Polycyclohexylenedimethylene terephthalate resin having enhanced crystallization speed and method for preparing same

Patent metadata

Field	Value
Publication number	US-10072118-B2
Application number	US-201515520181-A
Country	US
Kind code	B2
Filing date	Oct 23, 2015
Priority date	Oct 23, 2014
Publication date	Sep 11, 2018
Grant date	Sep 11, 2018

Abstract

The present invention relates to a polycyclohexylenedimethylene terephthalate (PCT) resin having enhanced crystallization speed and a method for preparing same. A PCT resin, according to an embodiment of the present invention, comprises: a reactant of (A) a dicarboxylic acid compound or a dicarboxylic acid ester compound and (B) a diol compound total of which 90 mol % or more is cyclohexanedimethanol; and 10-1000 ppm of antimony (Sb) atoms on the basis of the total weight of the resin, wherein the differential between the melting point (Tm) and a reduced crystallization temperature (Tmc) is 45° C. or lower. A PCT resin, according to the present invention, has high crystallization speed and thus enables fast production of various molded products. In particular, the PCT resin has high crystallization temperature and high heat resistance and thus enables fast production of a high-quality heat-resistant molded product by means of injection molding.

First claim

What is claimed is:

1. A polycyclohexylenedimethylene terephthalate resin comprising:
a reaction product of (A) a dicarboxylic acid compound or a dicarboxylic acid ester compound and (B) a diol compound in which at least 90 mol % of the total diol compound is cyclohexanedimethanol; and
10 to 1000 ppm of antimony atoms relative to a weight of the resin,
wherein a difference between a melting point and a melt crystallization temperature is 45° C. or less.

2. The polycyclohexylenedimethylene terephthalate resin of claim 1 , wherein:
an intrinsic viscosity value at 35° C. measured after dissolving the resin in an o-chlorophenol solution at a concentration of 1.2 g/dl is 0.35 dl/g or more.

3. The polycyclohexylenedimethylene terephthalate resin of claim 1 , wherein:
a half-crystallization time (t½) is 10 to 90 seconds, the half-crystallization time obtained by drawing an Avrami plot using a crystallization peak according to time which is obtained by increasing a temperature of the resin up to 320° C. at 10° C/min, maintaining the temperature at 320° C. for 2 minutes, decreasing the temperature up to 220° C. to 240° C. at −200° C/min to perform crystallization at 220° C. to 240° C. for 30 minutes, and then, decreasing the temperature up to 40° C. at −200° C/min, maintaining the temperature for 5 minutes, and increasing the temperature up to 320° C. at 10° C/min, using a differential scanning calorimeter, and then, calculating a crystallization speed constant (k) and an Avrami exponent (n) from an Avrami Equation represented by Equation 1 below, and substituting the crystallization speed constant (k) and the Avrami exponent (n) in Equation 2:
x ( t ) =1 − e−k ( t )^ n   [Equation 1]

t ½=(1 n 2/ k )(1/ n ).   [Equation 2]

4. A method for preparing the polycyclohexylenedimethylene terephthalate resin of claim 1 comprising:
a reaction step of reacting a mixture including (A) a dicarboxylic acid compound or a dicarboxylic acid ester compound, (B) a diol compound in which at least 90 mol % of the total diol compound is cyclohexanedimethanol, (C) a phosphorus stabilizer, and (D) an antimony-based catalyst added at 10 to 1000 ppm relative to a weight of the resin based on an antimony atom; and
a polycondensation step of polycondensing a reaction product obtained by the reaction.

5. The method of claim 4 , wherein:
the phosphorus stabilizer is at least one selected from the group consisting of a phosphoric acid, a phosphorous acid, triethyl phosphate, trimethyl phosphate, triphenyl phosphate, and triethyl phosphonoacetate.

6. The method of claim 4 , wherein:
the phosphorus stabilizer is added at 0.1 to 30 ppm relative to the weight of the resin based on a phosphorus atom.

7. The method of claim 4 , wherein:
the antimony-based catalyst is at least one selected from the group consisting of antimony trioxide, antimony tetraoxide, and antimony pentaoxide.

8. The method of claim 4 , wherein:
in the reaction step, a titanium-based catalyst is further added.

9. The method of claim 8 , wherein:
the titanium-based catalyst is selected from the group consisting of titanium oxide, tetra-n-propyl titanate, tetra-isopropyl titanate, tetra-n-butyl titanate, tetra-isobutyl titanate, and butyl-isopropyl titanate.

10. The method of claim 8 , wherein:
the titanium-based catalyst is added at 0.1 to 40 ppm relative to the weight of the resin based on a titanium atom.

11. The method of claim 4 , wherein:
the polycondensation step is performed at a temperature of 290 to 320° C. and under a pressure of 0.1 to 2.0 torr for 100 to 300 minutes.

12. A polycyclohexylenedimethylene terephthalate compound resin comprising:
the polycyclohexylenedimethylene terephthalate resin of claim 1 ; and
at least one component selected from the group consisting of an organic filler and an inorganic filler.

13. A molded article manufactured by using the polycyclohexylenedimethylene terephthalate compound resin of claim 12 .

Assignees

• Sk Chemicals Co Ltd

Inventors

• Moon Jung-Me
• Kim Tae-Young
• Lee Su-Min

Classifications

• G01N25/4866

  by using a differential method · CPC title

• C08G63/183 Primary

  Terephthalic acids · CPC title

• C08G63/866

  Antimony or compounds thereof · CPC title

• C08G63/78

  Preparation processes · CPC title

• C08L67/02

  Polyesters derived from dicarboxylic acids and dihydroxy compounds (C08L67/06 takes precedence) · CPC title