English:
[0003] Also, there is a commercial need for a polymeric material with a combination of properties making it desirable for certain applications, for example, thermoformed film and sheet applications, including a combination of three or more of high notched Izod impact strength, certain glass transition temperature (T 9 ), certain inherent viscosities, certain flexural modulus, good clarity, and good color.
[0023] In one aspect, this invention relates to a process comprising the following steps:
[0024] In one aspect, the invention relates to a process for making a polyester comprising the following steps:
[0026] In one aspect, the invention relates to a process for making a polyester comprising the following steps:
[0027] In one aspect, the invention relates to a process for making a polyester comprising the following steps:
[0030] In one aspect, the polyesters useful in the invention can comprise at least one phosphate ester whether or not present as a thermal stabilizer.
[0031] In one aspect, the polyesters useful in the invention can comprise at least one phosphate ester described herein which is present as a thermal stabilizer.
[0032] In one aspect, the polyesters useful in the invention contain no branching agent, or alternatively, at least one branching agent is added either prior to or during polymerization of the polyester.
[0035] In one aspect, the polyesters, polyester compositions and/or processes of the invention useful in the invention can comprise at least one phosphorus compound.
[0036] In one aspect, the polyesters, polyester compositions and/or processes of the invention useful in the invention can comprise phosphorus atoms.
[0037] In one aspect, the polyesters and/or polyester compositions of the invention can comprise titanium atoms and tin atoms.
[0039] In one aspect, the polyesters, polyester compositions and/or processes of the invention useful in the invention can comprise phosphorus atoms and titanium atoms.
[0040] In one aspect, the invention can comprise phosphorus atoms, tin atoms, and titanium atoms.
[0041] In one aspect, any of the polyester(s), polyester compositions and/or processes of the invention may comprise at least one phosphorus compound.
[0042] In one aspect, any of the polyester(s), polyester; compositions and/or processes of the invention may comprise at least one titanium compound.
[0043] In one aspect, any of the polyester(s), polyester compositions and/or processes of the invention may comprise at least one titanium compound and at least one phosphorus compound.
[0044] In one aspect, any of the polyester(s), polyester compositions and/or processes of the invention may comprise (i) at least one titanium compound, at and optionally, at least one compound chosen from tin, gallium, zinc, antimony, cobalt, manganese, magnesium, germanium, lithium, aluminum compounds and an aluminum compound with lithium hydroxide or sodium hydroxide; and (ii) at least one phosphorus compound. The term "phosphorus compound" is intended to include reaction products thereof.
[0052] In one aspect, at least one phosphorus compound useful in the invention may comprise at least one aryl phosphate ester.
[0055] In one aspect, at least one phosphorus compound useful in the invention may comprise at least one triaryl phosphate ester.
[0056] In one aspect, at least one phosphorus compound useful in the invention may comprise at least one triaryl phosphate ester which is not substituted with benzyl groups.
[0057] In one aspect, at least one phosphorus compound useful in the invention may comprise at least one alkyl phosphate ester.
[0058] In one aspect, at least one phosphorus compound useful in the invention may comprise triphenyl phosphate and/or Merpol A. In one embodiment, any of the polyester compositions of the invention may comprise triphenyl phosphate.
[0059] In one aspect, any of the processes described herein for making any of the polyester compositions and/or polyesters can comprise at least one mixed alkyl aryl phosphite, such as, for example, bis(2,4-dicumylphenyl)pentaerythritol diphosphite also known as Doverphos S-9228 (Dover Chemicals, CAS# 154862-
[0060] In one aspect, any of the processes described herein for making any of the polyester compositions and/or polyesters can comprise at least one one phosphine oxide.
[0061] In one aspect, any of the processes described herein for making any of the polyester compositions and/or polyesters can comprise at least one salt of phosphoric acid such as, for example, KH 2 PO 4 and Zn3(PO 4 )2.
[0062] In one aspect, any of processes described herein for making the polyester compositions and/or polyesters comprise at least one of the phosphorus compounds described herein.
[0063] It is believed that any of the processes of making the polyesters useful in the invention may be used to make any of the polyesters useful in the invention.
[0064] In one aspect, the pressure used in Step (I) of any of the processes of the invention consists of at least one pressure chosen from 0 psig to 75 psig. In one embodiment, the pressure used in Step (I) of any of the processes of the invention consists of at least one pressure chosen from 0 psig to 50 psig.
[0065] In one aspect, the pressure used in Step (II) of any of the processes of the invention consists of at least one pressure chosen from 20 torr absolute to in Step (II) of any of the processes of the invention consists of at least one pressure chosen from 3 torr absolute to 0.02 ton * absolute; in one embodiment, the pressure used in Step (II) of any of the processes of the invention consists of at least one pressure chosen from 20 torr absolute to 0.1 torr absolute; in one embodiment, the pressure used in Step (II) of any of the processes of the invention consists of at least one pressure chosen from 10 torr absolute to 0.1 torr absolute; in one embodiment, the pressure used in Step (II) of any of the processes of the invention consists of at least one pressure chosen from 5 torr absolute to 0.1 torr absolute; in one embodiment, the pressure used in Step (II) of any of the processes of the invention consists of at least one pressure chosen from 3 torr absolute to 0.1 torr absolute.
[0066] In one aspect, the molar ratio of glycol component/dicarboxylic acid component added in Step (I) of any of the processes of the invention is 1.0- 3.0/1.0; in one aspect, the molar ratio of glycol component/dicarboxylic acid component added in Step (I) of any of the processes of the invention is 1.0- 2.5/1.0; in one aspect, the molar ratio of glycol component/dicarboxylic acid component added in Step (I) of any of the processes of the invention is 1.0- 2.0/1.0; in one aspect, the molar ratio of glycol component/dicarboxylic acid component added in Step (I) of any of the processes of the invention is 1.0- 1.75/1.0; in one aspect, the molar ratio of glycol component/dicarboxylic acid component added in Step (I) of any of the processes of the invention is 1.0- 1.5/1.0.
[0067] In one aspect, the molar ratio of glycol component/dicarboxylic acid component added in Step (I) of any of the processes of the invention is 1.01- 3.0/1.0; in one aspect, the molar ratio of glycol component/dicarboxylic acid component added in Step (I) of any of the processes of the invention is 1.01- 2.5/1.0; in one aspect, the molar ratio of glycol component/dicarboxylic acid component added in Step (I) of any of the processes of the invention is 1.01- 2.0/1.0; in one aspect, the molar ratio of glycol component/dicarboxylic acid component added in Step (I) of any of the processes of the invention is 1.01- 1.75/1.0; in one aspect, the molar ratio of glycol component/dicarboxylic acid component added in Step (I) of any of the processes of the invention is 1.01-
[0068] In any of the process embodiments for making the polyesters useful in the invention, the heating time of Step (II) may be from 1 to 5 hours. In any of the process embodiments for making the polyesters useful in the invention, the heating time of Step (II) may be from 1 to 4 hours. In any of the process embodiments for making the polyesters useful in the invention, the heating time of Step (II) may be from 1 to 3 hours. In any of the process embodiments for making the polyesters useful in the invention, the heating time of Step (II) may be from 1.5 to 3 hours. In any of the process embodiments for making the polyesters useful in the invention, the heating time of Step (II) may be from 1 to 2 hours.
[0074] For example, the weight of tin atoms and phosphorus atoms present in the final polyester can be measured in ppm and can result in a weight ratio of total phosphorus atoms to total tin atoms in the final polyester of any of the aforesaid weight ratios.
[0080] For example, the weight of titanium atoms and phosphorus atoms present in the final polyester can be measured in ppm and can result in a weight ratio of total phosphorus atoms to total titanium atoms in the final polyester of any of the aforesaid weight ratios.
[0083] In one aspect, the amount of titanium atoms in the polyesters useful in the invention can be from 0 to 400 ppm titanium atoms based on the weight of the final polyester.
[0084] In one aspect, the amount of titanium atoms in the polyesters useful in the invention can be from 15 to 400 ppm titanium atoms based on the weight of the final polyester.
[0086] In one aspect, the amount of phosphorus atoms in the polyesters useful in the invention can be from 1 to 500 ppm phosphorus atoms based on the weight of the final polyester and the amount of titanium atoms in the polyester can be from 1 to 100 ppm titanium atoms based on the weight of the final polyester.
[0087] In one aspect, the amount of phosphorus atoms in the polyesters useful in the invention can be from 1 to 500 ppm phosphorus atoms based on the weight of the final polyester and the amount of titanium atoms in the polyester can be from 1 to 400 ppm titanium atoms based on the weight of the final polyester.
[0088] In one aspect, the amount of phosphorus atoms in the polyesters useful in the invention can be from 1 to 500 ppm phosphorus atoms based on the weight of the final polyester and the amount of titanium atoms in the polyester can be from 1 to 100 ppm titanium atoms based on the weight of the final polyester.
[0097] 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.
[00105] In one embodiment, the processes of making the polyesters useful in the invention can comprise a batch or continuous process.
[00109] When titanium is added to to the polyesters and/or polyester compositions and/or process of making the polyesters of the invention, it is added to the process of making the polyester in the form of a titanium compound. The amount of the titanium compound added to the polyesters of the invention and/or polyester compositions of the invention and/or processes of the invention can be measured in the form of titanium atoms present in the final polyester, for example, by weight measured in ppm.
[00112] The polyesters used in the present invention typically can be prepared from dicarboxylic acids and diols which react in substantially equal proportions and are incorporated into the polyester polymer as their corresponding residues. The polyesters of the present invention, therefore, can contain substantially equal molar proportions of acid residues (100 mole%) and diol (and/or multifunctional hydroxyl compound) residues (100 mole%) such that the total moles of repeating units is equal to 100 mole%. The mole percentages provided in the present disclosure, therefore, may be based on the total moles of acid residues, the total moles of diol residues, or the total moles of repeating units. For example, a polyester containing 10 mole% isophthalic acid, based on the total acid residues, means the polyester contains 10 mole% isophthalic acid residues out of a total of 100 mole% acid residues. Thus, there are 10 moles of isophthalic acid residues among every 100 moles of acid residues. In another example, a polyester containing 30 mole% 2,2,4 ,4-tetramethyl-1 ,3-cyclobutanediol, based on the total diol residues, means the polyester contains 30 mole% 2,2,4,4-tetramethyl-1 ,3- cyclobutanediol residues out of a total of 100 mole% diol residues. Thus, there are 30 moles of 2,2,4,4-tetramethyl-1 ,3-cyclobutanediol residues among every 100 moles of diol residues.
[00169] In one embodiment, the polyesters useful in the invention and/or the polyester compositions of the invention, [in one embodiment, in the presence of and/or in the absence of toner(s)], can have color values L * , a * and b* which can be determined using a Hunter Lab Ultrascan Spectra Colorimeter manufactured by Hunter Associates Lab Inc., Reston, Va. The color determinations are averages of values measured on either pellets of the polyesters or plaques or other items injection molded or extruded from them. They are determined by the L*a*b* color system of the CIE (International Commission on Illumination) (translated), wherein L* represents the lightness coordinate, a * represents the red/green coordinate, and b* represents the yellow/blue coordinate. In certain embodiments, the b * values for the polyesters useful in the invention [in one embodiment, in the presence of and/or in the absence of toner(s)] can be from - 12 to less than 12 and the L* values can be from 50 to 90. In other embodiments, the b * values for the polyesters useful in the invention [in one embodiment, in the presence of and/or in the absence of toner(s)] can be present in one of the following ranges: from -10 to 10; -10 to less than 10; -10 to 9; -10 to 8; -10 to 7; -10 to 6; -10 to 5; -10 to 4; -10 to 3; -10 to 2; from -5 to 9; -5 to 8; -5 to 7; -5 to 6; -5 to 5; -5 to 4; -5 to 3; -5 to 2; 0 to 9; 0 to 8; 0 to 7; 0 to 6; 0 to 5; 0 to 4; 0 to 3; 0 to 2; 1 to 10; 1 to 9; 1 to 8; 1 to 7; 1 to 6; 1 to 5; 1 to 4; 1 to
[00177] In some embodiments, use of the polyester compositions useful in the invention minimizes and/or eliminates the drying step prior'to melt processing and/or thermoforming.
[00194] In one aspect, at least one phosphorus compound useful in the invention comprises at least one aryl phosphate ester which is not substituted with benzyl groups.
[00195] In one aspect, any of the phosphorus compounds useful in the invention may comprise at least one alkyl phosphate ester.
[00197] In one embodiment, the phosphate esters useful in the invention as thermal stabilizers and/or color stabilizers include but are not limited to, at least one of the following: triaryl phosphates, alkyl diaryl phosphates, and mixed alkyl aryl phosphates.
[00198] In one embodiment, the phosphate esters useful as thermal stabilizers and/or color stabilizers in the invention can include but are not limited to, at least one of the following: triaryl phosphates and mixed alkyl aryl phosphates.
[00199] In one embodiment, at least one phosphorus compound useful in the invention can comprise, but is not limited to, triaryl phosphates, such as, for example, triphenyl phosphate. In one embodiment, at least one one thermal stabilizer comprises, but is not limited to Merpol A. In one embodiment, at least one thermal stabilizer useful in the invention comprises, but is not limited to, at least one of triphenyl phosphate and Merpol A. Merpol A is a phosphate ester commercially available from Stepan Chemical Co and/or E.I. duPont de Nemours
[00203] In one embodiment, any of the processes described herein for making any of the polyester compositions and/or polyesters can comprise at least one one phosphine oxide.
[00210] In one embodiment, suitable catalysts for use in the processes of the invention to make the polyesters useful in the invention include at least one titanium compound. The polyester compositions of the invention may also comprise at least one of the titanium compounds useful in the processes of the invention. Other catalysts could possibly be used in the invention in combination with the at least one titanium compound Other catalysts may include, but are not limited to, those based on tin, gallium, zinc, antimony, cobalt, manganese, magnesium, germanium, lithium, aluminum compounds, and an aluminum compound with lithium hydroxide or sodium hydroxide. In one embodiment, the catalyst can be a combination of at least one tin compound and at least one titanium compound.
[00211] Catalyst amounts can range from 10 ppm to 20,000 ppm or 10 to10,000 ppm, or 10 to 5000 ppm or 10 to 1000 ppm or 10 to 500 ppm, or 10 to 300 ppm or 10 to 250 ppm based on the catalyst metal and based on the weight of the final polymer. The process can be carried out in either a batch or continuous process. In one embodiment, the process is carried out in a continuous process.
[00213] When titanium is added to to the polyesters and/or polyester compositions and/or process of making the polyesters of the invention, It is added to the process of making the polyester in the form of a titanium compound. The amount of the titanium compound added to the polyesters of the invention and/or polyester compositions of the invention and/or processes of the invention can be measured in the form of titanium atoms present in the final polyester, for example, by weight measured in ppm.
[00216] The novel bimetallic alkoxide catalysts can be made as described by Meerwein, Ann. 476, 113 (1929). As shown by Meerwein, these catalysts are not merely mixtures of the two metallic alkoxides. They are definite compounds having a salt-like structure. These are the compounds depicted above by the Formulas A through H. Those not specifically described by Meerwein can be prepared by procedures analogous to the working examples and methods set forth by Meerwein.
[00231] In one embodiment, step (A) can be carried out until 50% by weight or more of the 2,2,4 ,4-tetramethyl-1 ,3-cyclobutanediol has been reacted. Step (A) may be carried out under pressure, ranging from 0 psig 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.
[00232] Typically, Step (B) and Step (C) 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.
[00237] It is believed that any of the processes of making the polyesters useful in the invention may be used to make any of the polyesters useful in the invention.
[00239] In one embodiment, the pressure used in Step (II) of any of the processes of the invention consists of at least one pressure chosen from 20 torr absolute to 0.02 torr absolute; in one embodiment, the pressure used in Step (II) of any of the processes of the invention consists of at least one pressure chosen from 10 torr absolute to 0.02 torr absolute; in one embodiment, the pressure used in Step (II) of any of the processes of the invention consists of at least one pressure chosen from 5 torr absolute to 0.02 torr absolute; in one embodiment, the pressure used in Step (II) of any of the processes of the invention consists of at least one pressure chosen from 3 torr absolute to 0.02 torr absolute; in one embodiment, the pressure used in Step (II) of any of the processes of the invention consists of at least one pressure chosen from 20 torr absolute to 0.1 torr absolute; in one embodiment, the pressure used in Step (II) of any of the processes of the invention consists of at least one pressure chosen from 10 torr absolute to 0.1 torr absolute; in one embodiment, the pressure used in Step (II) of any of the processes of the invention consists of at least one pressure chosen from 5 torr absolute to 0.1 torr absolute; in one embodiment, the pressure used in Step (II) of any of the processes of the invention consists of at least one pressure chosen from 3 torr absolute to 0.1 torr absolute.
[00241] In any of the process embodiments for making the polyesters useful in the invention, the heating time of Step (II) may be from 1 to 5 hours or 1 to 4 hours or 1 to 3 hours or 1.5 to 3 hours or 1 to 2 hours. In one embodiment, the heating time of Step (II) can be from 1.5 to 3 hours.
[00242] In one aspect, the polyesters, polyester compositions and/or processes of the invention useful in the invention can comprise phosphorus atoms.
[00243] In one aspect, the polyesters and/or polyester compositions and/or processes useful in the invention can comprise titanium atoms and tin atoms.
[00244] In one aspect, the polyesters, polyester compositions and/or processes of the invention useful in the inventioncan comprise phosphorus atoms and titanium atoms.
[00245] In one aspect, the polyesters, polyester compositions and/or processes of the invention useful in the invention can comprise phosphorus atoms, tin atoms, and titanium atoms.
[00247] In one embodiment, any of the polyester(s), polyester compositions and/or processes of the invention may comprise at least one titanium compound.
[00248] In one embodiment, any of the polyester(s), polyester compositions and/or processes of the invention may comprise at least one titanium compound and at least one phosphorus compound.
[00254] In one embodiment, the amount of titanium atoms in the polyesters useful in the invention can be from 0 to 400 ppm titanium atoms based on the weight of the final polyester.
[00255] In one embodiment, the amount of titanium atoms in the polyesters useful in the invention can be from 15 to 400 ppm titanium atoms based on the weight of the final polyester.
[00258] In one embodiment, the amount of phosphorus atoms in the polyesters useful in the invention can be from 1 to 500 ppm phosphorus atoms based on the weight of the final polyester and the amount of titanium atoms in the polyester can be from 1 to 100 ppm titanium atoms based on the weight of the final polyester.
[00260] In one embodiment, the amount of phosphorus atoms in the polyesters useful in the invention can be from 1 to 500 ppm phosphorus atoms based on the weight of the final polyester and the amount of titanium atoms in the polyester can be from 1 to 100 ppm titanium atoms based on the weight of the final polyester.
[00263] The invention further relates to a polymer blend. The blend comprises:
[00283] Ink resin(s) normally can be solvated or dispersed in one or more solvents. Typical solvents employed include, but are not limited to, water, alcohols (e.g., ethanol, 1-propanol, isopropanol, etc.), acetates (e.g., n-propyl acetate), aliphatic hydrocarbons, aromatic hydrocarbons (e.g., toluene), and ketones. Such solvents typically can be incorporated in amounts sufficient to provide inks having viscosities, as measured on a #2 Zahn cup as known in the art, of at least 15 seconds, such as at least 20 seconds, at least 25 seconds, or from 25 to 35 seconds.
[00316] In one embodiment, the sound barrier comprises a plurality of panels connected and arranged to achieve the desired barrier outline. The sound barriers can be used along streets and highways to dampen automotive noises. Alternatively, the sound barriers can be used in the home or office, either as a discrete panel or panels, or inserted within the architecture of the walls, floors, ceilings, doors, and/or windows.
[00333] The following examples further illustrate how the polyesters of the invention can be made and evaluated, and are intended to be purely exemplary of the invention and are not intended to limit the scope thereof. Unless indicated otherwise, parts are parts by weight, temperature is in degrees C or is at room temperature, and pressure is at or near atmospheric.
[00340] The amount of tin (Sn) and titanium (Ti) in the examples below is reported in parts per million (ppm) of metal and was measured by x-ray fluorescence (xrf) using a PANanalytical Axios Advanced wavelength dispersive x-ray fluorescence spectrometer. The amount of phosphorous is similarly reported as ppm of elemental phosphorus and was also measured by xrf using the same instrument. The values reported in the column "P measured" in the following examples were obtained by measuring phosphorous as described above.
[00347] A variety of polyesters were prepared as described above from 100 mole% dimethyl terephthalate. However, different amounts of triphenyl phosphate were added to the initial reaction mixture as indicated in Table 1. The mole% of TMCD and CHDM for the experiments of this example is also reported in Table 1 , with the glycol balance being EG. The glycol/acid ratio was 1.5/1 with the glycol feed having 20 mole% CHDM, 35 mole% TMCD and 45 mole% EG. 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. The Camile sequence shown below was used in the preparation of these copolyesters.
[00349] In stage 10, the stir rate was dropped to 25 rpm and even to 10 rpm if the viscosity was too high. The holding time in stage 10 for Examples G and H was 130 minutes.
[00351] A mixture of 99.71 g of dimethyl terephthalate, 21.63 g of 1,4-cyclohexanedimethanol, 37.86 g of 2,2,4 ,4-tetramethyl-1,3-cyclobutanediol, and 20.95 g of ethylene glycol was placed in a 500-milliliter flask equipped with an inlet for nitrogen, a metal stirrer, and a short distillation column. In addition, 0.0077 g of dibutyltin (IV) oxide and 0.0218 g of titanium (IV) isopropoxide were added to the 500-milliliter flask. The flask was placed in a Wood's metal bath already heated to 200 0 C. The stirring speed was set to 200 RPM at the beginning of 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 60 minutes and then heated up to 275°C in 90 minutes. Once at 275°C, vacuum was gradually applied over the next 10 minutes with a set point of 100 mm of Hg and the stirring speed was also reduced to 100 RPM. The pressure inside the flask was further reduced to a set point of 0.3 mm of Hg over the next 5 minutes and the stirring speed was reduced to 50 RPM. This pressure was maintained for a total time of 220 minutes to remove excess unreacted diols. This process resulted in a polymer with a glass transition temperature of 117.7°C and an inherent viscosity of 1.011 dl_/g. NMR analysis showed that the copolyester was composed of 29 mole % 1 ,4-cyclohexanedimethanol residues, 37 mole % 2,2,4,4-tetramethyl- 1 ,3-cyclobutanediol residues, and 34 mole % ethylene glycol residues. While outside the scope of the originally-filed claims, this example is included here to show the effect of the level of thermal stabilizer on color and inherent viscosity.
[00352] A variety of polyesters were prepared as described above from 100 mole% dimethyl terephthalate. However, different amounts of triphenyl phosphate were added to the initial reaction mixture as indicated in Table 2. The mole% of TMCD and CHDM for the experiments of this example is also reported in Table 2, with the glycol balance being EG. The glycol/acid ratio was 1.5/1 with the glycol feed having 20 mole% CHDM 1 35 mole% TMCD and 45 mole% EG. 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. The Camile sequence shown below was used in the preparation of these copolyesters.
[00354] In stage 10, the stir rate was dropped to 25 rpm and even to 10 rpm if the viscosity was too high. o
[00356] A mixture of 99.71 g of dimethyl terephthalate, 21.63 g of 1,4-cyclohexanedimethanol, 37.86 g of 2,2,4,4-tetramethyM ,3-cyclobutanediol, and 20.95 g of ethylene glycol was placed in a 500-milliliter flask equipped with an inlet for nitrogen, a metal stirrer, and a short distillation column. Various amounts of dibutyltin (IV) oxide, titanium (IV) isopropoxide, and triphenyl phosphate were added to the 500-milliliter flask. The flask was placed in a Wood's metal bath already heated to 200 0 C. The stirring speed was set to 200 RPM at the beginning of 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 60 minutes and then heated up to 275°C in 90 minutes. Once at 275°C, vacuum was gradually applied over the next 10 minutes with a set point of 100 mm of Hg and the stirring speed was also reduced to 100 RPM. The pressure inside the flask was further reduced to a set point of 0.3 mm of Hg over the next 5 minutes and the stirring speed was reduced to 50 RPM. This pressure was maintained for a total time of 220 minutes to remove excess unreacted diols. All samples were prepared by the same method using the catalyst and triphenyl phosphate levels reported in Table 3. The final TMCD and CHDM mole % for these copolyesters is reported also in Table 3, with the diol balance being EG. The effect of the catalyst system and thermal stabilizer on 2,2,4,4-tetramethyl-1 ,3-cyclobutanediol incorporation, copolyester color, and inherent viscosity are shown in Table 3. Examples G, H, and I in Table 3 below correspond to Example 2A, Example 2D, and Example IA respectively and are included in Table 3 to facilitate comparison among polyesters prepared using different catalyst systems and different levels of phosphorous.
[00362] In stage 10, the stir rate was dropped to 25 rpm and even to 10 rpm if the viscosity was too high.
[00367] In stage 10, the stir rate was dropped to 25 rpm and even to 10 rpm if the viscosity was too high. While outside the scope of the originally-filed claims, Example A is included here to show the effect of the level of thermal stabilizer on color and inherent viscosity.

中文:
[0003]同样,商业上需要一种聚合物材料,其具有对于某些应用例如热成型的膜和片应用来说所期望的组合性能,包括下面的三种或多种性能的组合:高缺口冲击强度,某些玻璃化转变温度(Tg),某些特性粘度,某些挠曲模量,良好的透明性,和良好的颜色。
[0023]在一方面,本发明涉及一种方法,其包含下面的步骤:
[0024]在一方面,本发明涉及一种制造聚酯的方法,其包含下面的步骤:
[0026]在一方面,本发明涉及一种制造聚酯的方法,其包含下面的步骤:
[0027]在一方面,本发明涉及一种制造聚酯的方法,其包含下面的步骤:
[0030]在一方面,在本发明中有用的聚酯可以包含至少一种磷酸酯,无论是否作为热稳定剂而存在。
[0031]在一方面,在本发明中有用的聚酯可以包含至少一种此处所述的磷酸酯,其作为热稳定剂而存在。
[0032]在一方面,在本发明中有用的聚酯不包含支化剂,或者可选择的,至少一种支化剂在聚酯的聚合之前或者聚合过程中被加入。
[0035]在一方面,在本发明中有用的聚酯,聚酯组合物和/或本发明的方法可以包含至少一种磷化合物。
[0036]在一方面,在本发明中有用的聚酯,聚酯组合物和/或本发明的方法可以包含磷原子。
[0037]在一方面,本发明的聚酯和/或聚酯组合物可以包含钛原子和锡原子。
[0039]在一方面,在本发明中有用的聚酯,聚酯组合物和/或本发明的方法可以包含磷原子和钛原子。
[0040]在一方面,本发明可以包含磷原子,锡原子,和钛原子。
[0041]在一方面,任何一个本发明的聚酯,聚酯组合物和/或方法可以包含至少一种磷化合物。
[0042]在一方面,任何一个本发明的聚酯,聚酯组合物和/或方法可以包含至少一种钛化合物。
[0043]在一方面,任何一个本发明的聚酯,聚酯组合物和/或方法可以包含至少一种钛化合物和至少一种磷化合物。
[0044]在一方面,任何一个本发明的聚酯,聚酯组合物和/或方法可以包含(i)至少一种钛化合物,和任选的至少一种选自下面的化合物:锡,镓,锌,锑,钴,锰,镁,锗,锂,铝化合物和带有氢氧化锂或者氢氧化钠的铝化合物;和(ii)至少一种磷化合物。术语“磷化合物”目的是包括其反应产物。
[0052]在一方面,至少一种在本发明中有用的磷化合物可以包含至少一种磷酸芳基酯。
[0055]在一方面,至少一种在本发明中有用的磷化合物可以包含至少一种磷酸三芳基酯。
[0056]在一方面,至少一种在本发明中有用的磷化合物可以包含至少一种未被苄基基团取代的磷酸三芳基酯。
[0057]在一方面,至少一种在本发明中有用的磷化合物可以包含至少一种磷酸烷基酯。
[0058]在一方面,至少一种在本发明中有用的磷化合物可以包含磷酸三苯基酯和/或Merpol A。在一种实施方案中,任何一种本发明的聚酯组合物可以包含磷酸三苯基酯。
[0059]在一方面,任何一种此处所述的制造任何一种聚酯组合物和/或聚酯的方法可以包含至少一种混合的亚磷酸烷基芳基酯,例如诸如双(2,4-二枯基苯基)季戊四醇二亚磷酸酯,也称为DoverphosS-9228(Dover Chemicals,CAS#154862-43-8)。
[0060]在一方面,任何一种此处所述的制造任何一种聚酯组合物和/或聚酯的方法可以包含至少一种的氧化膦。
[0061]在一方面,任何一种此处所述的制造任何一种聚酯组合物和/或聚酯的方法可以包含至少一种磷酸的盐,例如诸如,KH2PO4和Zn3(PO4)2。
[0062]在一方面,任何一种此处所述的制造任何一种聚酯组合物和/或聚酯的方法包含至少一种此处所述的磷化合物。
[0063]据信任何一种制造在本发明中有用的聚酯的方法可以用来制造任何一种在本发明中有用的聚酯。
[0064]在一方面,在本发明的任何一种方法的步骤(I)中所用的压力由至少一个选自0psig-75psig的压力组成。在一种实施方案中,在本发明的任何一种方法的步骤(I)中所用的压力由至少一个选自0psig-50psig的压力组成。
[0065]在一方面,在本发明的任何一种方法的步骤(II)中所用的压力由至少一个选自20绝对托-0.02绝对托的压力组成;在一种实施方案中,在本发明的任何一种方法的步骤(II)中所用的压力由至少一个选自10绝对托-0.02绝对托的压力组成;在一种实施方案中,在本发明的任何一种方法的步骤(II)中所用的压力由至少一个选自5绝对托-0.02绝对托的压力组成;在一种实施方案中,在本发明的任何一种方法的步骤(II)中所用的压力由至少一个选自3绝对托-0.02绝对托的压力组成;在一种实施方案中,在本发明的任何一种方法的步骤(II)中所用的压力由至少一个选自20绝对托-0.1绝对托的压力组成;在一种实施方案中,在本发明的任何一种方法的步骤(II)中所用的压力由至少一个选自10绝对托-0.1绝对托的压力组成;在一种实施方案中,在本发明的任何一种方法的步骤(II)中所用的压力由至少一个选自5绝对托-0.1绝对托的压力组成;在一种实施方案中,在本发明的任何一种方法的步骤(II)中所用的压力由至少一个选自3绝对托-0.1绝对托的压力组成。
[0066]在一方面,在本发明的任何一种方法的步骤(I)中所加入的二元醇成分/二羧酸成分的摩尔比是1.0-3.0/1.0;在一方面,在本发明的任何一种方法的步骤(I)中所加入的二元醇成分/二羧酸成分的摩尔比是1.0-2.5/1.0;在一方面,在本发明的任何一种方法的步骤(I)中所加入的二元醇成分/二羧酸成分的摩尔比是1.0-2.0/1.0;在一方面,在本发明的任何一种方法的步骤(I)中所加入的二元醇成分/二羧酸成分的摩尔比是1.0-1.75/1.0;在一方面,在本发明的任何一种方法的步骤(I)中所加入的二元醇成分/二羧酸成分的摩尔比是1.0-1.5/1.0。
[0067]在一方面,在本发明的任何一种方法的步骤(I)中所加入的二元醇成分/二羧酸成分的摩尔比是1.01-3.0/1.0;在一方面,在本发明的任何一种方法的步骤(I)中所加入的二元醇成分/二羧酸成分的摩尔比是1.01-2.5/1.0;在一方面,在本发明的任何一种方法的步骤(I)中所加入的二元醇成分/二羧酸成分的摩尔比是1.01-2.0/1.0;在一方面,在本发明的任何一种方法的步骤(I)中所加入的二元醇成分/二羧酸成分的摩尔比是1.01-1.75/1.0;在一方面,在本发明的任何一种方法的步骤(I)中所加入的二元醇成分/二羧酸成分的摩尔比是1.01-1.5/1.0。
[0068]在任何一种制造在本发明中有用的聚酯的方法实施方案中,步骤(II)的加热时间可以是1-5小时。在任何一种制造在本发明中有用的聚酯的方法实施方案中,步骤(II)的加热时间可以是1-4小时。在任何一种制造在本发明中有用的聚酯的方法实施方案中,步骤(II)的加热时间可以是1-3小时。在任何一种制造在本发明中有用的聚酯的方法实施方案中,步骤(II)的加热时间可以是1.5-3小时。在任何一种制造在本发明中有用的聚酯的方法实施方案中,步骤(II)的加热时间可以是1-2小时。
[0074]例如,在最终的聚酯中存在的锡原子和磷原子的重量可以用ppm为单位进行测量,并且可以在最终的聚酯中产生上述的任何一个重量比的总磷原子与总锡原子的重量比。
[0080]例如,在最终的聚酯中存在的钛原子和磷原子的重量可以用ppm为单位进行测量,并且可以在最终的聚酯中产生上述的任何一个重量比的总磷原子与总钛原子的重量比。
[0083]在一方面,在本发明中有用的聚酯中的钛原子的量可以是0-400ppm钛原子,基于最终的聚酯的重量。
[0084]在一方面,在本发明中有用的聚酯中的钛原子的量可以是15-400ppm钛原子,基于最终的聚酯的重量。
[0086]在一方面,在本发明中有用的聚酯中的磷原子的量可以是1-500ppm磷原子,基于最终的聚酯的重量,并且在该聚酯中的钛原子的量可以是1-100ppm钛原子,基于最终的聚酯的重量。
[0087]在一方面,在本发明中有用的聚酯中的磷原子的量可以是1-500ppm磷原子,基于最终的聚酯的重量,并且在该聚酯中的钛原子的量可以是1-400ppm钛原子,基于最终的聚酯的重量。
[0088]在一方面,在本发明中有用的聚酯中的磷原子的量可以是1-500ppm磷原子,基于最终的聚酯的重量,并且在该聚酯中的钛原子的量可以是1-100ppm钛原子,基于最终的聚酯的重量。
[0097]本发明可以通过参考下面的对本发明某些实施方案和工作实施例的更详细的说明而变得更容易理解。与本发明的目的一致,本发明的某些实施方案描述在发明概述中,并进一步在下面进行描述。此处同样描述了本发明的其它实施方案。
[00105]在一种实施方案中,制造在本发明中有用的聚酯的方法可以包含分批的或者连续的方法。
[00109]当钛加入到本发明的聚酯和/或聚酯组合物和/或制造该聚酯的方法中时,它是以钛化合物的形式被加入到聚酯的制造方法中。加入到本发明的聚酯和/或本发明的聚酯组合物和/或本发明的方法中的钛化合物的量可以通过测量在最终的聚酯中存在的钛原子来进行,例如通过重量ppm来测量。
[00112]本发明所用的聚酯典型的可以从二羧酸和二醇来制备,它们以基本相等的比例进行反应,并且作为它们相应的残基而被引入到聚酯聚合物中。所以,本发明的聚酯可以包含基本等摩尔比例的酸残基(100mol%)和二醇(和/或多官能羟基化合物)残基(100mol%),目的是重复单元的总摩尔数等于100mol%。因此在本发明中所提供的摩尔百分数可以基于酸残基的总摩尔数,二醇残基的总摩尔数,或者重复单元的总摩尔数。例如,含有基于总酸残基为10mol%间苯二酸的聚酯表示该聚酯包含来自总共100mol%酸残基的10mol%的间苯二酸残基。因此,这里在每100mol的酸残基中有10mol的间苯二酸残基。在另一个例子中,含有基于总二醇残基为30mol%的2,2,4,4-四甲基-1,3-环丁二醇的聚酯表示该聚酯包含来自总共100mol%二醇残基的30mol%的2,2,4,4-四甲基-1,3-环丁二醇残基。因此,这里在每100mol的二醇残基中有30mol的2,2,4,4-四甲基-1,3-环丁二醇残基。
[00169]在一种实施方案中,在本发明中有用的聚酯和/或本发明的聚酯组合物,[在一种实施方案中,存在和/或不存在调色剂],可以具有颜色值L*,a*和b*,其可以使用由Hunter Associates Lab Inc.,Reston,Va制造的Hunter Lab Ultrascan Spectra Colorimeter来测量。该颜色测量是在聚酯球上或者聚酯片上或者其它的用它们制成的注射模塑件或者挤出件上测量的平均值。它们是通过CIE(国际照明委员会)(翻译意思)的L*a*b*颜色体系来确定的,其中L*表示亮度坐标,a*表示红色/绿色坐标,和b*表示黄色/蓝色坐标。在某些实施方案中,在本发明中有用的聚酯的b*值[在一种实施方案中,存在和/或不存在调色剂]可以是-12到小于12,并且L*值可以是50-90。在其它的实施方案中,在本发明中有用的聚酯的b*值[在一种实施方案中,存在和/或不存在调色剂]可以是下面的一种范围:-10到10;-10到小于10;-10到9;-10到8;-10到7;-10到6;-10到5;-10到4;-10到3;-10到2;-5到9;-5到8;-5到7;-5到6;-5到5;-5到4;-5到3;-5到2;0-9;0-8;0-7;0-6;0-5;0-4;0-3;0-2;1-10;1-9;1-8;1-7;1-6;1-5;1-4;1-3;和1-2。在其它的实施方案中,在本发明中有用的聚酯的L*值可以是下面的一个范围:50-60;50-70;50-80;50-90;60-70;60-80;60-90;70-80;79-90。
[00177]在一些实施方案中,使用在本发明中有用的聚酯组合物使得熔融加工和/或热成型之前的干燥步骤最少和/或取消了该干燥步骤。
[00194]在一方面,至少一种在本发明中有用的磷化合物包含至少一种未被苄基基团取代的磷酸芳基酯。
[00195]在一方面,任何一种在本发明中有用的磷化合物可以包含至少一种磷酸烷基酯。
[00197]在一种实施方案中,在本发明中有用的作为热稳定剂和/或颜色稳定剂的磷酸酯包括但不限于下面的至少一种:磷酸三芳基酯,磷酸烷基二芳基酯,和混合的磷酸烷基芳基酯。
[00198]在一种实施方案中,在本发明中有用的作为热稳定剂和/或颜色稳定剂的磷酸酯可以包括但不限于下面的至少一种:磷酸三芳基酯和混合的磷酸烷基芳基酯。
[00199]在一种实施方案中,至少一种在本发明中有用的磷化合物可以包含但不限于磷酸三芳基酯,例如诸如磷酸三苯基酯。在一种实施方案中,至少一种热稳定剂包含但不限于Merpol A。在一种实施方案中,至少一种在本发明中有用的热稳定剂包含但不限于磷酸三苯基酯和Merpol A的至少一种。Merpol A是一种市售的磷酸酯,其获自Stepan Chemical Co和/或E.I.duPont de Nemours & Co。Merpol A的CAS登记号是CAS登记号#37208-27-8。
[00203]在一种实施方案中,任何一种此处所述的制造任何一种的聚酯组合物和/或聚酯的方法可以包含至少一种的氧化膦。
[00210]在一种实施方案中,用于本发明的方法中来制造在本发明中有用的聚酯的合适的催化剂包括至少一种钛化合物。本发明的聚酯组合物还可以包含至少一种的在本发明的方法中有用的钛化合物。其它的催化剂也可以与至少一种钛化合物相组合而用于本发明中,该其它的催化剂可以包括但不限于下面的这些:基于锡,镓,锌,锑,钴,锰,镁,锗,锂,铝化合物,和带有氢氧化锂或者氢氧化钠的铝化合物。在一种实施方案中,该催化剂可以与至少一种锡化合物和至少一种钛化合物相结合来使用。
[00211]催化剂量可以是10ppm-20000ppm或者10-10000ppm,或者10-5000ppm或者10-1000ppm或者10-500ppm,或者10-300ppm或者10-250ppm,基于催化剂金属和基于最终的聚合物的重量。所述的方法可以以分批的或者连续的方法来进行。在一种实施方案中,所述的方法以连续的方法来进行的。
[00213]当钛被加入到聚酯和/或聚酯组合物和/或制造本发明聚酯的方法中时,它是以钛化合物的形式被加入到制造该聚酯的方法中的。加入到本发明的聚酯和/或本发明的聚酯组合物和/或本发明的方法中的钛化合物的量可以通过测量在最终的聚酯中存在的钛原子来进行,例如通过测量重量ppm来进行。
[00216]该新颖的双金属醇盐催化剂可以如Meerwein,Ann.476,113(1929)所述来制备。如Meerwein所示,这些催化剂不仅仅是两种金属醇盐的混合物。它们是具有类似盐结构的确定的化合物。这些是上述的式A-H的化合物。这些Meerwein没有明确描述的化合物可以通过类似于Meerwein所提出的工作实施例和方法的程序来制备的。
[00231]在一种实施方案中,步骤(A)可以进行到50重量%或者更多的2,2,4,4-四甲基-1,3-环丁二醇已经被反应。步骤(A)可以在0psig-100psig的压力范围内进行。与在本发明中有用的任何催化剂相关使用的术语“反应产物”指的是带有该催化剂和制造聚酯所用的任何单体的缩聚或者酯化反应的任何产物以及在催化剂和任何的其他类型添加剂之间的缩聚或者酯化反应的产物。
[00232]典型的,步骤(B)和步骤(C)可以同时进行。这些步骤可以通过本领域已知的方法来进行例如通过将反应混合物置于0.002psig到低于大气压的压力下进行,或者将热氮气吹过该混合物而进行。
[00237]据信任何的制造在本发明中有用的聚酯的方法可以用于制造任何一种在本发明中有用的聚酯。
[00239]在一种实施方案中,任何一个本发明方法的步骤(II)所用的压力由至少一个选自20绝对托-0.02绝对托的压力组成;在一种实施方案中,任何一个本发明方法的步骤(II)所用的压力由至少一个选自10绝对托-0.02绝对托的压力组成;在一种实施方案中,任何一个本发明方法的步骤(II)所用的压力由至少一个选自5绝对托-0.02绝对托的压力组成;在一种实施方案中,任何一个本发明方法的步骤(II)所用的压力由至少一个选自3绝对托-0.02绝对托的压力组成;在一种实施方案中,任何一个本发明方法的步骤(II)所用的压力由至少一个选自20绝对托-0.1绝对托的压力组成;在一种实施方案中,任何一个本发明方法的步骤(II)所用的压力由至少一个选自10绝对托-0.1绝对托的压力组成;在一种实施方案中,任何一个本发明方法的步骤(II)所用的压力由至少一个选自5绝对托-0.1绝对托的压力组成;在一种实施方案中,任何一个本发明方法的步骤(II)所用的压力由至少一个选自3绝对托-0.1绝对托的压力组成。
[00241]在任何的制造在本发明中有用的聚酯的本发明的方法实施方案中,步骤(II)的加热时间可以是1-5小时或者1-4小时或者1-3小时或者1.5-3小时或者1-2小时。在一种实施方案中,步骤(II)的加热时间可以是1.5-3小时。
[00242]在一方面,在本发明中有用的聚酯,聚酯组合物和/或本发明的方法可以包含磷原子。
[00243]在一方面,在本发明中有用的聚酯,聚酯组合物和/或本发明的方法可以包含钛原子和锡原子。
[00244]在一方面,在本发明中有用的聚酯,聚酯组合物和/或本发明的方法可以包含磷原子和钛原子。
[00245]在一方面,在本发明中有用的聚酯,聚酯组合物和/或本发明的方法可以包含磷原子,锡原子和钛原子。
[00247]在一种实施方案中,任何的本发明的聚酯,聚酯组合物和/或方法可以包含至少一种钛化合物。
[00248]在一种实施方案中,任何的本发明的聚酯,聚酯组合物和/或方法可以包含至少一种钛化合物和至少一种磷化合物。
[00254]在一种实施方案中,在本发明中有用的聚酯中的钛原子的量可以是0-400ppm钛原子,基于最终的聚酯的重量。
[00255]在一种实施方案中,在本发明中有用的聚酯中的钛原子的量可以是15-400ppm钛原子,基于最终的聚酯的重量。
[00258]在一种实施方案中,在本发明中有用的聚酯中的磷原子的量可以是1-500ppm磷原子,基于最终的聚酯的重量,并且该聚酯中的钛原子的量可以是1-100ppm钛原子,基于最终的聚酯的重量。
[00260]在一种实施方案中,在本发明中有用的聚酯中的磷原子的量可以是1-500ppm磷原子,基于最终的聚酯的重量,并且该聚酯中的钛原子的量可以是1-100ppm钛原子,基于最终的聚酯的重量。
[00263]本发明进一步涉及一种聚合物共混物。该共混物包含:
[00283]油墨树脂通常可以溶解或者分散在一种或多种溶剂中。所用的典型的溶剂包括但不限于水,醇类(例如乙醇,1-丙醇,异丙醇等等),醋酸酯类(例如醋酸正丙酯),脂肪族烃,芳香族烃(例如甲苯)和酮类。这样的溶剂典型的可以以足够的量加入来提供具有下面的通过本领域已知的#2粘度杯所测定的粘度的油墨:至少15s,例如至少20s,至少25s,或者25-35s。
[00316]在一种实施方案中,声障包含多个连接和排布来达到期望的屏障轮廓的面板。声障可以用在街道和高速公路沿线来阻止汽车噪音。可选择的,声障可以用于家庭或者办公室中,作为不连续的一种或者多种面板,或者嵌入到建筑物的墙壁、地板、天花板、门和/或窗户中。
[00333]下面的实施例进一步说明如何制造和评价本发明的聚酯,并且其目的纯粹是例举本发明而非对其范围的限制。除非另有指示,否则份数是重量份,温度是摄氏度或者处于室温,压力处于或者接近于大气压。
[00340]在下面的实施例中的锡(Sn)和钛(Ti)的量是以金属的每百万份的份数(ppm)来报告的,并且是通过x射线荧光(xrf)使用PANanalytical Axios Advanced波长分散性x射线荧光分光计来测量的。磷量是类似的以元素磷的ppm来报告的,并且同样通过xrf使用相同的仪器来测量。在下面的实施例中在“所测量的P”列中所报道的值是通过测量如上所述的磷来获得的。
[00347]如上所述从100mol%对苯二甲酸二甲酯来制备多种聚酯。但是,如表1所示在初始的反应混合物中加入不同量的磷酸三苯酯。该实施例的试验所用的TMCD和CHDM的mol%也报告在表1中,并且二元醇平衡是EG。二元醇/酸的比例是1.5/1,并且二元醇供料具有20mol%的CHDM,35mol%的TMCD和45mol%的EG。设定点和数据收集是通过Camile加工控制系统来进行的。一旦反应物被熔融,则开始搅拌并缓慢增加。下面所示的Camile次序被用于这些共聚酯的制备中。
[00349]在阶段10中,如果粘度过高,则搅拌速度降低到25rpm和甚至降低到10rpm。实施例G和H的阶段10中的保持时间是130分钟。
[00351]将99.71g的对苯二甲酸二甲酯、21.63g的1,4-环己二甲醇、37.86g的2,2,4,4-四甲基-1,3-环丁二醇和20.95g的乙二醇的混合物置于500毫升的装备有氮气入口、金属搅拌器和短蒸馏柱的烧瓶中。另外,将0.0077g的氧化二丁基锡(IV)和0.0218g的异丙醇钛(IV)加入到该500毫升烧瓶中。将该烧瓶放入已经加热到200°C的Wood金属浴中。在试验开始时将搅拌速度设定为200RPM。将烧瓶中的内容物在200°C加热60分钟,然后在5分钟内逐渐升温到210°C。将该反应混合物在210°C保持60分钟,然后在90分钟内加热最高到275°C。一旦处于275°C,则在接下来的10分钟内逐渐施加真空,设定点是100mmHg,搅拌速度也降低到100RPM。在接下来的5分钟内将烧瓶中的压力进一步降低到0.3mmHg的设定点,并将搅拌速度降低到50RPM。在该压力保持总共220分钟的时间来除去多余的未反应的二醇。该方法产生了玻璃化转变温度是117.7°C和特性粘度是1.011dL/g的聚合物。NMR分析显示该共聚酯包含29mol%的1,4-环己二甲醇残基,37mol%的2,2,4,4-四甲基-1,3-环丁二醇残基和34mol%的乙二醇残基。虽然处于初始提出的权利要求的范围之外,但是这个实施例仍然包括于此来显示热稳定剂的量对于颜色和特性粘度的影响。
[00352]如上所述从100mol%对苯二甲酸二甲酯来制备多种聚酯。但是,如表2所示在初始的反应混合物中加入不同量的磷酸三苯酯。该实施例的试验所用的TMCD和CHDM的mol%也报告在表2中,并且二元醇平衡是EG。二元醇/酸的比例是1.5/1,并且二元醇供料具有20mol%的CHDM,35mol%的TMCD和45mol%的EG。设定点和数据收集是通过Camile加工控制系统来进行的。一旦反应物被熔融,则开始搅拌并缓慢增加。下面所示的Camile次序被用于这些共聚酯的制备中。
[00354]在阶段10中,如果粘度过高,则搅拌速度降低到25rpm和甚至降低到10rpm。
[00356]将99.71g的对苯二甲酸二甲酯、21.63g的1,4-环己二甲醇、37.86g的2,2,4,4-四甲基-1,3-环丁二醇和20.95g的乙二醇的混合物置于500毫升的装备有氮气入口、金属搅拌器和短蒸馏柱的烧瓶中。将不同量的氧化二丁基锡(IV)、异丙醇钛(IV)和磷酸三苯基酯加入到该500毫升烧瓶中。将该烧瓶放入已经加热到200°C的Wood金属浴中。在试验开始时将搅拌速度设定为200RPM。将烧瓶中的内容物在200°C加热60分钟,然后在5分钟内逐渐升温到210°C。将该反应混合物在210°C保持60分钟,然后在90分钟内加热最高到275°C。一旦处于275°C,则在接下来的10分钟内逐渐施加真空,设定点是100mmHg,搅拌速度也降低到100RPM。在接下来的5分钟内将烧瓶中的压力进一步降低到0.3mmHg的设定点,并将搅拌速度降低到50RPM。在该压力保持总共220分钟的时间来除去多余的未反应的二醇。全部的样品是通过相同的方法使用表3所示的催化剂和磷酸三苯基酯含量来制备的。这些共聚酯中最终的TMCD和CHDM的mol%也报告在表3中,并且二元醇平衡是EG。催化剂体系和热稳定剂对于2,2,4,4-四甲基-1,3-环丁二醇的引入、共聚酯颜色和特性粘度的影响表示在表3中。下面的表3中的实施例G,H和I分别对应于实施例2A,实施例2D和实施例IA,并且被包括在表3中来便于比较使用不同的催化剂体系和不同含量的磷所制备的聚酯。
[00362]在阶段10中,如果粘度过高,则搅拌速度降低到25rpm和甚至降低到10rpm。
[00367]在阶段10中,如果粘度过高,则搅拌速度降低到25rpm和甚至降低到10rpm。虽然处于初始要求的权利要求的范围之外,但是实施例A被在此包括来表示热稳定剂的量对于颜色和特性粘度的影响。