US2007255020A1PendingUtilityA1

Process for the preparation of polyesters containing 1,4-cyclohexanedimethanol

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Assignee: MARTIN DANIEL LEEPriority: Apr 28, 2006Filed: Feb 20, 2007Published: Nov 1, 2007
Est. expiryApr 28, 2026(expired)· nominal 20-yr term from priority
Inventors:Daniel L. MartinJoseph Franklin KnightBenjamin Fredrick BartonDamon Bryan Shackelford
C08G 63/78C08G 63/199C08G 63/183
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Claims

Abstract

Disclosed is a process for the preparation of high molecular weight polyesters by reacting one or more dicarboxylic acids directly with 1,4-cyclohexanedimethanol and, optionally, one or more diols. The process uses an overall diol to dicarboxylic acid molar ratio of about 0.97 to about 1.2 and an incremental addition of either the diacid or diol components. The process provides a shorter total reaction time and, thus, lessens the thermal degradation of polyester which may result in high color and reduced molecular weight.

Claims

exact text as granted — not AI-modified
1 . A process for the preparation of a polyester consisting essentially of heating a mixture of a diol component comprising about 10 to about 100 mole percent 1,4-cyclohexanedimethanol, based on the total moles of diol component, and a diacid component comprising about 5 to about 40 mole percent isophthalic acid, based on the total moles of diacid component, the mixture having total diol:diacid component molar ratio of about 1.0 to about 1.15, at a temperature of about 220 to about 300° C. to produce a substantially linear, thermoplastic polyester having an inherent viscosity of at least 0.60 dL/g. 
   
   
       2 . The process according to  claim 1  wherein the temperature is about 220 to about 240° C. 
   
   
       3 . The process according to  claim 1  wherein the diacid component further comprises about 0 to 20 mole percent of one or more dicarboxylic acids selected from the group consisting of fumaric, succinic, adipic, glutaric, azelaic, sebacic, resorcinol diacetic, diglycolic, 4,4′-oxybis(benzoic), biphenyldicarboxylic, 4,4′-methylenedibenzoic, trans-4,4′-stilbenedicarboxylic, and sulfoisophthalic acids. 
   
   
       4 . The process according to  claim 3  wherein the diol component comprises about 10 to about 99 mole percent of 1,4-cyclohexanedimethanol, 0 to about 90 mole percent of ethylene glycol, and about 1 to about 25 mole percent of diethylene glycol. 
   
   
       5 . The process according to  claim 3  wherein the diol component comprises about 50 to about 90 mole percent 1,4-cyclohexanedimethanol and about 10 to about 50 mole percent ethylene glycol. 
   
   
       6 . The process according to  claim 1  wherein the total diol:diacid component molar ratio is about 1.0 to about 1.10. 
   
   
       7 . The process according to  claim 6  wherein the total diol:diacid component molar ratio is about 1.0 to about 1.05. 
   
   
       8 . The process according to  claim 1  wherein the diacid component is added in at least 2 stages to a reaction zone. 
   
   
       9 . The process according to  claim 1  wherein the diacid component is added continuously to a reaction zone. 
   
   
       10 . The process according to  claim 3  wherein the diacid component is added as a mixture in water, an alcohol, or one or more diols. 
   
   
       11 . The process according to  claim 3  wherein a reaction zone comprises at least 2 reactors. 
   
   
       12 . The process according to  claim 9  wherein the inherent viscosity of the thermoplastic polyester is at least 0.65 dL/g. 
   
   
       13 . The process according to  claim 9  wherein the inherent viscosity of the thermoplastic polyester is at least 0.7 dL/g. 
   
   
       14 . A process for the preparation of a polyester, comprising: adding a diol component and a diacid component to a reaction zone at a total diol:diacid component molar ratio of about 0.97 to about 1.15 to produce a substantially linear, thermoplastic polyester having an inherent viscosity of at least 0.5 dL/g, wherein the diol component is added incrementally to the reaction zone at a temperature of about 210 to about 250° C. and the molar ratio of diol:diacid components added to the reaction zone is less than the total molar ratio until the addition of the diol component is completed. 
   
   
       15 . The process according to  claim 14  wherein the temperature is about 210 to about 240° C. 
   
   
       16 . The process according to  claim 15  wherein the temperature is about 220 to about 240° C. 
   
   
       17 . The process according to  claim 14  wherein the diacid component comprises at least 80 mole percent, based on the total moles of diacid component, of one or more dicarboxylic acids selected from the group consisting of terephthalic acid, naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and isophthalic acid; and the diol component comprises about 10 to 100 mole percent, based on the total moles of the diol component, 1,4-cyclohexanedimethanol and 0 to about 90 mole percent of one or more diols selected from the group consisting of neopentyl glycol, diethylene glycol, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,3-cyclohexanedimethanol, bisphenol A, and polyalkylene glycol. 
   
   
       18 . The process according to  claim 17  wherein the diacid component further comprises about 0 to 20 mole percent of one or more dicarboxylic acids selected from the group consisting of fumaric, succinic, adipic, glutaric, azelaic, sebacic, resorcinol diacetic, diglycolic, 4,4′-oxybis(benzoic), biphenyldicarboxylic, 4,4′-methylenedibenzoic, trans-4,4′-stilbenedicarboxylic, and sulfoisophthalic acids. 
   
   
       19 . The process according to  claim 18  wherein the diacid component comprises from about 60 to 100 mole percent terephthalic acid and 0 to about 40 mole percent isophthalic acid and the diol residue comprises about 100 mole percent 1,4-cyclohexanedimethanol. 
   
   
       20 . The process according to  claim 19  wherein the diacid component comprises about 95 mole percent terephthalic acid and about 5 mole percent isophthalic acid. 
   
   
       21 . The process according to  claim 19  wherein the diacid component comprises 100 mole percent terephthalic acid. 
   
   
       22 . The process according to  claim 18  wherein the diacid component comprises 80 to 100 mole percent terephthalic acid and the diol component comprises about 50 to about 90 mole percent 1,4-cyclohexanedimethanol and about 10 to about 50 mole percent 1,3-cyclohexanedimethanol. 
   
   
       23 . The process according to  claim 18  wherein the diacid component comprises 100 mole percent terephthalic acid and the diol component comprises about 10 to about 40 mole percent 1,4-cyclohexanedimethanol and 60 to about 90 mole percent ethylene glycol. 
   
   
       24 . The process according to  claim 18  wherein the diol component comprises about 10 to about 99 mole percent of 1,4-cyclohexanedimethanol, 0 to about 90 mole percent of ethylene glycol, and about 1 to about 25 mole percent of diethylene glycol. 
   
   
       25 . The process according to  claim 18  wherein the diol component comprises about 50 to about 90 mole percent 1,4-cyclohexanedimethanol and about 10 to about 50 mole percent ethylene glycol. 
   
   
       26 . The process according to  claim 18  wherein the diacid component comprises about 90 to 100 mole percent 1,4-cyclohexanedicarboxylic acid and the diol component comprises 90 to 100 mole percent 1,4-cyclohexanedimethanol. 
   
   
       27 . The process according to  claim 14  wherein the total diol:diacid component molar ratio is about 1.0 to about 1.10. 
   
   
       28 . The process according to  claim 27  wherein the total diol:diacid component molar ratio is about 1.0 to about 1.05. 
   
   
       29 . The process according to  claim 14  wherein the diacid component is added in at least 2 stages to the reaction zone. 
   
   
       30 . The process according to  claim 14  wherein the diacid component is added continuously to the reaction zone. 
   
   
       31 . The process according to  claim 30  wherein the diacid component is added as a mixture in water, an alcohol, or one or more diols. 
   
   
       32 . The process according to  claim 30  wherein the reaction zone comprises at least 2 reactors. 
   
   
       33 . The process according to  claim 30  wherein the inherent viscosity of the polyester is at least 0.65 dL/g. 
   
   
       34 . The process according to  claim 30  wherein the inherent viscosity of the polyester is at least 0.7 dL/g. 
   
   
       35 . A process for the preparation of a polyester, comprising:
 (i) contacting a portion of a diacid component with a diol component comprising a diol having a boiling point of at least 230° C. at 101 kPa, under esterification conditions and at a diol:diacid component molar ratio greater than 1.2, while recovering a distillate comprising substantially water, to form an oligomer,   (ii) adding at least one additional portion of the diacid component to the oligomer to give a total diol:diacid component molar ratio of 1.2 or less; and   (iii) heating the oligomer under polymerization conditions for a period of 4 hours or less to produce a linear, thermoplastic polyester having an inherent viscosity of at least 0.65 dL/g.   
   
   
       36 . The process according to  claim 35  wherein the diacid component comprises at least 80 mole percent, based on the total moles of diacid component, of one or more dicarboxylic acids selected from the group consisting of terephthalic acid, naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and isophthalic acid; and the diol component comprises about 10 to 100 mole percent, based on the total moles of the diol component, 1,4-cyclohexanedimethanol and 0 to about 90 mole percent of one or more diols selected from the group consisting of neopentyl glycol, diethylene glycol, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,3-cyclohexanedimethanol, bisphenol A, and polyalkylene glycol. 
   
   
       37 . The process according to  claim 36  wherein the diacid component further comprises about 0 to 20 mole percent of one or more dicarboxylic acids selected from the group consisting of fumaric, succinic, adipic, glutaric, azelaic, sebacic, resorcinol diacetic, diglycolic, 4,4′-oxybis(benzoic), biphenyldicarboxylic, 4,4′-methylenedibenzoic, trans-4,4′-stilbenedicarboxylic, and sulfoisophthalic acids. 
   
   
       38 . The process according to  claim 37  wherein the diacid component comprises from about 60 to 100 mole percent terephthalic acid and 0 to about 40 mole percent isophthalic acid and the diol residue comprises about 100 mole percent 1,4-cyclohexane-dimethanol. 
   
   
       39 . The process according to  claim 38  wherein the diacid component comprises about 95 mole percent terephthalic acid and about 5 mole percent isophthalic acid. 
   
   
       40 . The process according to  claim 38  wherein the diacid component comprises 100 mole percent terephthalic acid. 
   
   
       41 . The process according to  claim 37  wherein the diacid component comprises 80 to 100 mole percent terephthalic acid and the diol component comprises about 50 to about 90 mole percent 1,4-cyclohexanedimethanol and about 10 to about 50 mole percent 1,3-cyclohexanedimethanol. 
   
   
       42 . The process according to  claim 37  wherein the diacid component comprises 100 mole percent terephthalic acid and the diol component comprises about 10 to about 40 mole percent 1,4-cyclohexanedimethanol and 60 to about 90 mole percent ethylene glycol. 
   
   
       43 . The process according to  claim 37  wherein the diol component comprises about 10 to about 99 mole percent of 1,4-cyclohexanedimethanol, 0 to about 90 mole percent of ethylene glycol, and about 1 to about 25 mole percent of diethylene glycol. 
   
   
       44 . The process according to  claim 37  wherein the diol component comprises about 50 to about 90 mole percent 1,4-cyclohexanedimethanol and about 10 to about 50 mole percent ethylene glycol. 
   
   
       45 . The process according to  claim 37  wherein the diacid component comprises about 90 to 100 mole percent 1,4-cyclohexanedicarboxylic acid and the diol component comprises 90 to 100 mole percent 1,4-cyclohexanedimethanol. 
   
   
       46 . The process according to  claim 35  wherein the total diol:diacid component molar ratio is about 1.0 to about 1.10. 
   
   
       47 . The process according to  claim 46  wherein the total diol:diacid component molar ratio is about 1.0 to about 1.05. 
   
   
       48 . The process according to  claim 35  wherein the diacid component is added in at least 2 stages to the reaction zone. 
   
   
       49 . The process according to  claim 35  wherein the diacid component is added continuously to the reaction zone. 
   
   
       50 . The process according to  claim 37  wherein the diacid component is added as a mixture in water, an alcohol, or one or more diols. 
   
   
       51 . The process according to  claim 37  wherein the reaction zone comprises at least 2 reactors. 
   
   
       52 . The process according to  claim 49  wherein the inherent viscosity of the thermoplastic polyester is at least 0.7 dL/g. 
   
   
       53 . A process for the preparation of a polyester, comprising:
 (i) contacting a portion of a diacid component comprising about 60 to 100 mole percent, based on the total moles of diacid component, of terephthalic acid with a diol component comprising about 10 to 100 mole percent, based on the total moles of diol component, of 1,4-cyclohexanedimethanol, under esterification conditions and at a diol:diacid component molar ratio greater than 1.2, while recovering a distillate comprising substantially water, to form an oligomer having a inherent viscosity of less than 0.4 dL/g,   (ii) adding at least one additional portion of the diacid component to the oligomer to give a total diol:diacid component molar ratio of 1.2 or less; and   (iii) heating the oligomer under polymerization conditions for a period of 4 hours or less to produce a linear, thermoplastic polyester having an inherent viscosity of at least 0.7 dL/g.   
   
   
       54 . The process according to  claim 53  further comprising heating the diol and diacid components at a temperature of about 210 to about 250° C. at an absolute pressure of about 48 kPa to about 552 kPa after the addition of the diacid component is completed. 
   
   
       55 . The process according to  claim 54  wherein the temperature is about 210 to about 240° C. 
   
   
       56 . The process according to  claim 55  wherein the temperature is about 220 to about 240° C. 
   
   
       57 . The process according to  claim 54  wherein the diacid component further comprises about 0 to 20 mole percent of one or more dicarboxylic acids selected from the group consisting of fumaric, succinic, adipic, glutaric, azelaic, sebacic, resorcinol diacetic, diglycolic, 4,4′-oxybis(benzoic), biphenyldicarboxylic, 4,4′-methylenedibenzoic, trans-4,4′-stilbenedicarboxylic, and sulfoisophthalic acids. 
   
   
       58 . The process according to  claim 57  wherein the diacid component comprises from about 60 to 100 mole percent terephthalic acid and 0 to about 40 mole percent isophthalic acid and the diol residue comprises about 100 mole percent 1,4-cyclohexane-dimethanol. 
   
   
       59 . The process according to  claim 58  wherein the diacid component comprises about 95 mole percent terephthalic acid and about 5 mole percent isophthalic acid. 
   
   
       60 . The process according to  claim 59  wherein the diacid component comprises 100 mole percent terephthalic acid. 
   
   
       61 . The process according to  claim 57  wherein the diacid component comprises 80 to 100 mole percent terephthalic acid and the diol component comprises about 50 to about 90 mole percent 1,4-cyclo-hexanedimethanol and about 10 to about 50 mole percent 1,3-cyclohexanedimethanol. 
   
   
       62 . The process according to  claim 57  wherein the diacid component comprises 100 mole percent terephthalic acid and the diol component comprises about 10 to about 40 mole percent 1,4-cyclohexanedimethanol and 60 to about 90 mole percent ethylene glycol. 
   
   
       63 . The process according to  claim 57  wherein the diol component comprises about 50 to about 90 mole percent 1,4-cyclohexanedimethanol and about 10 to about 50 mole percent ethylene glycol. 
   
   
       64 . The process according to  claim 53  wherein the total diol:diacid component molar ratio is about 1.0 to about 1.10. 
   
   
       65 . The process according to  claim 64  wherein the total diol:diacid component molar ratio is about 1.0 to about 1.05. 
   
   
       66 . The process according to  claim 53  wherein the diacid component is added in at least 2 stages to the reaction zone. 
   
   
       67 . The process according to  claim 53  wherein the diacid component is added continuously to the reaction zone. 
   
   
       68 . The process according to  claim 57  wherein the diacid component is added as a mixture in water, an alcohol, or one or more diols. 
   
   
       69 . The process according to  claim 57  wherein the reaction zone comprises at least 2 reactors.

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