CA1057734A - Process and catalyst-inhibitor systems for preparing synthetic linear polyesters - Google Patents
Process and catalyst-inhibitor systems for preparing synthetic linear polyestersInfo
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- CA1057734A CA1057734A CA236,847A CA236847A CA1057734A CA 1057734 A CA1057734 A CA 1057734A CA 236847 A CA236847 A CA 236847A CA 1057734 A CA1057734 A CA 1057734A
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- manganese
- acetate
- benzoate
- lithium
- acetylacetonate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
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- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Abstract of the Disclosure Catalyst system for the polymerization of poly-(ethylene terephthalate) having excellent properties for fabrication of fibers and films. The catalyst system comprises a combination of organic or inorganic salts of manganese and cobalt with titanium alkoxides, organic salts of alkali metals or alkaline earth metals. Phos-phate esters can be used with the catalyst to serve as a color stabilizer for the poly (ethylene terephthalate).
Description
105'~734 This invention relates to an improved method for preparing a synthetic linear polyester and a new and improved catalyst system.
Poly(ethylene terephthalate) may be derived from a process comprising carrying out an ester interchange between ethylene glycol and dimethyl terephthalate to form bis-2-hydroxy ethyl terephthalate which is polycondensed to poly(ethylene terephthalate) under reduced pressure and at elevated temperatures.
Difficulties have been encountered in the manufacture of poly(ethylene terephthalate) by the ester interchange reaction.
Obviously, highly purified dimethyl terephthalate and highly purified glycol are preferred starting mater~als in order to form a uniform high quality product. However, even these highly purified materials are very sluggish with respect to ester inter-change and in the case of less purified materials the reaction is too slow for practical commercial operation. Because of this slow rate of reaction it has been found essential, in commercial operation, to employ a suitable catalyst to speed up the reaction.
Many catalysts have heretofore been proposed for the ester interchange reaction in the manufacture of poly(ethylene tereph-thalate). Such catalysts are described in U.S. 2,465,319, U.S.
Poly(ethylene terephthalate) may be derived from a process comprising carrying out an ester interchange between ethylene glycol and dimethyl terephthalate to form bis-2-hydroxy ethyl terephthalate which is polycondensed to poly(ethylene terephthalate) under reduced pressure and at elevated temperatures.
Difficulties have been encountered in the manufacture of poly(ethylene terephthalate) by the ester interchange reaction.
Obviously, highly purified dimethyl terephthalate and highly purified glycol are preferred starting mater~als in order to form a uniform high quality product. However, even these highly purified materials are very sluggish with respect to ester inter-change and in the case of less purified materials the reaction is too slow for practical commercial operation. Because of this slow rate of reaction it has been found essential, in commercial operation, to employ a suitable catalyst to speed up the reaction.
Many catalysts have heretofore been proposed for the ester interchange reaction in the manufacture of poly(ethylene tereph-thalate). Such catalysts are described in U.S. 2,465,319, U.S.
2,647,885 and U.S. 2,650,213. These catalysts have not proven to be entirely satisfactory since fibers and filaments produced from the condensation polymers using such heretofore known cat-alysts do not possess the desired whiteness or lack of color.
Therefore, there has been a great need in the art to find a catalyst system which not only speeds up the reaction into the realm of that con~idered necessary for economic purposes and ~hich is useful over approximately the entire range o ~ lecular weights deslred in the finished polynl~r, bu~ aLso, a cat~lyst which produces a condensation polymer of good color.
Anthraquinone dyes can be metallized to give dull off-shade dyeings. Certain catalyst systems used for the prepara-tion of polyesters can cause a bathochromic shift of the dye color during dyeing, or during subsequent yarn or fabric treat-ment. This leads to dull, undesirable colors, particularly when dyeing to pastel shades. Examples of shades that are adversely affected by this metallization process are Palanil Brilliant Pink REL (C. I. Disperse Red 91), Eastman Polyester Blue GLL
(C. I. Disperse Blue 27) and Eastman Polyester Red FFBL. Many other hydroxy or amino anthraquinone dyes will also undergo a color shift when used to dye polyester yarns or fabrics subject to this bathochromic shift. It is believed that any dye contain-ing active hydrogens will undergo this reaction to some degree.
The present invention comprises preparing poly(ethylene terephthalate) by reacting dimethyl terephthalate and ethylene glycol in the presence of a catalytic amount of a catalyst, characterized in that said catalyst comprises a mixture of organic or inorganic salts of manganese and cobalt with a titanium alkoxide and an organic salt of an alkali metal or an alkaline earth metal.
Examples of suitable manganese salts used in the invention are manganous benzoate tetrahydrate, manganese chloride, man-ganese oxide, manganese acetate, manganese acetylacetonate, manganese succinate, manganése diethyldithiocamate, manganese antimonate, manganic phosphate monohydrate, manganese glycol-oxide, manganese naphthenate and manganese salicyl salicylate.
.
105773~
Fxalllple~ of suitable cobalt s~lts us~d ill the inv~ntioll are cobaltous acetate tetrahydrate, cobaltous nitrate, cobaltous chloride, cobalt acetylacetonate, cobalt naphthenate and cobalt salicyl salicylate.
Examples of useful titanium alkoxides used in the invention are acetyl triisopropyl titanate, titanium tetraisopropoxide, titanium glycolates, titanium butoxide, and hexylene glycol titanate, tetraisooctyl titanate, and the like.
Examples of suitable organic salts of alkali metals or alkaline earth metals used in this invention are sodium acetate, sodium benzoate, sodium succinate, sodium acetylacetonate sodium methoxide, sodium ethoxide, sodium glycoxide, lithium acetate, lithium benzoate, lithium succinate, lithium acetylacetonate, lithium methoxide, lithium ethoxide, lithium glycoxide, potassium acetate, potassium benzoate, potassium succinate, potassium acetyl-acetonate, potassium methoxide, potassium ethoxide, potassium glycoY.ide, calcium acetate, calcium benzoate, calcium succinate, caLcium acetylacetonate, calcium methoxide, calcium ethoxide, calcium glycoxide, magnesium acetate, magnesium benzoate, magnesium succinate, magnesium acetylacetonate, magnesium methoxide, magnesium ethoxide, magnesium glycoxide, barium acetate, barium benzoate, barium succinate, and barium acetylacetonate.
In the preparation of poly(ethylene terephthalate) in accordance with the invention, the process can be considered as comprising two steps. In the first step, ethylene glycol and di-methyl terephthalate are reacted at elevated temperatures and atmospheric pressure to form bis-2-hydroxyethyl terephthalate (BHET) and methanol, which methanol is removed. Thereafter the BHET is heated under still higher temperatures and under reduced pressure 1~5773'~
to form poly(ethylene terephthalate) with the elimination of glycol, which is readily volatilized under these conditions and removed from the system. The second step, or polyconden-sation step, is continued until a fiber-forming polymer having the desired degree of polymerization, determined by inherent viscosity, is obtained. Without the aid of a suitable catalyst, the above reactions do not proceed at a noticeable rate.
Inherent viscosity for the poly(ethylene terephthalate) prepared in accordance with the invention is determined by measuring the flow time of a solution of known polymer con-tentration and the flow time of the polymer solvent in a capillary viscometer with a 0.55 mm. capillary and a 0.5 ml.
bulb having a flow time of 100 + 15 seconds and then by cal-culating the inherent viscosity using the equation:
Inherent Viscosity (I.V.) nO 50C% PTCE = ts C
where: ln = Natural logarithm t = Sample flow time s t = Solvent blank flow time C = Concentration in grams per 100 ml. of solvent PTCE = 60% phenol, 40% tetrachloroethane The basic method is set forth in ASTM D2857-70.
The method used for calculating catalyst metal concen-trations in poly(ethylene tetephthalate) for purposes of this specification may be illustrated as follows. The poly(ethylene terephthalate) is prepared in 0.60 gram mole batches. The polymer's repeat unit empirical formula is CloH8O4, and its gram molecular weight thus is 192.16 g. A 0.60 mole batch is, therefore, 115.30 g.
A 0.60 mole batch of polymer requires 0.60 mole of 105773~
terephthalic acid or its alkyl esters such as dimethyl tere-phthalate (DMT:mol. wt. = 194.19). Thus, 0.60 mole of this "acid fraction" as DMT is determined to be:
0.60 mole x 194.19 g./mole = 116.51 g.
Catalyst metals levels are reported in parts by weight of metal per million parts by weight of DMT. Thus, 48 ppm Ti is deter-mined as 1 x 194-19 g-/mole x 48 = 0.00559267 g. Ti 1,000,000 The weight of other catalyst metals or other additives is cal-culated similarly.
This invention involves conducting the ester inter-change reaction in the presence of a catalyst system comprising a catalytic amount of a mixture of a titanium alkoxide such as acetyl triisopropyl titanate and organic or inorganic salts of manganese and cobalt and organic salts of alkali metals or alkaline earth metals. The manganese salts are preferably present in the amount of 35-110 parts per million manganese;
the cobalt salts are preferably present in the amount of 5-35 parts per million cobalt; the titanium alkoxides are preferably present in the amount of 30-60 parts per million titanium and the alkali metal or alkaline earth metal salts are preferably present in the amount of 14-35 ppm of alkali or alkaline earth metal. All parts by weight are based on the acid fraction of the polymer weight to be produced. The preferred manganese salt is manganous benzoate tetrahydrate and the preferred cobalt salt is cobaltous acetate tetrahydrate. The preferred alkali metal salt is lithium acetate dihydrate.
A phosphate ester is preferably used in the reaction mixture during the process of the invention, the phosphate ester 1057'73~
typically being present during the polycondensation step.
Phosphate esters function as color stabilizers for the poly (ethylene terephthalate) prepared in accordance with the invention. The preferred phosphate ester that can be used in the invention has the formula pR QR
0~~ 2 4 tnoRo wherein n has an average value of 1.5 to 3.0 with about 1.8 being most preferred, and each R is hydrogen or an alkyl radical having from 6 to 10 carbon atoms with octyl being most preferred.
The ratio of the number of R groups of hydrogen atoms to the number of phosphorus atoms is generally 0.25 to 0.50, with about 0.35 being most preferred. The ester generally has a free acidity equivalent of about 0.2 to 0.5 and is generally present in the amount of 480-2225 parts per million (or typically 35 to 180 parts per million phosphorous) based on the acid fraction of the polyester to be produced. A particularly useful phosphate ester of this preferred type has a molecular weight of 771 and has the composition: C = 52.84~; H = 9.98~;
P = 8.04% and O = 29.14~ by weight and is referred to herein-after as "Phosphate Ester A". Other phosphate esters useful in this invention include ethyl acid phosphate, diethyl acid phosphate, triethyl acid phosphate, aryl alkyl phosphates, tris-2-ethylhexyl phosphate and the like.
The process and catalyst-inhibitor system of this invention provides for the manufacture at high production rates of high quality poly(ethylene terephthalate) polyester having excellent properties for the fabrication of fibers and films. Poly(ethylene terephthalate) produced in accordance with this invention has excellent color (whiteness), low concentration of diethylene glycol (ether linkages), -:1~)5'7734 excellent stability against thermooxidative, hydrolytic, and ultra-violet radiation degradation effects, and when melt spun into fibers or filaments re`sults in essentially no deposits on spinneret faces.
The data set forth in the following examples illustrate these effects. Examples 9, 10, 19 and 20 are examples of the inven-tion. The data in Table 1 illustrates that the catalysts of the invention are as useful as other catalysts as to the color of polyester prepared, and the data in Table 2 illustrates that the catalysts of the invention have the added advantage of preparing polyester having improved thermo-oxidative stability. The data in Table 3 illustrates that bathochromic shift can be controlled when the feature catalysts are used.
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a) 0 0 ~ ~ ~ X 3 n 0 r~~ S O O
~ .,~ h X ,~ o K~ H a * *,1 ~ ~ ~r ~ 8 --The poly(ethylene erephthalate) polymers shown in Examples 1-10 of Table 1 were prepared as follows:
EXA~IPLE 1 (65) Zn-(230) Sb-(31) P Catalyst - A ten mole ester inter-change reaction was run by weighing 1942 g. (10.0 moles) dimethyl terephthalate (DMT) and 1390 g. (22.4 moles) ethylene glycol (EG) into a 5000 ml reactor flask equipped with a mechanical stirrer, thennometer well, and a packed distillation column such that .0 methyl alcohol is permitted to distill from the reactor system, but the EG is refluxed with the system. A weighed amount of zinc acetate dihydrate (Zn(CH3CO2)2 . 2H2O, M.W. 219) and antimony triacetate (Sb(CH3C02)3, M.W. 299) were added to the reaction mix-ture so as to provide 65 ppm Zn and 230 ppm Sb based on the weight of the DMT fraction. Heat was applied (about 155C.) and the temp-erature of the reaction mixture was permitted to rise (to about 225 C.) as the reaction proceeded and methanol was distilled off.
Heat was removed when the theoretical amount of methanol (20.0 moles) had been recovered and the temperature of the reaction mix-20 ture had leveled off. Weighed amounts of the ester interchangereaction product were transferred to 500 ml reactor flasks in which the polycondensation reactions were then carried out. Subsequent to transferring the ester interchange reaction product to 500 ml reactor flasks and prior to heating up for the polycondensation reactions, the desired amount of the "Phosphate Ester A" describ-ed hereinbefore was added to the reaction mixture. (The phosphate ester may be weighed in directly or may be added volumetrically, having first been dissolved in a suitable solvent such as EG, n-butyl alcohol, methanol, etc.) Thus, the phosphate ester was 30 added as a solution in n-butyl alcohol in an amount to provide 31 ppm P bafied on the weight o~ t:he I~Ml ~raction of: t:he ester interchan~7e reactlorl prodtlct. (Other addil:ives of intcrest such ~.()S77;~
as stabilizers, delusterants, etc., may also be added at this time if desired).
The polycondensation reactor was then heated by immer-sing in a molten metal bath regulated at 275 + 2C., the reactor system having first been flushed with dry nitrogen, and the reactor system was maintained under a dry nitrogen blanket until placed under vacuum.
The polycondensation reactor was equipped with a mechan-ical stirrer having suitable seals and with a system for con-densing and collecting the excess EG removed during the poly-condensation reaction and with suitable connections to permit evacuation of the reactor system during the polycondensation reaction. Thus, the polycondensation reactions were run at 275 + 2C. and ~0.3. mm Hg absolute pressure for sufficient time (usually 1-2 hours) as to permit the inherent viscosity (I.V.) of the polyester to reach a level of 0.58 or higher.
(mhis time varies depending upon the activity of the catalyst.) Example 2 (48) Ti - (62) P (Ti as titanium tetraisopropoxide) -These polymers were prepared by the same procedures as described in Example 1 except that titanium catalyst was used, and the phos~phate ester was added at the start of the ester interchange reaction instead of at the end of same. Titanium was added as a solution of titanium tetraisopropoxide [Ti(OCH(CH3)2)4-M.W. 284] in n-butyl alcohol in an amount to provide 48 ppm Ti based on the weight of the DMT fraction of the ester inter-change reaction mixture. The phosphate ester was added as a solution in n-butyl alcohol in an amount to provide 62 ppm P
based on the weight of the DMT fraction of the ester inter-change reaction mixture.
-iO5773~
(12) Mg - (48) Ti - (62) P Catalyst - These polymers were prepared by the same procedures as described in Example 2 except that a magnesium-titanium-n-butoxide Meerwein complex was used. The magnesium-titanium-n-butoxide Meerwein complex, prepared as described in U.S. Patent 2,720,502, was added as a solution in n-butyl alcohol in an amount to provide 48 ppm Ti based on the weight of the DMT fraction of the ester interchange reaction mixture.
(48) Ti - (62) P (Ti as acetyl triisopropyl titanate) -Acetyl triisopropyl titanate, M.W. 284 was prepared by adding slowly with stirring and cooling and under a dry atmosphere glacial acetic acid (CH3COOH, M.W. 60) to titanium tetraiso-propoxide in an amount to provide a 1/l molar ratio of ace~ic acid/titanium tetraisopropoxide. (The isopropyl alcohol thus displaced by the acetic acid was not removed.) This catalyst may be added to the ester interchange reaction mixture un-diluted or as a solution in any of a number of suitable solvents such as n-butyl alcohol, methyl alcohol, ethylene glycol, etc.
Thus, these polymers were prepared by the same pro-cedures as described in Example 2 except that titanium was added as a solution of acetyl triisopropyl titanate (ATIP) in n-butyl alcohol in an amount to provide 48 ppm Ti based on the weight of the DMT fraction of the ester interchange reaction mixture. Above said phosphate ester was added as a solution in n-butyl alcohol in an amount t~ provide 62 ppm P based on the weight of the DMT fraction of the ester interchange reaction mixture.
Thus the results listed in Table l for the above four catalyst systems are averages of three polycondensation reactions run on the product of each of the four ester interchange reactions.
(232) Mn - (374) Sb - (44) P Catalyst - The poly (ethyleneterephthalate) polymer was prepared by a continuous melt phase process on production scale polyester manufacturing equipment. Thus, manganese benzoate tetrahydrate (Mn(O2CC6H5)2 4H2O, M.W. 369) and antimony triacetate, were metered continuously with EG as solutions, separately or combined in one solution, to said polyester production unit containing dimethyl terephthalate (DMT) at such a rate as to provide 236 ppm Mn and 374 ppm Sb based on the weight of pro-duct polyester. DMT and EG were present in substantially the same proportions as in Example l. "Phosphate Ester A" was like-wise metered continuously to said production unit at a point after the ester interchange reaction section of said unit as a solution in a suitable solvent and at a rate such as to provide 44 ppm P based on the weight of product polyester.
(50) Mn - (48) TI - (50) P (Ti as acetyl triiso-propyl titanate) - These polymers were prepared as described in Example l, except that a Mn-Ti-P catalyst system was used.
Manganese benzoate tetrahydrate was added as a solution in EG to the ester interchange reaction mixture in an amount to provide 50 ppm Mn based on the weight of the DMT fraction.
Acetyl triisopropyl titanate (ATIP) was added as a solution in n-butyl alcohol in an amount to provide 48 ppm Ti based on the DMT fraction of the ester interchange reaction mixture.
Abovesaid phosphate ester was added as a solution in EG to the product of the ester interchange reaction in an amount to provide 50 ppm P based on the weight of the DMT fraction of said reaction product and prior to the polycondensation of said product. The polycondensation r~actions were run as lOS7734 described in Example 1. Thus, these results are averages of three such polycondensation reactions.
EXAMPLES 7 and 8 (50) Mn - (60) Ti - (20) Co - (80) P (Ti ATIP) (70) Mn - (60) Ti - (20) Co - (80) P as These polymers were prepared by running the ester in-terchange reaction and the polycondensation reaction consecutively in the 500 ml reaction flasks described in Example 1. Thus 116.4 g. (0.6 mole) DMT and 93.0 g. (1.5 moles) EG were placed in said reaction flask. To this mixture was added titanium as ATIP, manganese benzoate tetrahydrate, cobalt acetate tetrahydrate [Co(OOCCH3)2-4H2O, N.W. 249], all in separate EG solutions, or alternatively in one com-bined EG solution in the amounts necessary to provide the indicated levels of catalyst metals based on the weight of the DMT fraction of the said ester interchange reaction mixture. Additionally, the aforesaid phosphate ester was added as a solution in EG in an amount t~o provide the indicated 80 ppm P based on the weight of the DMT fractionOf said ester exchange reaction mixture.
The reactor flask was subsequently immersed in a molten metal bath regulated at 195 + 2C. with a dry nitrogen atmosphere maintained in the reactor flask, and the ester interchange reaction was run for such time as required to re-cover the theoretical amount of methyl alcohol (1.2 moles).
The temperature of the metal bath was then raised to 275 ~
2C., the reactor system placed under vacuum, and the poly-condensation reaction run as described in Example 1.
EXAMPLES 9 and 10 (76) Mn - (48) Ti - (13) Co - (17) Li - (74) P
(63) Mn - (58) Ti - (13) Co - (28) Li - (98) P
The poly(ethylene terephthalate) polymers were pre-pared by a continuous melt phase process on production scale 10~i ~7~
polyester manufacturing equipment. Manganese benzoate tetrahydrate, in an ethylene glycol (EG) solution, acetyl triisopropyl titanate in an ethylene glycol solution, cobalt acetate tetrahydrate in an ethylene glycol solution, and lithium acetate dihydrate in an ethylene glycol solution were metered continuously as solutions, separately or combined in one solution, to the polyester production equipment containing dimethyl terephthalate (DMT) at such a rate as to provide 76 ppm Mn; 48 ppm Ti; 13 ppm Co; and 17 ppm Li based on the weight of product polyester. The EG and the DMT were present in substantially the same proportions as in Example 1. The phosphate ester, "Phosphate Ester A", was metered contin-uously to the production unit at a point after the ester inter-change reaction section of the unit as an ethylene glycol solution such as to provide 74 ppm P based on the weight o~
product polyester. The procedure was repeated for the system of (63) Mn - (58) Ti - (13) Co - (29) Li and (98) P changing only the amounts of catalyst stabilizer components as indicated.
The properties of the polymers produced are set forth in Table 1, Examples 9 and 10, respectively.
Table 2 Thermo-oxidative Stability of PET Made With Various Catalysts Example Catalyst System (ppm ) Thermo-oxidative Stability2 11 (lOO)Ca-(12)Co-(286)Sb-(190)P 1.000*
12 (99)Zn-(217)Sb-(281)P 2.89**
13 (53)Mn-(353)Sb-(170)P 1.876 14 (76)Mn-(132)Sb-(25)P 1.323 (ll9)Mn-(lO)Co-(292)Sb-(170)P 1.278 16 (113)Mn-(35)Co-(269)Sb-(130)P 1.043 17 (15)Mg-(60)Ti-(120)P 3.103 ~ - 14 -1057'73~
Table 2 (Continued) Example Catalyst System (ppml) Thermo-ox dative 18 (50)Mn-(60)Ti-(20)Co-(80)P 0.930 19 (72)Mn-(48)Ti-(16)CO-(20)Li-(118)P 0.530 20 (62)Mn-(36)Ti-(14)CO-(18)Li-(108)P 0.590 *Standard to which all other results are normalized.
- 14a -lOS~7~4 **Normalized percent crosslinker (thermo-oxidation product). Percent crosslinker correlates with percent weight loss (see 2).
ppm metal based on wt. of polymer.
Percent weight loss of pressed films 1 mil in thickness after 6 hours @ 300C. in air circulat-ing oven. All results are normalized by divid-ing percent weight loss by the percent weight loss by the standard.
0 3Ti as acetyl triisopropyl titanate.
The poly(ethylene terephthalate) polymers set forth in Examples 11-20 in Table 2 were prepared as follows:
(100) Ca - (12) CO - (286) Sb - (190) P - This polymer was a commercially available product manufactured by Teijin, Ltd. having an inherent viscosity of 0.62 and which was made using this four-component catalyst system as determined by analysis of the polymer. The polymer is used as an arbitrary standard in thermo-oxidative stability studies.
(99) Zn - (217) Sb - (281) P (Zn as zinc acetate di-hydrate, Sb as antimony triacetate and P as the phosphate ester used in Example 1) - This polymer was produced as - described in Example 5, except that the phosphate ester was added by blending50.0 g. of the polymer pellets with the required amount of phosphate ester in 25 ml. of dry benzene to provide 281 ppm of P based on the weight of polyester. The benzene was then evaporated off under vacuum, and the coated pellets dried and then extruded on a Brabender Plasticorder melt extruder to obtain homogeneous mixing of the said phosphate ester, lOS7734 FX~P~F ~ 3 (53) Mn - (353) Sb - (170) P (Mn as manganese benzoate, Sb as ~imony triacetate and P as the phosphate ester used in Example 1) - This polymer was prepared using procedures describ-ed in Example 1.
(76) Mn - (132) Sb - (25) P - This polymer was produc-ed as described in Example 5.
EXA~IPLES 15 and 16 ~0 -(119) Mn - (10) Co - (292) Sb - (170) P
(113) Mn - (35) Co - (269JSb - (130) P
(Mn as manganese benzoate, Co as cobalt acetate, Sb as antimony triacetate and P as the phosphate ester used in Example 1) These polymers were prepared as described in Example 7 except that the phosphate ester was coated on the polymer as follows: the polymer was ground through a 2 mm screen and then 20 g. were blended with a sufficient amount of said phosphate ester in 50 ml of dichloromethane (CH2C12, M.W. 85) '0 to give the indicated levels of P (ppm based on the weight of polyester). The dichloromethane was then evaporated off under vacuum.
(15) Mg - (60) Ti - (120) P (Mg and Ti as magnesium-titanium butoxide Meerwein complex as described in U.S. 2,720,502 and P as the phosphate ester used in Example 1). This polymer was produced by a continuous melt phase process described in Example 5, EX~PLE 18 (50) Mn - (60) Ti - (20) Co - (80) P - This polymer ~a~ prepared as described in Example 7.
-]6-EXA~IPLE 19 and 20 72) Mn - (48) Ti - (16) Co - (20) Li - (118) P
(62) Mn - (36) Ti - (14) Co - (18) Li - (108) P
These polymers were prepared by the procedure describ-ed in Examples 9 and 10.
Table 3 Effect of Catalyst-Inhibitor Systems on Color Shift of Dyed Yarn Heat Set 1 2 Color Shift, Catalyst System (ppm ) I.V. A K/S _ 0 (80)Mn-(56)Ti-(22)Co-(99)P 0.61 b (803Mn-(48)Ti-(15)Co-(84)P 0.56 b (90)Mn-(56)Ti-(18)Co-(23)Li (134)P 0.53 a (56)Mn-(65)Ti-(18)Co-(13)Li-(73)p 0.57 0.0130,c (40)Mn-(22)Ti-(15)Co-(67)P 0 54 0.0254,b (51)Mn-(57)Ti-(l9)Co-(lOO)Na-(64)P 0.63 0.0014,c (236)Mn-(374)Sb-(44)P 0.65 a !0 ppm metal based on polyester polymer.
Inherent viscosity of 0.5g/100 ml of 60/40 (w/w) phenol/tetrachloroethane at 25C.
Color shift after heat set treatment equal to or better than the control by visual comparison.
Color shift compared to the control is too great for acceptance by visual comparison.
Acceptable(catalyst system of the invention) (The "control" is a commercial poly(ethylene terephthalate) that does not have a color shift problem.) The data set forth in Table 3 particularly illustrates the effects o~ lithium and sodiurn when used with Mn-Co-Ti-P
system3 a~ to bathochromic color shift of dyed yarn. Thei polymers were made in the rnanner shown in Examples 7 and 8 ~o~ the ~n-Co~ P Systern and in Examples 9 and 10 for the Mn-Ti-Co-Li-P system. The polymer made using the Mn-Ti-Co-Na-P
system was run in the manner described in Examples 7 and 8, the sodium being added as sodium acetate (anhydrous) in an ethylene glycol solution. The K/S value used is determined by use of color measurement with a spectrophotometer. The spectrophotometer can be used to measure the percent diffuse reflectance of a sàmple for a given wavelength frDm 800 to 380 nm. The K/S term is the ratio of the absorptivity .0 coefficient (K) to the scattering coefficient (S) and is related to the diffuse reflectance (R) as follows:
K/S = (I-R) Further K/S = k log10 Conc., but if the dyeing level for all samples is maintained constant (in the table above the dye-ing level was 0.3% by weight) then an observed color shift in a dyed sample manifests itself as a change in the constant k. The term ~ K/S was chosen to represent the change in K/S
which occurred upon heat-setting of certain dyed polyester samples as set forth above. Diffuse reflectance was measured 0 at 620 nm for each sample before and after heatsetting. The respective K/S values were calculated, and the difference, K/S heatset minus K/S nonheatset, is reported as a K/s. The equipment used is a Spectrosystem 100 Spectrophotometer sold by Cary Instruments of Monrovia, California.
Therefore, there has been a great need in the art to find a catalyst system which not only speeds up the reaction into the realm of that con~idered necessary for economic purposes and ~hich is useful over approximately the entire range o ~ lecular weights deslred in the finished polynl~r, bu~ aLso, a cat~lyst which produces a condensation polymer of good color.
Anthraquinone dyes can be metallized to give dull off-shade dyeings. Certain catalyst systems used for the prepara-tion of polyesters can cause a bathochromic shift of the dye color during dyeing, or during subsequent yarn or fabric treat-ment. This leads to dull, undesirable colors, particularly when dyeing to pastel shades. Examples of shades that are adversely affected by this metallization process are Palanil Brilliant Pink REL (C. I. Disperse Red 91), Eastman Polyester Blue GLL
(C. I. Disperse Blue 27) and Eastman Polyester Red FFBL. Many other hydroxy or amino anthraquinone dyes will also undergo a color shift when used to dye polyester yarns or fabrics subject to this bathochromic shift. It is believed that any dye contain-ing active hydrogens will undergo this reaction to some degree.
The present invention comprises preparing poly(ethylene terephthalate) by reacting dimethyl terephthalate and ethylene glycol in the presence of a catalytic amount of a catalyst, characterized in that said catalyst comprises a mixture of organic or inorganic salts of manganese and cobalt with a titanium alkoxide and an organic salt of an alkali metal or an alkaline earth metal.
Examples of suitable manganese salts used in the invention are manganous benzoate tetrahydrate, manganese chloride, man-ganese oxide, manganese acetate, manganese acetylacetonate, manganese succinate, manganése diethyldithiocamate, manganese antimonate, manganic phosphate monohydrate, manganese glycol-oxide, manganese naphthenate and manganese salicyl salicylate.
.
105773~
Fxalllple~ of suitable cobalt s~lts us~d ill the inv~ntioll are cobaltous acetate tetrahydrate, cobaltous nitrate, cobaltous chloride, cobalt acetylacetonate, cobalt naphthenate and cobalt salicyl salicylate.
Examples of useful titanium alkoxides used in the invention are acetyl triisopropyl titanate, titanium tetraisopropoxide, titanium glycolates, titanium butoxide, and hexylene glycol titanate, tetraisooctyl titanate, and the like.
Examples of suitable organic salts of alkali metals or alkaline earth metals used in this invention are sodium acetate, sodium benzoate, sodium succinate, sodium acetylacetonate sodium methoxide, sodium ethoxide, sodium glycoxide, lithium acetate, lithium benzoate, lithium succinate, lithium acetylacetonate, lithium methoxide, lithium ethoxide, lithium glycoxide, potassium acetate, potassium benzoate, potassium succinate, potassium acetyl-acetonate, potassium methoxide, potassium ethoxide, potassium glycoY.ide, calcium acetate, calcium benzoate, calcium succinate, caLcium acetylacetonate, calcium methoxide, calcium ethoxide, calcium glycoxide, magnesium acetate, magnesium benzoate, magnesium succinate, magnesium acetylacetonate, magnesium methoxide, magnesium ethoxide, magnesium glycoxide, barium acetate, barium benzoate, barium succinate, and barium acetylacetonate.
In the preparation of poly(ethylene terephthalate) in accordance with the invention, the process can be considered as comprising two steps. In the first step, ethylene glycol and di-methyl terephthalate are reacted at elevated temperatures and atmospheric pressure to form bis-2-hydroxyethyl terephthalate (BHET) and methanol, which methanol is removed. Thereafter the BHET is heated under still higher temperatures and under reduced pressure 1~5773'~
to form poly(ethylene terephthalate) with the elimination of glycol, which is readily volatilized under these conditions and removed from the system. The second step, or polyconden-sation step, is continued until a fiber-forming polymer having the desired degree of polymerization, determined by inherent viscosity, is obtained. Without the aid of a suitable catalyst, the above reactions do not proceed at a noticeable rate.
Inherent viscosity for the poly(ethylene terephthalate) prepared in accordance with the invention is determined by measuring the flow time of a solution of known polymer con-tentration and the flow time of the polymer solvent in a capillary viscometer with a 0.55 mm. capillary and a 0.5 ml.
bulb having a flow time of 100 + 15 seconds and then by cal-culating the inherent viscosity using the equation:
Inherent Viscosity (I.V.) nO 50C% PTCE = ts C
where: ln = Natural logarithm t = Sample flow time s t = Solvent blank flow time C = Concentration in grams per 100 ml. of solvent PTCE = 60% phenol, 40% tetrachloroethane The basic method is set forth in ASTM D2857-70.
The method used for calculating catalyst metal concen-trations in poly(ethylene tetephthalate) for purposes of this specification may be illustrated as follows. The poly(ethylene terephthalate) is prepared in 0.60 gram mole batches. The polymer's repeat unit empirical formula is CloH8O4, and its gram molecular weight thus is 192.16 g. A 0.60 mole batch is, therefore, 115.30 g.
A 0.60 mole batch of polymer requires 0.60 mole of 105773~
terephthalic acid or its alkyl esters such as dimethyl tere-phthalate (DMT:mol. wt. = 194.19). Thus, 0.60 mole of this "acid fraction" as DMT is determined to be:
0.60 mole x 194.19 g./mole = 116.51 g.
Catalyst metals levels are reported in parts by weight of metal per million parts by weight of DMT. Thus, 48 ppm Ti is deter-mined as 1 x 194-19 g-/mole x 48 = 0.00559267 g. Ti 1,000,000 The weight of other catalyst metals or other additives is cal-culated similarly.
This invention involves conducting the ester inter-change reaction in the presence of a catalyst system comprising a catalytic amount of a mixture of a titanium alkoxide such as acetyl triisopropyl titanate and organic or inorganic salts of manganese and cobalt and organic salts of alkali metals or alkaline earth metals. The manganese salts are preferably present in the amount of 35-110 parts per million manganese;
the cobalt salts are preferably present in the amount of 5-35 parts per million cobalt; the titanium alkoxides are preferably present in the amount of 30-60 parts per million titanium and the alkali metal or alkaline earth metal salts are preferably present in the amount of 14-35 ppm of alkali or alkaline earth metal. All parts by weight are based on the acid fraction of the polymer weight to be produced. The preferred manganese salt is manganous benzoate tetrahydrate and the preferred cobalt salt is cobaltous acetate tetrahydrate. The preferred alkali metal salt is lithium acetate dihydrate.
A phosphate ester is preferably used in the reaction mixture during the process of the invention, the phosphate ester 1057'73~
typically being present during the polycondensation step.
Phosphate esters function as color stabilizers for the poly (ethylene terephthalate) prepared in accordance with the invention. The preferred phosphate ester that can be used in the invention has the formula pR QR
0~~ 2 4 tnoRo wherein n has an average value of 1.5 to 3.0 with about 1.8 being most preferred, and each R is hydrogen or an alkyl radical having from 6 to 10 carbon atoms with octyl being most preferred.
The ratio of the number of R groups of hydrogen atoms to the number of phosphorus atoms is generally 0.25 to 0.50, with about 0.35 being most preferred. The ester generally has a free acidity equivalent of about 0.2 to 0.5 and is generally present in the amount of 480-2225 parts per million (or typically 35 to 180 parts per million phosphorous) based on the acid fraction of the polyester to be produced. A particularly useful phosphate ester of this preferred type has a molecular weight of 771 and has the composition: C = 52.84~; H = 9.98~;
P = 8.04% and O = 29.14~ by weight and is referred to herein-after as "Phosphate Ester A". Other phosphate esters useful in this invention include ethyl acid phosphate, diethyl acid phosphate, triethyl acid phosphate, aryl alkyl phosphates, tris-2-ethylhexyl phosphate and the like.
The process and catalyst-inhibitor system of this invention provides for the manufacture at high production rates of high quality poly(ethylene terephthalate) polyester having excellent properties for the fabrication of fibers and films. Poly(ethylene terephthalate) produced in accordance with this invention has excellent color (whiteness), low concentration of diethylene glycol (ether linkages), -:1~)5'7734 excellent stability against thermooxidative, hydrolytic, and ultra-violet radiation degradation effects, and when melt spun into fibers or filaments re`sults in essentially no deposits on spinneret faces.
The data set forth in the following examples illustrate these effects. Examples 9, 10, 19 and 20 are examples of the inven-tion. The data in Table 1 illustrates that the catalysts of the invention are as useful as other catalysts as to the color of polyester prepared, and the data in Table 2 illustrates that the catalysts of the invention have the added advantage of preparing polyester having improved thermo-oxidative stability. The data in Table 3 illustrates that bathochromic shift can be controlled when the feature catalysts are used.
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ul a ~ a) ,1 ~r ~Int~ o ~ ~ co o ~ co 0 o ~ ~ ~ ~ ~ ~ ~ ~ ~ ~l s s C~ o U~ ~
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rn -- ~E~ ~ er 00 0 o o~ oo t,q O ~ O
~1U~ ~ ~DC~ -- ~ -- -- -- -- -- 0 Q~
O ~ O ~ 0 3 ~ _ , _ .,, , ~ ~ 0 0 a ~,~~1 w ~ _ o o o ~ ~ h -1 O O
1 _ 00 _ ~ ~ a 0 u ~J ~
0 ~ ~ * ~ * * * * * -1 ~1 0 U ~1 0 O _ * _ * -- * * * * * ~ 0 0 t~
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a) 0 0 ~ ~ ~ X 3 n 0 r~~ S O O
~ .,~ h X ,~ o K~ H a * *,1 ~ ~ ~r ~ 8 --The poly(ethylene erephthalate) polymers shown in Examples 1-10 of Table 1 were prepared as follows:
EXA~IPLE 1 (65) Zn-(230) Sb-(31) P Catalyst - A ten mole ester inter-change reaction was run by weighing 1942 g. (10.0 moles) dimethyl terephthalate (DMT) and 1390 g. (22.4 moles) ethylene glycol (EG) into a 5000 ml reactor flask equipped with a mechanical stirrer, thennometer well, and a packed distillation column such that .0 methyl alcohol is permitted to distill from the reactor system, but the EG is refluxed with the system. A weighed amount of zinc acetate dihydrate (Zn(CH3CO2)2 . 2H2O, M.W. 219) and antimony triacetate (Sb(CH3C02)3, M.W. 299) were added to the reaction mix-ture so as to provide 65 ppm Zn and 230 ppm Sb based on the weight of the DMT fraction. Heat was applied (about 155C.) and the temp-erature of the reaction mixture was permitted to rise (to about 225 C.) as the reaction proceeded and methanol was distilled off.
Heat was removed when the theoretical amount of methanol (20.0 moles) had been recovered and the temperature of the reaction mix-20 ture had leveled off. Weighed amounts of the ester interchangereaction product were transferred to 500 ml reactor flasks in which the polycondensation reactions were then carried out. Subsequent to transferring the ester interchange reaction product to 500 ml reactor flasks and prior to heating up for the polycondensation reactions, the desired amount of the "Phosphate Ester A" describ-ed hereinbefore was added to the reaction mixture. (The phosphate ester may be weighed in directly or may be added volumetrically, having first been dissolved in a suitable solvent such as EG, n-butyl alcohol, methanol, etc.) Thus, the phosphate ester was 30 added as a solution in n-butyl alcohol in an amount to provide 31 ppm P bafied on the weight o~ t:he I~Ml ~raction of: t:he ester interchan~7e reactlorl prodtlct. (Other addil:ives of intcrest such ~.()S77;~
as stabilizers, delusterants, etc., may also be added at this time if desired).
The polycondensation reactor was then heated by immer-sing in a molten metal bath regulated at 275 + 2C., the reactor system having first been flushed with dry nitrogen, and the reactor system was maintained under a dry nitrogen blanket until placed under vacuum.
The polycondensation reactor was equipped with a mechan-ical stirrer having suitable seals and with a system for con-densing and collecting the excess EG removed during the poly-condensation reaction and with suitable connections to permit evacuation of the reactor system during the polycondensation reaction. Thus, the polycondensation reactions were run at 275 + 2C. and ~0.3. mm Hg absolute pressure for sufficient time (usually 1-2 hours) as to permit the inherent viscosity (I.V.) of the polyester to reach a level of 0.58 or higher.
(mhis time varies depending upon the activity of the catalyst.) Example 2 (48) Ti - (62) P (Ti as titanium tetraisopropoxide) -These polymers were prepared by the same procedures as described in Example 1 except that titanium catalyst was used, and the phos~phate ester was added at the start of the ester interchange reaction instead of at the end of same. Titanium was added as a solution of titanium tetraisopropoxide [Ti(OCH(CH3)2)4-M.W. 284] in n-butyl alcohol in an amount to provide 48 ppm Ti based on the weight of the DMT fraction of the ester inter-change reaction mixture. The phosphate ester was added as a solution in n-butyl alcohol in an amount to provide 62 ppm P
based on the weight of the DMT fraction of the ester inter-change reaction mixture.
-iO5773~
(12) Mg - (48) Ti - (62) P Catalyst - These polymers were prepared by the same procedures as described in Example 2 except that a magnesium-titanium-n-butoxide Meerwein complex was used. The magnesium-titanium-n-butoxide Meerwein complex, prepared as described in U.S. Patent 2,720,502, was added as a solution in n-butyl alcohol in an amount to provide 48 ppm Ti based on the weight of the DMT fraction of the ester interchange reaction mixture.
(48) Ti - (62) P (Ti as acetyl triisopropyl titanate) -Acetyl triisopropyl titanate, M.W. 284 was prepared by adding slowly with stirring and cooling and under a dry atmosphere glacial acetic acid (CH3COOH, M.W. 60) to titanium tetraiso-propoxide in an amount to provide a 1/l molar ratio of ace~ic acid/titanium tetraisopropoxide. (The isopropyl alcohol thus displaced by the acetic acid was not removed.) This catalyst may be added to the ester interchange reaction mixture un-diluted or as a solution in any of a number of suitable solvents such as n-butyl alcohol, methyl alcohol, ethylene glycol, etc.
Thus, these polymers were prepared by the same pro-cedures as described in Example 2 except that titanium was added as a solution of acetyl triisopropyl titanate (ATIP) in n-butyl alcohol in an amount to provide 48 ppm Ti based on the weight of the DMT fraction of the ester interchange reaction mixture. Above said phosphate ester was added as a solution in n-butyl alcohol in an amount t~ provide 62 ppm P based on the weight of the DMT fraction of the ester interchange reaction mixture.
Thus the results listed in Table l for the above four catalyst systems are averages of three polycondensation reactions run on the product of each of the four ester interchange reactions.
(232) Mn - (374) Sb - (44) P Catalyst - The poly (ethyleneterephthalate) polymer was prepared by a continuous melt phase process on production scale polyester manufacturing equipment. Thus, manganese benzoate tetrahydrate (Mn(O2CC6H5)2 4H2O, M.W. 369) and antimony triacetate, were metered continuously with EG as solutions, separately or combined in one solution, to said polyester production unit containing dimethyl terephthalate (DMT) at such a rate as to provide 236 ppm Mn and 374 ppm Sb based on the weight of pro-duct polyester. DMT and EG were present in substantially the same proportions as in Example l. "Phosphate Ester A" was like-wise metered continuously to said production unit at a point after the ester interchange reaction section of said unit as a solution in a suitable solvent and at a rate such as to provide 44 ppm P based on the weight of product polyester.
(50) Mn - (48) TI - (50) P (Ti as acetyl triiso-propyl titanate) - These polymers were prepared as described in Example l, except that a Mn-Ti-P catalyst system was used.
Manganese benzoate tetrahydrate was added as a solution in EG to the ester interchange reaction mixture in an amount to provide 50 ppm Mn based on the weight of the DMT fraction.
Acetyl triisopropyl titanate (ATIP) was added as a solution in n-butyl alcohol in an amount to provide 48 ppm Ti based on the DMT fraction of the ester interchange reaction mixture.
Abovesaid phosphate ester was added as a solution in EG to the product of the ester interchange reaction in an amount to provide 50 ppm P based on the weight of the DMT fraction of said reaction product and prior to the polycondensation of said product. The polycondensation r~actions were run as lOS7734 described in Example 1. Thus, these results are averages of three such polycondensation reactions.
EXAMPLES 7 and 8 (50) Mn - (60) Ti - (20) Co - (80) P (Ti ATIP) (70) Mn - (60) Ti - (20) Co - (80) P as These polymers were prepared by running the ester in-terchange reaction and the polycondensation reaction consecutively in the 500 ml reaction flasks described in Example 1. Thus 116.4 g. (0.6 mole) DMT and 93.0 g. (1.5 moles) EG were placed in said reaction flask. To this mixture was added titanium as ATIP, manganese benzoate tetrahydrate, cobalt acetate tetrahydrate [Co(OOCCH3)2-4H2O, N.W. 249], all in separate EG solutions, or alternatively in one com-bined EG solution in the amounts necessary to provide the indicated levels of catalyst metals based on the weight of the DMT fraction of the said ester interchange reaction mixture. Additionally, the aforesaid phosphate ester was added as a solution in EG in an amount t~o provide the indicated 80 ppm P based on the weight of the DMT fractionOf said ester exchange reaction mixture.
The reactor flask was subsequently immersed in a molten metal bath regulated at 195 + 2C. with a dry nitrogen atmosphere maintained in the reactor flask, and the ester interchange reaction was run for such time as required to re-cover the theoretical amount of methyl alcohol (1.2 moles).
The temperature of the metal bath was then raised to 275 ~
2C., the reactor system placed under vacuum, and the poly-condensation reaction run as described in Example 1.
EXAMPLES 9 and 10 (76) Mn - (48) Ti - (13) Co - (17) Li - (74) P
(63) Mn - (58) Ti - (13) Co - (28) Li - (98) P
The poly(ethylene terephthalate) polymers were pre-pared by a continuous melt phase process on production scale 10~i ~7~
polyester manufacturing equipment. Manganese benzoate tetrahydrate, in an ethylene glycol (EG) solution, acetyl triisopropyl titanate in an ethylene glycol solution, cobalt acetate tetrahydrate in an ethylene glycol solution, and lithium acetate dihydrate in an ethylene glycol solution were metered continuously as solutions, separately or combined in one solution, to the polyester production equipment containing dimethyl terephthalate (DMT) at such a rate as to provide 76 ppm Mn; 48 ppm Ti; 13 ppm Co; and 17 ppm Li based on the weight of product polyester. The EG and the DMT were present in substantially the same proportions as in Example 1. The phosphate ester, "Phosphate Ester A", was metered contin-uously to the production unit at a point after the ester inter-change reaction section of the unit as an ethylene glycol solution such as to provide 74 ppm P based on the weight o~
product polyester. The procedure was repeated for the system of (63) Mn - (58) Ti - (13) Co - (29) Li and (98) P changing only the amounts of catalyst stabilizer components as indicated.
The properties of the polymers produced are set forth in Table 1, Examples 9 and 10, respectively.
Table 2 Thermo-oxidative Stability of PET Made With Various Catalysts Example Catalyst System (ppm ) Thermo-oxidative Stability2 11 (lOO)Ca-(12)Co-(286)Sb-(190)P 1.000*
12 (99)Zn-(217)Sb-(281)P 2.89**
13 (53)Mn-(353)Sb-(170)P 1.876 14 (76)Mn-(132)Sb-(25)P 1.323 (ll9)Mn-(lO)Co-(292)Sb-(170)P 1.278 16 (113)Mn-(35)Co-(269)Sb-(130)P 1.043 17 (15)Mg-(60)Ti-(120)P 3.103 ~ - 14 -1057'73~
Table 2 (Continued) Example Catalyst System (ppml) Thermo-ox dative 18 (50)Mn-(60)Ti-(20)Co-(80)P 0.930 19 (72)Mn-(48)Ti-(16)CO-(20)Li-(118)P 0.530 20 (62)Mn-(36)Ti-(14)CO-(18)Li-(108)P 0.590 *Standard to which all other results are normalized.
- 14a -lOS~7~4 **Normalized percent crosslinker (thermo-oxidation product). Percent crosslinker correlates with percent weight loss (see 2).
ppm metal based on wt. of polymer.
Percent weight loss of pressed films 1 mil in thickness after 6 hours @ 300C. in air circulat-ing oven. All results are normalized by divid-ing percent weight loss by the percent weight loss by the standard.
0 3Ti as acetyl triisopropyl titanate.
The poly(ethylene terephthalate) polymers set forth in Examples 11-20 in Table 2 were prepared as follows:
(100) Ca - (12) CO - (286) Sb - (190) P - This polymer was a commercially available product manufactured by Teijin, Ltd. having an inherent viscosity of 0.62 and which was made using this four-component catalyst system as determined by analysis of the polymer. The polymer is used as an arbitrary standard in thermo-oxidative stability studies.
(99) Zn - (217) Sb - (281) P (Zn as zinc acetate di-hydrate, Sb as antimony triacetate and P as the phosphate ester used in Example 1) - This polymer was produced as - described in Example 5, except that the phosphate ester was added by blending50.0 g. of the polymer pellets with the required amount of phosphate ester in 25 ml. of dry benzene to provide 281 ppm of P based on the weight of polyester. The benzene was then evaporated off under vacuum, and the coated pellets dried and then extruded on a Brabender Plasticorder melt extruder to obtain homogeneous mixing of the said phosphate ester, lOS7734 FX~P~F ~ 3 (53) Mn - (353) Sb - (170) P (Mn as manganese benzoate, Sb as ~imony triacetate and P as the phosphate ester used in Example 1) - This polymer was prepared using procedures describ-ed in Example 1.
(76) Mn - (132) Sb - (25) P - This polymer was produc-ed as described in Example 5.
EXA~IPLES 15 and 16 ~0 -(119) Mn - (10) Co - (292) Sb - (170) P
(113) Mn - (35) Co - (269JSb - (130) P
(Mn as manganese benzoate, Co as cobalt acetate, Sb as antimony triacetate and P as the phosphate ester used in Example 1) These polymers were prepared as described in Example 7 except that the phosphate ester was coated on the polymer as follows: the polymer was ground through a 2 mm screen and then 20 g. were blended with a sufficient amount of said phosphate ester in 50 ml of dichloromethane (CH2C12, M.W. 85) '0 to give the indicated levels of P (ppm based on the weight of polyester). The dichloromethane was then evaporated off under vacuum.
(15) Mg - (60) Ti - (120) P (Mg and Ti as magnesium-titanium butoxide Meerwein complex as described in U.S. 2,720,502 and P as the phosphate ester used in Example 1). This polymer was produced by a continuous melt phase process described in Example 5, EX~PLE 18 (50) Mn - (60) Ti - (20) Co - (80) P - This polymer ~a~ prepared as described in Example 7.
-]6-EXA~IPLE 19 and 20 72) Mn - (48) Ti - (16) Co - (20) Li - (118) P
(62) Mn - (36) Ti - (14) Co - (18) Li - (108) P
These polymers were prepared by the procedure describ-ed in Examples 9 and 10.
Table 3 Effect of Catalyst-Inhibitor Systems on Color Shift of Dyed Yarn Heat Set 1 2 Color Shift, Catalyst System (ppm ) I.V. A K/S _ 0 (80)Mn-(56)Ti-(22)Co-(99)P 0.61 b (803Mn-(48)Ti-(15)Co-(84)P 0.56 b (90)Mn-(56)Ti-(18)Co-(23)Li (134)P 0.53 a (56)Mn-(65)Ti-(18)Co-(13)Li-(73)p 0.57 0.0130,c (40)Mn-(22)Ti-(15)Co-(67)P 0 54 0.0254,b (51)Mn-(57)Ti-(l9)Co-(lOO)Na-(64)P 0.63 0.0014,c (236)Mn-(374)Sb-(44)P 0.65 a !0 ppm metal based on polyester polymer.
Inherent viscosity of 0.5g/100 ml of 60/40 (w/w) phenol/tetrachloroethane at 25C.
Color shift after heat set treatment equal to or better than the control by visual comparison.
Color shift compared to the control is too great for acceptance by visual comparison.
Acceptable(catalyst system of the invention) (The "control" is a commercial poly(ethylene terephthalate) that does not have a color shift problem.) The data set forth in Table 3 particularly illustrates the effects o~ lithium and sodiurn when used with Mn-Co-Ti-P
system3 a~ to bathochromic color shift of dyed yarn. Thei polymers were made in the rnanner shown in Examples 7 and 8 ~o~ the ~n-Co~ P Systern and in Examples 9 and 10 for the Mn-Ti-Co-Li-P system. The polymer made using the Mn-Ti-Co-Na-P
system was run in the manner described in Examples 7 and 8, the sodium being added as sodium acetate (anhydrous) in an ethylene glycol solution. The K/S value used is determined by use of color measurement with a spectrophotometer. The spectrophotometer can be used to measure the percent diffuse reflectance of a sàmple for a given wavelength frDm 800 to 380 nm. The K/S term is the ratio of the absorptivity .0 coefficient (K) to the scattering coefficient (S) and is related to the diffuse reflectance (R) as follows:
K/S = (I-R) Further K/S = k log10 Conc., but if the dyeing level for all samples is maintained constant (in the table above the dye-ing level was 0.3% by weight) then an observed color shift in a dyed sample manifests itself as a change in the constant k. The term ~ K/S was chosen to represent the change in K/S
which occurred upon heat-setting of certain dyed polyester samples as set forth above. Diffuse reflectance was measured 0 at 620 nm for each sample before and after heatsetting. The respective K/S values were calculated, and the difference, K/S heatset minus K/S nonheatset, is reported as a K/s. The equipment used is a Spectrosystem 100 Spectrophotometer sold by Cary Instruments of Monrovia, California.
Claims (20)
1. Process for producing poly(ethylene terephthalate) comprising reacting dimethyl terephthalate and ethylene glycol at a temperature sufficient to effect ester interchange and in the presence of a catalytic amount of a catalyst, characteriz-ed in that said catalyst comprises a mixture of organic or in-organic salts of manganese and cobalt with a titanium alkoxide and an organic salt of an alkali metal or an alkaline earth metal.
2. Process of Claim 1 wherein the manganese salt is present in the amount of 35-110 ppm Mn, the cobalt salt is present in the amount of 5-35 ppm Co, the titanium alkoxide is present in the amount of 30-60 ppm Ti, and the organic salt of an alkali metal or alkaline earth metal is present in the amount of 14-35 ppm metal, all parts by weight based on the acid fraction of the polyester.
3. Process of Claim 2 wherein said manganese salt is selected from manganous benzoate tetrahydrate, manganese chloride, manganese oxide, manganese acetate, manganese acetylacetonate, manganese succinate, manganese diethyldith-iocamate, manganese antimonate, manganic phosphate monohydrate, manganese glycoloxide, manganese naphthenate and manganese salicyl salicylate.
4. Process of Claim 2 wherein said cobalt salt is selected from cobaltous acetate tetrahydrate, cobaltous nitrate, cobaltous chloride, cobalt acetylacetonate, cobalt naphthenate and cobalt salicyl salicylate.
5. Process of Claim 2 wherein said titanium alkoxide is selected from acetyl triisopropyl titanate, titanium tetra-isopropoxide, titanium glycolates, titanium butoxide, hexylene glycol titanate and tetraisooctyl titanate.
6. Process of Claim 2 wherein said organic salt of alkali metals and alkaline earth metals is selected from sodium acetate, sodium benzoate, sodium succinate, sodium acetylacetonate, sodium methoxide, sodium ethoxide, sodium glycoxide, lithium acetate, lithium benzoate, lithium succinate, lithium acetylacetonate, lithium methoxide, lithium ethoxide, lithium glycoxide, potassium acetate, potassium benzoate, potassium succinate, potassium acetylacetonate, potassium methoxide, potassium ethoxide, potassium glycoxide, calcium acetate, calcium benzoate, calcium succinate, calcium acetyl-acetonate, calcium methoxide, calcium ethoxide, calcium glycoxide, magnesium acetate, magnesium benzoate, magnesium succinate, magnesium acetylacetonate, magnesium methoxide, magnesium ethoxide, magnesium glycoxide, barium acetate, barium benzoate, barium succinate, and barium acetylacetonate.
7. Process of Claim 2 wherein the said manganese salt is manganous benzoate tetrahydrate and the cobalt salt is cobaltous acetate tetrahydrate, the titanium alkoxide is acetyl triisopropyl titanate and the organic salt of an alkali metal or alkaline earth metal is lithium acetate dihydrate.
8. Process of Claim 2 wherein a phosphate ester is added to the reaction product of the ester interchange and said reaction product is polycondensed, said phosphate ester being present in the amount of 35 to 180 ppm P based on the acid fraction of the polyester.
9. Process of Claim 8 wherein said phosphate ester is selected from ethyl acid phosphate, diethyl acid phosphate, triethyl acid phosphate, aryl alkyl phosphate, tris-2-ethyl-hexyl phosphate and a phosphate ester having the formula wherein n has an average value of 1.5 to 3.0 and each R is hydrogen or an alkyl radical having from 6 to 10 carbon atoms, the ratio of the number of R groups of hydrogen atoms to the number of phosphorus atoms being 0.25 to 0.50, and the ester has a free acidity equivalent of 0.2 to 0.5.
10. Process of Claim 9 wherein said phosphate ester is present in the amount of 480-2225 ppm based on the acid fraction of the polyester.
11. Process of Claim 9 wherein n is about 1.8, R is hydrogen or octyl and the ratio of the number of R
hydrogen atoms to the number of phosphorus atoms is about 0.35.
hydrogen atoms to the number of phosphorus atoms is about 0.35.
12. Process of Claim 9 wherein said phosphate ester has a molecular weight of 771 and the composition is as follows:
C = 52.84% H = 9.98%, P = 8.04%; and O = 29.14% by weight.
C = 52.84% H = 9.98%, P = 8.04%; and O = 29.14% by weight.
13. Catalyst system comprising a mixture of organic or inorganic salts of manganese and cobalt with a titanium alkoxide and an organic salt of an alkali metal or an alkaline earth metal.
14. Catalyst system of Claim 13 suitable for catalyz-ing the reaction of dimethyl terephthalate and ethylene glycol to prepare a polyester wherein the manganese salt is present in the amount of 35-110 ppm Mn, the cobalt salts is present in the amount of 5-35 ppm Co, the titanium alkoxide is present in the amount of 30-60 ppm Ti, and the organic salt of an alkali metal or alkaline earth metal is present in the amount of 14-35 ppm metal, all parts by weight based on the acid ??
fraction of the polyester.
fraction of the polyester.
15. Catalyst system of Claim 14 wherein a phos-phate ester present in the amount of 35-180 ppm P by weight based on the acid fraction of the polyester.
16. Catalyst system of Claim 14 wherein said manganese salt is selected from manganous benzoate tetra-hydrate, manganese chloride, manganese oxide, manganese ace-tate, manganese acetylacetonate, manganese succinate, man-ganese diethyldithiocamate, manganese antimonate, manganic phosphate monohydrate, manganese glycoloxide, manganese naphthenate and manganese salicyl salicylate.
17. Catalyst system of Claim 14 wherein said cobalt salt is selected from cobaltous acetate tetrahydrate, cobaltous nitrate, cobaltous chloride, cobalt acetylacetonate, cobalt naphthenate and cobalt salicyl salicylate.
18. Catalyst system of Claim 14 wherein said titanium alkoxide is selected from acetyl triisopropyl titanate, titanium tetraisopropoxide titanium glycolates, titanium butoxide, and hexylene glycol titanate, and tetra-isooctyl titanate.
19. Catalyst system of Claim 14 wherein said organic salt of alkali metals and alkaline earth metals is selected from sodium acetate, sodium benzoate, sodium succinate, sodium acetylacetonate sodium methoxide, sodium ethoxide, sodium glycoxide, lithium acetate, lithium benzoate, lithium succinate, lithium acetylacetonate, lithium methoxide, lithium ethoxide, lithium glycoxide, potassium acetate, potassium benzoate, potassium succinate, potassium acetyl-acetonate, potassium methoxide, potassium ethoxide, potassium glycoxide, calcium acetate, calcium benzoate, calcium succinate, calcium acetylacetonate, calcium methoxide, calcium ethoxide, calcium glycoxide, magnesium acetate, magnesium benzoate, magnesium succinate, magnesium acetylacetonate, magnesium methoxide, magnesium ethoxide, magnesium glycoxide, barium acetate, barium benzoate, barium succinate, and barium acetylacetonate.
20. Catalyst system of Claim 15 wherein said phos-phate ester is selected from ethyl acid phosphate, diethyl acid phosphate, triethyl acid phosphate, aryl alkyl phos-phate, tris-2-ethylhexyl phosphate and a phosphate ester having the formula wherein n has an average value of 1.5 to 3.0 and each R
is hydrogen or an alkyl radical having from 6 to 10 carbon atoms, the ratio of the number of R groups of hydrogen atoms to the number of phosphorus atoms being 0.25 to 0.50, and the ester has a free acidity equivalent of 0.2 to 0.5.
is hydrogen or an alkyl radical having from 6 to 10 carbon atoms, the ratio of the number of R groups of hydrogen atoms to the number of phosphorus atoms being 0.25 to 0.50, and the ester has a free acidity equivalent of 0.2 to 0.5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/662,672 US4010145A (en) | 1975-05-12 | 1976-03-01 | Process and catalyst inhibitor systems for preparing synthetic linear polyesters |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US51995374A | 1974-11-01 | 1974-11-01 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1057734A true CA1057734A (en) | 1979-07-03 |
Family
ID=24070560
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA236,847A Expired CA1057734A (en) | 1974-11-01 | 1975-10-01 | Process and catalyst-inhibitor systems for preparing synthetic linear polyesters |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPS5168489A (en) |
| CA (1) | CA1057734A (en) |
| DE (1) | DE2548630A1 (en) |
| FR (1) | FR2289524A1 (en) |
| GB (1) | GB1522656A (en) |
| IT (1) | IT1044090B (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2637814A1 (en) * | 1976-08-21 | 1978-02-23 | Bayer Ag | PROCESS FOR THE PRODUCTION OF HIGH MOLECULAR POLYESTER |
| DE2637813A1 (en) * | 1976-08-21 | 1978-02-23 | Bayer Ag | PROCESS FOR THE PRODUCTION OF HIGH MOLECULAR POLYESTER |
| US5019640A (en) * | 1989-10-23 | 1991-05-28 | Hoechst Celanese Corporation | Producing a polyethylene terephthalate based polymer from a lower dialkyl ester of a dicarboxylic acid and a glycol |
| US4990594A (en) * | 1990-03-07 | 1991-02-05 | Hoechst Celanese Corporation | Producing a copolyester from a lower dialkyl ester of terephthalic acid, a glycol and a dicarboxylic acid |
| US5101008A (en) * | 1990-03-07 | 1992-03-31 | Hoechst Celanese Corporation | Producing a copolyester from two lower dialkyl esters of dicarboxylic acid and a glycol |
| US5106944A (en) * | 1990-07-03 | 1992-04-21 | Eastman Kodak Company | Process and catalyst-inhibitor systems for preparing poly(1,4-cyclohexenedimethylene terephthalate) |
| WO1999011709A1 (en) * | 1997-09-03 | 1999-03-11 | Asahi Kasei Kogyo Kabushiki Kaisha | Polyester resin composition |
| US6034202A (en) * | 1998-03-06 | 2000-03-07 | Alliedsignal Inc. | Polymerization catalysts for polyesters |
| US8445555B2 (en) | 2006-07-13 | 2013-05-21 | Air Products And Chemicals, Inc. | Stabilized carbanions as trimerization catalysts |
| US9957360B2 (en) | 2015-03-17 | 2018-05-01 | Niagara Bottling, Llc | Graphene reinforced polyethylene terephthalate |
| WO2017007568A1 (en) | 2015-07-08 | 2017-01-12 | Niagara Bottling, Llc | Graphene reinforced polyethylene terephthalate |
| CN114790282B (en) * | 2021-12-30 | 2023-03-21 | 康辉新材料科技有限公司 | Preparation method and application of nano-microparticle in-situ polymerization catalyst |
| CN116003821B (en) * | 2023-02-23 | 2024-03-05 | 西安交通大学 | MOF nano material and preparation method thereof, preparation method and application of metal-loaded single-atom MOF nano material |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1235867A (en) * | 1958-09-17 | 1960-07-08 | Westinghouse Electric Corp | Polyester resins |
| FR1424811A (en) * | 1965-02-16 | 1966-01-14 | Schwarza Chemiefaser | Process for making yarns, fibers, sheets and the like from polyesters and linear mixed polyesters |
| US3907754A (en) * | 1974-06-19 | 1975-09-23 | Eastman Kodak Co | Process and catalyst-inhibitor system for preparing synthetic linear polyester |
-
1975
- 1975-10-01 CA CA236,847A patent/CA1057734A/en not_active Expired
- 1975-10-30 JP JP13095175A patent/JPS5168489A/en active Pending
- 1975-10-30 IT IT2884675A patent/IT1044090B/en active
- 1975-10-30 DE DE19752548630 patent/DE2548630A1/en not_active Withdrawn
- 1975-10-31 FR FR7533316A patent/FR2289524A1/en active Granted
- 1975-10-31 GB GB4535375A patent/GB1522656A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| IT1044090B (en) | 1980-03-20 |
| DE2548630A1 (en) | 1976-05-06 |
| JPS5168489A (en) | 1976-06-14 |
| GB1522656A (en) | 1978-08-23 |
| FR2289524B1 (en) | 1979-06-22 |
| FR2289524A1 (en) | 1976-05-28 |
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