crystallization half time of the polyester, as used herein, may be measured using methods well-known to persons of skill in the art. For example, the crystallization half time of the polyester, 1 1/2 , can be determined by measuring the light transmission of a sample via a laser and photo detector as a function of time on a temperature controlled hot stage. This measurement can be done by exposing the polymers to a temperature, T max , and then cooling it to the desired temperature. The sample can then be held at the desired temperature by a hot stage while transmission measurements are made as a function of time. Initially, the sample can be visually clear with high light transmission and becomes opaque as the sample crystallizes. The crystallization half-time is the time at which the light transmission is halfway between the initial transmission and the final transmission. T max is defined as the temperature required to melt the crystalline domains of the sample (if crystalline domains are present). The sample can be heated to Tmax to condition the sample prior to crystallization half time measurement. The absolute Tmax temperature is different for each composition. For example PCT can be heated to some temperature greater than 290 0 C to melt the crystalline domains.
[00100] Typically, step (I) can be carried out until 50% by weight or more of the 2,2,4,4-tetramethyl-1 ,3-cyclobutanediol has been reacted. Step (I) may be carried out under pressure, ranging from atmospheric pressure to 100 psig. The term "reaction product" as used in connection with any of the catalysts useful in the invention refers to any product of a polycondensation or esterification reaction with the catalyst and any of the monomers used in making the polyester as well as the product of a polycondensation or esterification reaction between the catalyst and any other type of additive.
[00101] Typically, Step (II) and Step (III) can be conducted at the same time. These steps can be carried out by methods known in the art such as by placing the reaction mixture under a pressure ranging from 0.002 psig to below atmospheric pressure, or by blowing hot nitrogen gas over the mixture.
[00103] The invention further relates to a polymer blend. The blend comprises:
[00112] In addition, the polyester compositions and the polymer blend compositions useful in the ophthalmic product(s) of this invention may also contain from 0.01 to 25% by weight of the overall composition 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. For example, UV additives can be incorporated into the ophthalmic product(s) through addition to the bulk, through application of a hard coat, or through the coextrusion of a cap layer. 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. Residues of such additives are also contemplated as part of the polyester composition.
[00114] Thermal stabilizers are compounds that stabilize polyesters during polyester manufacture and/or post polymerization, including, but not limited to, phosphorous compounds, including, but not limited to, phosphoric acid, phosphorous acid, phosphonic acid, phosphinic acid, phosphonous acid, and various esters and salts thereof. The esters can be alky!, branched alkyl, substituted alkyl, difunctional alkyl, alkyl ethers, aryl, and substituted aryl. In one embodiment, the number of ester groups present in the particular phosphorous compound can vary from zero up to the maximum allowable based on the number of hydroxyl groups present on the thermal stabilizer used. The term "thermal stabilizer" is intended to include the reaction product(s) thereof. The term "reaction product" as used in connection with the thermal stabilizers of the invention refers to any product of a polycondensation or esterification reaction between the thermal stabilizer and any of the monomers used in making the polyester as well as the product of a polycondensation or esterification reaction between the catalyst and any other type of additive. These can be present in the polyester compositions useful in the invention.
[00133] For purposes of this example, the samples had sufficiently similar inherent viscosities thereby effectively eliminating this as a variable in the crystallization rate measurements.
[00136] As shown in Table 1 and Figure 1 , 2,2,4 ,4-tetramethyl-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. [00137] Preparation of the polyesters shown on Table 1 is described below.
[00141] 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°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°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 0 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.
[00147] 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°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°C for 120 minutes and then heated up to 280°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.
[00162] 21.24 Ib (49.71 gram-mol) dimethyl terephthalate, 14.34 Ib (45.21 gram-mol) 1 ,4-cyclohexanedimethanol, and 4.58 Ib (14.44 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 0 C and at a pressure of 20 psig. 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 <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 (70 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 0.736 dL/g and a Tg of 104 0 C. NMR analysis showed that the polymer was composed of 85.4 mol% 1 ,4-cyclohexane- dimethanol residues and 14.6 mol% 2,2,4,4-tetramethyl-1 ,3-cyclobutanediol residues. The polymer had color values of: L*= 78.20, a*= -1.62, and b*= 6.23.
[00163] 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.
[00164] 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 psjg/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°C, and the pressure was decreased to <1 mm of Hg. The reaction mixture was held at 290°C and at a pressure of <1 mm of Hg for 60 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 0.715 dL/g and a Tg of 110 0 C. X-ray analysis showed that the polyester had 223 ppm tin. NMR analysis showed that the polymer was composed of 78.6 mol% 1 ,4-cyclohexane- dimethanol residues and 21.4 mol% 2,2,4,4-tetramethyl-1 ,3-cyclobutanediol residues. The polymer had color values of: L*= 76.45, a*= -1.65, and b*= 6.47.
[00165] 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.
[00166] 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 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 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.
[00167] 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 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°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 4 mm of Hg. The reaction mixture was hejd 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.
[00171] 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 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. 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 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.
[00172] 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.
[00176] 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 250 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-dirnethanol 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.
[00177] The polyesters described in Example 5B to Example 5D were prepared following a procedure similar to the one described for Example 5A. The composition and properties of these polyesters are shown in Table 5.
[00178] 21.24 Ib (49.71 gram-mol) dimethyl terephthalate, 6.43 Ib (20.28 gram-mol 1,4-cyclohexanedimethanol, and 12.49 Ib (39.37 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 290 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 <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 0.604 dL/g and a Tg of 139 0 C. NMR analysis showed that the polymer was composed of 40.8 mol% 1 ,4-cyclohexanedimethanol residues and 59.2 mol% 2,2,4,4-tetramethyl-1 ,3-cyclobutanediol residues. The polymer had color values of: L*= 80.48, a*= -1.30, and b*= 6.82.
[00179] 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 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 and the pressure was decreased to 4 mm of Hg. When the reaction mixture temperature was 270 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 0.475 dL/g and a Tg of 121 0 C. NMR analysis showed that the polymer was composed of 55.5 mol% 1 ,4- cyclohexane-dimethanol residues and 44.5 mol% 2,2,4,4-tetramethyl-1 ,3- cyclobutanediol residues. The polymer had color values of: L*= 85.63, a*= -0.88, and b*= 4.34.
[00180] This example shows data for comparative materials in Table 6. The PC was Makrolon 2608 from Bayer, with a nominal composition of 100 mole% bisphenol A residues and 100 mole% diphenyl carbonate residues. Makrolon 2608 has a nominal melt flow rate of 20 grams/10 minutes measured at 300C using a 1.2 kg weight. The PET was Eastar 9921 from Eastman Chemical Company, with a nominal composition of 100 mole% terephthalic acid, 3.5 mole% cyclohexanedimethanol (CHDM) and 96.5 mole% ethylene glycol. The PETG was Eastar 6763 from Eastman Chemical Company, with a nominal composition of 100 mole% terephthalic acid, 31 mole% cyclohexanedimethanol (CHDM) and 69 mole % ethylene glycol. The PCTG was Eastar DN001 from Eastman Chemical Company, with a nominal composition of 100 mole% terephthalic acid, 62 mole% cyclohexanedimethanol (CHDM) and 38 mole % ethylene glycol. The PCTA was Eastar AN001 from Eastman Chemical Company, with a nominal composition of 65 mole% terephthalic acid, 35 mole% isophthalic acid and 100 mole% cyclohexanedimethanol (CHDM). The Polysulfone was Udel 1700 from Solvay, with a nominal composition of 100 mole% bisphenol A residues and 100 mole% 4,4-dichlorosulfonyl sulfone residues. Udel 1700 has a nominal melt flow rate of 6.5 grams/10 minutes measured at 343C using a 2.16 kg weight. The SAN was Lustran 31 from Lanxess, with a nominal composition of 76 weight % styrene and 24 weight % acrylonitrile. Lustran 31 has a nominal melt flow rate of 7.5 grams/10 minutes measured at 230C using a 3.8 kg weight. The examples of the invention show improved toughness in 6.4mm thickness bars compared to all of the other resins.
[00182] Dimethyl terephthalate, 1 ,4-cyclohexanedimethanol, and 2,2,4,4-tetramethyl-1 ,3-cyclobutanediol were weighed into a 500-ml single neck round bottom flask. NMR analysis on the 2,2,4,4-tetramethyl- 1 ,3-cyclobutanediol starting material showed a cis/trans ratio of 53/47. The polyesters of this example were prepared with a 1.2/1 glycol/acid ratio with the entire excess coming from the 2,2,4,4-tetramethyl-1 ,3-cyclobutanediol. Enough dibutyltin oxide catalyst was added to give 300 ppm tin in the final polymer. The flask was under a 0.2 SCFC nitrogen purge with vacuum reduction capability. The flask was immersed in a Belmont metal bath at 200 0 C and stirred at 200 RPM after the reactants had melted. After about 2.5 hours, the temperature was raised to 21O 0 C and these conditions were held for an additional 2 hours. The temperature was raised to 285 0 C (in approximately 25 minutes) and the pressure was reduced to 0.3 mm of Hg over a period of 5 minutes. The stirring was reduced as the viscosity increased, with 15 RPM being the minimum stirring used. The total polymerization time was varied to attain the target inherent viscosities. After the polymerization was complete, the Belmont metal bath was lowered and the polymer was allowed to cool to below its glass transition temperature. After about 30 minutes, the flask was reimmersed in the Belmont metal bath (the temperature had been increased to 295 0 C during this 30 minute wait) and the polymer mass was heated until it pulled away from the glass flask. The polymer mass was stirred at mid level in the flask until the polymer had cooled. The polymer was removed from the flask and ground to pass a 3 mm screen. Variations to this procedure were made to produce the copolyesters described below with a targeted composition of 20 mol%. [00183] Inherent viscosities were measured as described in the "Measurement Methods" section above. The compositions of the polyesters were determined by 1 H NMR as explained before in the Measurement Methods section. The glass transition temperatures were determined by DSC, using the second heat after quench at a rate of 20°C/min.
[00184] 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 ( 4 moles) of dimethyl terephthalate,.230g (1.6 moles) of 2,2,4,4-tetramethyl-1 ,3,- cyclobutanediol, 460.8g (3.2 moles) 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
[00190] 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).
[00191] 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.
[00195] 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.
[00197] 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, 31 Jg 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.
[00198] 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.
[00208] 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).
[00217] Dimethyl terephthalate, 1 ,4-cyclohexanedimethanol, and 2,2,4,4-tetramethyI-1 ,3-cyclobutanediol were weighed into a 500-ml single neck round bottom flask. The polyesters of this example were prepared with a 1.2/1 glycol/acid ratio with the entire excess coming from the 2,2,4,4-tetramethyl- 1 ,3-cyclobutanediol. Enough dibutyltin oxide catalyst was added to give 300 ppm tin in the final polymer. The flask was under a 0.2 SCFC nitrogen purge with vacuum reduction capability. The flask was immersed in a Belmont metal bath at 200 0 C and stirred at 200 RPM after the reactants had melted. After about 2.5 hours, the temperature was raised to 21O 0 C and these conditions were held for an additional 2 hours. The temperature was raised to 285 0 C (in approximately 25 minutes) and the pressure was reduced to 0.3 mm of Hg over a period of 5 minutes. The stirring was reduced as the viscosity increased, with 15 RPM being the minimum stirring used. The total polymerization time was varied to attain the target inherent viscosities. After the polymerization was complete, the Belmont metal bath was lowered and the polymer was allowed to cool to below its glass transition temperature. After about 30 minutes, the flask was reimmersed in the Belmont metal bath (the temperature had been increased to 295 0 C during this 30 minute wait) and the polymer mass was heated until it pulled away from the glass flask. The polymer mass was stirred at mid level in the flask until the polymer had cooled. The polymer was removed from the flask and ground to pass a 3 mm screen. Variations to this procedure were made to produce the copolyesters described below with a targeted composition of 45 mol%.
[00219] 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.
[00221] Dimethyl terephthalate, 1 ,4-cydohexanedimethanol, and 2,2,4,4-tetramethyl-1 ,3-cyclobutanediol were weighed into a 500-ml single neck round bottom flask. The polyesters of this example were prepared with a 1.2/1 glycol/acid ratio with the entire excess coming from the 2,2,4,4-tetramethyl- 1 ,3-cyclobutanediol. Enough dibutyltin oxide catalyst was added to give 300 ppm tin in the final polymer. The flask was under a 0.2 SCFC nitrogen purge with vacuum reduction capability. The flask was immersed in a Belmont metal bath at 200 0 C and stirred at 200 RPM after the reactants had melted. After about 2.5 hours, the temperature was raised to 21O 0 C and these conditions were held for an additional 2 hours. The temperature was raised to 285 0 C (in approximately 25 minutes) and the pressure was reduced to 0.3 mm of Hg over a period of 5 minutes. The stirring was reduced as the viscosity increased, with 15 RPM being the minimum stirring used. The total polymerization time was varied to attain the target inherent viscosities. After the polymerization was complete, the Belmont metal bath was lowered and the polymer was allowed to cool to below its glass transition temperature. After about 30 minutes, the flask was reimmersed in the Belmont metal bath (the temperature had been increased to 295 0 C during this 30 minute wait) and the polymer mass was heated until it pulled away from the glass flask. The polymer mass was stirred at mid level in the flask until the polymer had cooled. The polymer was removed from the flask and ground to pass a 3 mm screen. Variations to this procedure were made to produce the copolyesters described below with a targeted composition of 45 mol%.
[00231] Sheets consisting of Kelvx 201 were produced using a 3.5 inch single screw extruder. Kelvx is a blend consisting of 69.85% PCTG (Eastar from Eastman Chemical Co. having 100 mole % terephthalic acid residues, 62 mole % 1 ,4-cyclohexanedimethanol residues, and 38 mole % ethylene glycol residues); 30% PC (bisphenol A polycarbonate); and 0.15% Weston 619 (stabilizer sold by Crompton Corporation). 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 50% relative humidity and 60 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 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 E). 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°C can be thermoformed under the conditions shown below, as evidenced by the production of sheets having at least 95% draw and no blistering, without predrying the sheets prior to thermoforming.
[00233] 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 0 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°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.
[00234] 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) 1 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.
[00235] 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.
[00236] 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 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 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.
[00237] 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 0 C. Sheets were then conditioned at 50% relative humidity and 6O 0 C for 4 weeks. The moisture level was measured to be 0.225 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°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.
[00238] 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.
[00239] 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.
[00240] 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 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.
[00241] Sheets consisting of Teijin L-1250 polycarbonate 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 149°C. Sheets were then conditioned at 50% relative humidity and 60 0 C for 4 weeks. The moisture level was measured to be 0.16 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 149°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.
[00242] 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.
[00243] 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:
[0020]在一个方面中,对本发明有用的聚酯不包含乙二醇残基。
[0023]在一个方面中,对本发明有用的聚酯包含至少一种支化剂,而这与其中添加其的方法或顺序无关。
[0028]此外,在一个方面中,使用本发明的聚酯组合物可以最小化和/或消除了在熔融加工和/或热成形之前的干燥步骤。
[0030]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。
[0032]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。
[0034]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。
[0035]据信本文中所述的被归入眼用产品的本发明聚酯和/或聚酯组合物可以具有例如以下两种或多种物理性能的独特的组合:高冲击强度、中等至高的玻璃化转变温度、耐化学性、水解稳定性、韧性、低韧脆性转变温度、良好的颜色和透明性、低密度、长结晶半衰期和良好的加工性能,由此容易允许它们成形为制品。在本发明的一些实施方案中,聚酯具有良好的冲击强度、耐热性、耐化学性、密度的独特的性能的组合和/或良好的冲击强度、耐热性和加工性能的性能的组合和/或所述性能的两种或更多种的组合,这些以前未被考虑存在于包括聚酯组合物的眼用产品中,所述聚酯组合物包括如本文中所公开的聚酯。
[0036]如本文中使用的,“眼用产品”是指处方性(prescription)眼镜镜片、非处方性眼镜镜片、太阳镜镜片和眼镜和太阳镜框。
[0079]可用于本发明的聚酯的玻璃化转变温度(Tg)使用ThermalAnalyst Instruments的TA DSC 2920以20°C/min的扫描速率测定。
[0081]在一种实施方案中,“无定形”聚酯可以具有在170°C大于5分钟或者在170°C大于10分钟或者在170°C大于50分钟或者在170°C大于100分钟的结晶半衰期。本发明的一种实施方案中,结晶半衰期在170°C大于1,000分钟。在本发明的另一实施方案中,可用于本发明的聚酯的结晶半衰期在170°C大于10,000分钟。如本文中使用的,聚酯的结晶半衰期可以使用本领域技术人员众所周知的方法来测量。例如,聚酯的结晶半衰期,t1/2,可以通过在温控热台上随着时间经激光器和光电检测器测量样品的透光率来测定。这种测量可以是这样进行的:通过将聚合物暴露于温度Tmax,并随后将其冷却到期望的温度。随后可以通过热台将样品保持在期望的温度,同时测量透光率随时间的变化。最初,样品可以在视觉上是透明的,具有高透光率,且随着样品结晶而变得不透明。结晶半衰期是透光率在初始透光率与最终透光率之间一半时的时间。Tmax定义为熔融样品晶畴所需的温度(如果存在晶畴的话)。可以在结晶半衰期测量之前将样品加热到Tmax以调理该样品。对于每一种组合物,绝对Tmax温度是不同的。例如,PCT可以被加热到高于290°C的某温度以熔融晶畴。
[00100]一般地,步骤(I)可以进行直到50wt%或更多的2,2,4,4-四甲基-1,3-环丁二醇已经反应。步骤(I)可以在压力下进行,压力范围为大气压力至100psig。如与任何对本发明有用的催化剂相结合使用的术语“反应产物”是指使用催化剂和用于制备聚酯的任何单体的缩聚或者酯化反应的任何产物以及催化剂和任何其它类型的添加剂间的缩聚或者酯化反应的产物。
[00101]一般地,步骤(II)和步骤(III)可以同时进行。这些步骤可以通过本领域已知的方法进行,例如通过将反应混合物置于压力下,压力范围为0.002psig至低于大气压力,或者通过在混合物上吹入热氮气。
[00103]本发明还涉及聚合物的共混物。The blend comprises:
[00112]另外,可用于本发明的眼用产品的聚酯组合物和聚合物共混物组合物还可包含总组合物的0.01-25wt%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。例如,通过经施加硬涂层或者经共挤压盖层而添加到本体中,可以将UV添加剂结合到本发明的眼用产品中。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。也预期将这种添加剂的残余物作为聚酯组合物的一部分。
[00114]热稳定剂是在聚酯制造和/或后聚合期间稳定聚酯的化合物,包括但不限于含磷化合物,包括但不限于磷酸、亚磷酸、膦酸、次膦酸、亚膦酸以及其各种酯和盐。酯可以是烷基、支链烷基、取代烷基、二官能烷基、烷基醚、芳基和取代芳基的酯。在一种实施方案中,存在于特定含磷化合物中的酯基的数目可以从零变化到至多基于存在于所用热稳定剂中的羟基的数目所允许的最大值。术语“热稳定剂”意图包括其反应产物。如与本发明的热稳定剂相联系使用的术语“反应产物”是指热稳定剂与用于制备聚酯的任何单体间的缩聚或者酯化反应的任何产物以及催化剂和任何其它类型的添加剂间的缩聚或者酯化反应的产物。这些可以存在于对本发明有用的聚酯组合物中。
[00133]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。
[00136]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。
[00141]将77.68g对苯二甲酸二甲酯、50.77g 1,4-环己烷二甲醇、27.81g乙二醇和0.0433g氧化二丁基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。
[00147]将81.3g对苯二甲酸二甲酯、42.85g的1,4-环己烷二甲醇、34.44g乙二醇和0.0419g氧化二丁基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。
[00162]在200ppm催化剂三(2-乙基己酸)丁基锡存在下,使21.24lb(49.71g-mol)对苯二甲酸二甲酯、14.34lb(45.21g-mol)1,4-环己烷二甲醇和4.58lb(14.44g-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(70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0.736dL/g,Tg为104°C。NMR分析表明聚合物包含85.4mol%1,4-环己烷二甲醇残基和14.6mol%2,2,4,4-四甲基-1,3-环丁二醇残基。聚合物的色值为L*=78.20,a*=-1.62,和b*=6.23。
[00163]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。
[00164]在200ppm催化剂三(2-乙基己酸)丁基锡存在下,使21.24lb(49.71g-mol)对苯二甲酸二甲酯、12.61lb(39.77g-mol)1,4-环己烷二甲醇、6.30lb(19.88g-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60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0.715dL/g,Tg为110°C。X射线分析表明聚酯具有223ppm锡。NMR分析表明聚合物包含78.6mol%1,4-环己烷二甲醇残基和21.4mol%2,2,4,4-四甲基-1,3-环丁二醇残基。聚合物的色值为L*=76.45;a*=-1.65;和b*=6.47。
[00165]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。
[00166]在200ppm催化剂三(2-乙基己酸)丁基锡存在下,使21.24lb(49.71g-mol)对苯二甲酸二甲酯、12.61lb(39.77g-mol)1,4-环己烷二甲醇、6.30lb(19.88g-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%的1,4-环己烷二甲醇残基和22.9mol%的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。
[00167]在200ppm催化剂三(2-乙基己酸)丁基锡存在下,使21.24lb(49.71g-mol)对苯二甲酸二甲酯、12.61lb(39.77g-mol)1,4-环己烷二甲醇、6.30lb(19.88g-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%的1,4-环己烷二甲醇残基和23.1mol%的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。
[00171]在200ppm催化剂三(2-乙基己酸)丁基锡存在下,使21.24lb(49.71g-mol)对苯二甲酸二甲酯、11.82lb(37.28g-mol)1,4-环己烷二甲醇和6.90lb(21.77g-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。
[00172]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。
[00176]在200ppm催化剂三(2-乙基己酸)丁基锡存在下,使21.24lb(49.71g-mol)对苯二甲酸二甲酯、8.84lb(27.88g-mol)1,4-环己烷二甲醇和10.08lb(31.77g-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。
[00177]实施例5B-实施例5D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5中。
[00178]在200ppm催化剂三(2-乙基己酸)丁基锡存在下,使21.24lb(49.71g-mol)对苯二甲酸二甲酯、6.43lb(20.28g-mol)1,4-环己烷二甲醇和12.49lb(39.37g-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2mmHg。反应混合物在290°C和<1mmHg的压力下保持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0.604dL/g,Tg为139°C。NMR分析表明聚合物包含40.8mol%的1,4-环己烷二甲醇残基和59.2mol%的2,2,4,4-四甲基-1,3-环丁二醇残基。聚合物的色值为L*=80.48;a*=-1.30,和b*=6.82。
[00179]在200ppm催化剂三(2-乙基己酸)丁基锡存在下,使21.24lb(49.71g-mol)对苯二甲酸二甲酯、8.84lb(27.88g-mol)1,4-环己烷二甲醇、10.08lb(31.77g-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并将压力降至4mmHg。当应混合物在270°C且压力为4mmHg时,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0.475dL/g,Tg为121°C。NMR分析表明聚合物包含55.5mol%的1,4-环己烷二甲醇残基和44.5mol%的2,2,4,4-四甲基-1,3-环丁二醇残基。聚合物的色值为L*=85.63;a*=-0.88;和b*=4.34。
[00180]本实施例显示了用于对比材料的数据,其示于表6中。PC为来自Bayer的Makrolon 2608,其标称组成为100mol%双酚A残基和100mol%碳酸二苯酯残基。Makrolon 2608具有使用1.2kg重量在300C测量的20g/10min的标称熔体流动速率。PET为来自Eastman ChemicalCompany的Eastar 9921,其标称组成为100mol%对苯二甲酸、3.5mol%环己烷二甲醇(CHDM)和96.5mol%乙二醇。PETG为来自EastmanChemical Company的Eastar 6763,其标称组成为100mol%对苯二甲酸、31mol%环己烷二甲醇(CHDM)和69mol%乙二醇。PCTG为来自EastmanChemical Company的Eastar DN001,其标称组成为100mol%对苯二甲酸、62mol%环己烷二甲醇(CHDM)和38mol%乙二醇。PCTA为来自Eastman Chemical Company的Eastar AN001,其标称组成为65mol%对苯二甲酸、35mol%间苯二甲酸和100mol%环己烷二甲醇(CHDM)。聚砜为来自Solvay的Udel 1700,其标称组成为100mol%双酚A残基和100mol%4,4-二氯磺酰基砜残基。Udel 1700具有使用2.16kg重量在343C测量的6.5g/10min的标称熔体流动速率。SAN为来自Lanxess的Lustran31,其标称组成为76wt%苯乙烯和24wt%丙烯腈。Lustran 31具有使用3.8kg重量在230C测量的7.5g/10min的标称熔体流动速率。与所有其它树脂相比,本发明的实施例在6.4mm厚试条中显示出改进的韧性。
[00182]将对苯二甲酸二甲酯、1,4-环己烷二甲醇和2,2,4,4-四甲基-1,3-环丁二醇称重加入500-毫升单颈圆底烧瓶中。2,2,4,4-四甲基-1,3-环丁二醇起始材料的NMR分析显示顺式/反式比例为53/47。本实施例的聚酯采用1.2/1二醇/酸比例制备,全部过量均来自2,2,4,4-四甲基-1,3-环丁二醇。加入足够的氧化二丁基锡催化剂以在最终聚合物中得到300ppm锡。烧瓶处于具有真空降低(reduction)能力的0.2SCFC氮气吹扫下。将烧瓶浸入200°C的Belmont金属浴并在反应物熔融之后以200RPM搅拌。约2.5小时后,将温度升高至210°C并将这些条件保持另外的2小时。将温度升高至285°C(约25分钟)并在5分钟内将压力降低至0.3mmHg。随着粘度增加,降低搅拌,15RPM是所用的最小搅拌。改变总聚合时间以获得目标比浓对数粘度。聚合完成后,使Belmont金属浴下降并允许聚合物冷却到低于其玻璃化转变温度。约30分钟后,再次将烧瓶浸入Belmont金属浴(在这30分钟的等待中温度已升至295°C)并加热聚合物物质直到其脱离玻璃烧瓶。在烧瓶中以中等水平搅拌聚合物物质直到聚合物冷却。从烧瓶中取出聚合物并研磨以便通过3mm筛。对该程序进行改变以生产目标的组成为20mol%的如下所述的共聚酯。
[00184]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(4mol)的对苯二甲酸二甲酯、230g(1.6mol)的2,2,4,4-四甲基-1,3-环丁二醇、460.8g(3.2mol)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。
[00190]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。
[00191]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。
[00195]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。
[00197]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。
[00198]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。
[00208]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。
[00217]将对苯二甲酸二甲酯、1,4-环己烷二甲醇和2,2,4,4-四甲基-1,3-环丁二醇称重加入500-毫升单颈圆底烧瓶中。本实施例的聚酯采用1.2/1二醇/酸比例制备,全部过量均来自2,2,4,4-四甲基-1,3-环丁二醇。加入足够的氧化二丁基锡催化剂以在最终聚合物中得到300ppm锡。烧瓶处于具有真空降低能力的0.2SCFC氮气吹扫下。将烧瓶浸入200°C的Belmont金属浴并在反应物熔融之后以200RPM搅拌。约2.5小时后,将温度升高至210°C并将这些条件保持另外的2小时。将温度升高至285°C(约25分钟)并在5分钟内将压力降低至0.3mmHg。随着粘度增加,降低搅拌,15RPM是所用的最小搅拌。改变总聚合时间以获得目标比浓对数粘度。聚合完成后,使Belmont金属浴下降并允许聚合物冷却到低于其玻璃化转变温度。约30分钟后,再次将烧瓶浸入Belmont金属浴(在这30分钟的等待中温度已升至295°C)并加热聚合物物质直到其脱离玻璃烧瓶。在烧瓶中以中等水平搅拌聚合物物质直到聚合物冷却。从烧瓶中取出聚合物并研磨以便通过3mm筛。对该程序进行改变以生产目标的组成为45mol%的如下所述的共聚酯。
[00219]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。
[00221]将对苯二甲酸二甲酯、1,4-环己烷二甲醇和2,2,4,4-四甲基-1,3-环丁二醇称重加入500-毫升单颈圆底烧瓶中。本实施例的聚酯采用1.2/1二醇/酸比例制备,全部过量均来自2,2,4,4-四甲基-1,3-环丁二醇。加入足够的氧化二丁基锡催化剂以在最终聚合物中得到300ppm锡。烧瓶处于具有真空降低能力的0.2SCFC氮气吹扫下。将烧瓶浸入200°C的Belmont金属浴并在反应物熔融之后以200RPM搅拌。约2.5小时后,将温度升高至210°C并将这些条件保持另外的2小时。将温度升高至285°C(约25分钟)并在5分钟内将压力降低至0.3mmHg。随着粘度增加,降低搅拌,15RPM是所用的最小搅拌。改变总聚合时间以获得目标比浓对数粘度。聚合完成后,使Belmont金属浴下降并允许聚合物冷却到低于其玻璃化转变温度。约30分钟后,再次将烧瓶浸入Belmont金属浴(在这30分钟的等待中温度已升至295°C)并加热聚合物物质直到其脱离玻璃烧瓶。在烧瓶中以中等水平搅拌聚合物物质直到聚合物冷却。从烧瓶中取出聚合物并研磨以便通过3mm筛。对该程序进行改变以生产目标的组成为45mol%的如下所述的共聚酯。
[00231]使用3.5英寸单螺杆挤出机生产由Kelvx 201组成的薄板。Kelvx是由69.85%PCTG(获自Eastman Chemical Co.的Eastar,其具有100mol%对苯二甲酸残基、62mol%1,4-环己烷二甲醇残基和38mol%乙二醇残基);30%PC(双酚A聚碳酸酯);和0.15%Weston 619(由Crompton Corporation出售的稳定剂)组成的共混物。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50%相对湿度和60°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E)。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,生产的薄板具有至少95%的拉伸和未起泡所证明的。
[00233]使用3.5英寸单螺杆挤出机生产由PCTG25976(100mol%对苯二甲酸残基、62mol%1,4-环己烷二甲醇残基和38mol%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。
[00234]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%Weston619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。
[00235]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。
[00236]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。
[00237]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。
[00238]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。
[00239]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。
[00240]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。
[00241]使用3.5英寸单螺杆挤出机生产由Teijin L-1250聚碳酸酯组成的薄板。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149°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0.16wt%。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149°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。
[00242]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。
[00243]本发明已经特别参考其优选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。